Sequence distributions in free-radical polymers

This thesis is concerned with demonstrating how the visual representation of the sequence distribution of individual monomer units, of a polymer, that would be observed upon polymerisation, may be utilised in designing and synthesizing polymers with relatively low cell adhesion characteristics, The initial part of this thesis is concerned with demonstrating the use of a computer simulation technique, in illustrating the sequence distribution that would be observed upon the polymerisation of a set of monomers. The power of the computer simulation technique has been demonstrated through the simulation of the sequence distributions of some generic contact lens materials. These generic contact lens materials were chosen simply because in the field of biomaterials their compositions are amongst the most systematically regulated and they present a wide range of compositions. The validity of the computer simulation technique has been assessed through the synthesis and analysis of linear free-radical polymers at different conversions. Two main parameters were examined, that of composition and the number-average sequence lengths of individual monomer units, at various conversions. The polymers were synthesized through the solution polymerisation process. The monomer composition was determined by elemental analysis and 13C nuclear magnetic analysis (NMR). Number-average sequence lengths were determined exclusively through 13C NMR. Although the computer simulation technique provides a visual representation of the monomer sequence distribution up to 100% conversion, these assessments were made on linear polymers at a reasonably high conversion (above 50%) but below 100% conversion of ease for analysis. The analyses proved that the computer simulation technique was reasonably accurate in predicting the sequence distribution of monomer units, upon polymerisation, in the polymer.An approach has been presented which allows one to manipulate the use of monomers, with their reactivity ratios, thereby enabling us to design polymers with controlled sequence distributions.Hydrogel membranes, with relatively controlled sequence distributions and polymerised to 100% conversion, were synthesized to represent prospective biomaterials. Cell adhesion studies were used as a biological probe to investigate the susceptibility of the surface of these membranes to cell adhesion. This was necessary in order to assess the surface biocompatibility or biotolerance of these prospective biomaterials.

Phase equilibrium studies at normal pressures

A total pressure apparatus has been developed to measure vapour-liquid equilibrium data on binary mixtures at atmospheric and sub-atmospheric pressures. The method gives isothermal data which can be obtained rapidly. Only measurements of total pressure are made as a direct function of composition of synthetic liquid phase composition, the vapour phase composition being deduced through the Gibbs-Duhem relationship. The need to analyse either of the phases is eliminated. As such the errors introduced by sampling and analysis are removed. The essential requirements are that the pure components be degassed completely since any deficiency in degassing would introduce errors into the measured pressures. A similarly essential requirement was that the central apparatus would have to be absolutely leak-tight as any leakage of air either in or out of the apparatus would introduce erroneous pressure readings. The apparatus was commissioned by measuring the saturated vapour pressures of both degassed water and ethanol as a function of temperature. The pressure-temperature data on degassed water measured were directly compared with data in the literature, with good agreement. Similarly the pressure-temperature data were measured for ethanol, methanol and cyclohexane and where possible a direct comparison made with the literature data. Good agreement between the pure component data of this work and those available in the literature demonstrates firstly that a satisfactory degassing procedure has been achieved and that secondly the measurements of pressure-temperature are consistent for any one component; since this is true for a number of components, the measurements of both temperature and pressure are both self-consistent and of sufficient accuracy, with an observed compatibility between the precision/accuracy of the separate means of measuring pressure and temperature. The liquid mixtures studied were of ethanol-water, methanol-water and ethanol-cyclohexane. The total pressure was measured as the composition inside the equilibrium cell was varied at a set temperature. This gave P-T-x data sets for each mixture at a range of temperatures. A standard fitting-package from the literature was used to reduce the raw data to yield y-values to complete the x-y-P-T data sets. A consistency test could not be applied to the P-T-x data set as no y-values were obtained during the experimental measurements. In general satisfactory agreement was found between the data of this work and those available in the literature. For some runs discrepancies were observed, and further work recommended to eliminate the problems identified.

Silica-clad neodymium-doped lanthanum phosphate fibers and fiber lasers

We have fabricated a neodymium-doped phosphate glass fiber with a silica cladding and used it to form a fiber laser. Phosphate and silicate glasses have considerably different glass transition temperatures and softening points making it hard to draw a fiber from these two glasses. A bulk phosphate glass of composition (Nd2O3)(0.011)(La2O3)(0.259)(P2O5)(0.725)(Al2O3)(0.005) was prepared and the resultant material was transparent, free from bubbles and visibly homogeneous. The bulk phosphate glass was drawn to a fiber while being jacketed with silica and the resultant structure was of good optical quality, free from air bubbles and major defects. The attenuation at a wavelength of 1.06 mu m was 0.05 dB/cm and the refractive index of the core and cladding at the pump wavelength of 488 nm was 1.56 and 1.46, respectively. The fibers were mechanically strong enough to allow for ease of handling and could be spliced to conventional silica fiber. The fibers were used to demonstrate lasing at the F-4(3/2) - I-4(11/2) (1.06 mu m) transition. Our work demonstrates the potential to form silica clad optical fibers with phosphate cores doped with very high levels of rare-earth ions (27-mol % rare-earth oxide).

Multi-frequency segmental bio-impedance device:design, development and applications

Bio-impedance analysis (BIA) provides a rapid, non-invasive technique for body composition estimation. BIA offers a convenient alternative to standard techniques such as MRI, CT scan or DEXA scan for selected types of body composition analysis. The accuracy of BIA is limited because it is an indirect method of composition analysis. It relies on linear relationships between measured impedance and morphological parameters such as height and weight to derive estimates. To overcome these underlying limitations of BIA, a multi-frequency segmental bio-impedance device was constructed through a series of iterative enhancements and improvements of existing BIA instrumentation. Key features of the design included an easy to construct current-source and compact PCB design. The final device was trialled with 22 human volunteers and measured impedance was compared against body composition estimates obtained by DEXA scan. This enabled the development of newer techniques to make BIA predictions. To add a ‘visual aspect’ to BIA, volunteers were scanned in 3D using an inexpensive scattered light gadget (Xbox Kinect controller) and 3D volumes of their limbs were compared with BIA measurements to further improve BIA predictions. A three-stage digital filtering scheme was also implemented to enable extraction of heart-rate data from recorded bio-electrical signals. Additionally modifications have been introduced to measure change in bio-impedance with motion, this could be adapted to further improve accuracy and veracity for limb composition analysis. The findings in this thesis aim to give new direction to the prediction of body composition using BIA. The design development and refinement applied to BIA in this research programme suggest new opportunities to enhance the accuracy and clinical utility of BIA for the prediction of body composition analysis. In particular, the use of bio-impedance to predict limb volumes which would provide an additional metric for body composition measurement and help distinguish between fat and muscle content.

Pau e lata para uma educação musical: uma partitura de vidas

The field of experience and reflection in this dissertation is the Pau and Lata: Artisticpedagogical project and its activities in the field of music education It was created in 1996, by the Community School Sementes da Luz, located on Tabuleiro do Martins district, Maceió / AL. The work extended to the Rio Grande do Norte and later returned to Alagoas, keeping their activities in both states, involving approximately 280 people. The issues that moved us front the experience of Pau e Lata were: What are the main references and theoretical-methodological elements that constitute the formation of the musician in Pau e Lata? How members perceive this project and include themselves in the educational process of music formation? How it works and what is the meaning of the use of instruments and the learning of musical writing and reading? These questions lead us to undertake this dissertation, in order to deepen reflection on the processes of musical training on Pau e Lata, relating the experiences of its members in the process and the theoretical references governing their educational practice. In this sense, we outline the research objectives, which are: describe the Pau e Lata project, focusing on their context of action and their methodological processes; investigate the relationship between the effective participation of its members in the process of composition of the artistic and pedagogical repertoire and its performance in the field of cultural militancy in the environment where it operates. The writing process of this research is based on the phenomenological perspective. Therefore constitute our methodological research path two roads that communicate: 1) the organization and description of historical record of Pau e Lata (supporting documents, certificates, posters, etc.) and memories of the researcher and from other members of the group. 2) the formation of focal groups and writing and sending, via online, testimonials the participants of Pau and Lata relating to issues scrap and onomatopoeia, respectively. Participated in this process 11 components, adding the presence of the researcher, with the age between 21-45 years, all members of Pau e Lata, Core UFRN. The results of this research are focused on the discussion of three axes that describe and guide the work of the Pau e Lata: collective work, the use of the scrap as instrument and the onomatopoeia as base of a methodological process of musical training. This score was composed of three parts. The first part is presented from a collection of references from Pau e Lata, composed of printed and videographic records. The second part refers to the instrument used by Pau e Lata, and the perception of group members on these instruments, which occurs so that they are integrated in the training of the musician.The third axis tells how and what it means learning of music writing and reading, that occurs in two related aspects: the teaching-learning process and the body as a musical element in this process, associated with other actions characterized as studies and theoretical deepening

Evaporation maps for ternary non-ideal liquid mixtures

This thesis deals with the evaporation of non-ideal liquid mixtures using a multicomponent mass transfer approach. It develops the concept of evaporation maps as a convenient way of representing the dynamic composition changes of ternary mixtures during an evaporation process. Evaporation maps represent the residual composition of evaporating ternary non-ideal mixtures over the full range of composition, and are analogous to the commonly-used residue curve maps of simple distillation processes. The evaporation process initially considered in this work involves gas-phase limited evaporation from a liquid or wetted-solid surface, over which a gas flows at known conditions. Evaporation may occur into a pure inert gas, or into one pre-loaded with a known fraction of one of the ternary components. To explore multicomponent masstransfer effects, a model is developed that uses an exact solution to the Maxwell-Stefan equations for mass transfer in the gas film, with a lumped approach applied to the liquid phase. Solutions to the evaporation model take the form of trajectories in temperaturecomposition space, which are then projected onto a ternary diagram to form the map. Novel algorithms are developed for computation of pseudo-azeotropes in the evaporating mixture, and for calculation of the multicomponent wet-bulb temperature at a given liquid composition. A numerical continuation method is used to track the bifurcations which occur in the evaporation maps, where the composition of one component of the pre-loaded gas is the bifurcation parameter. The bifurcation diagrams can in principle be used to determine the required gas composition to produce a specific terminal composition in the liquid. A simple homotopy method is developed to track the locations of the various possible pseudo-azeotropes in the mixture. The stability of pseudo-azeotropes in the gas-phase limited case is examined using a linearized analysis of the governing equations. Algorithms for the calculation of separation boundaries in the evaporation maps are developed using an optimization-based method, as well as a method employing eigenvectors derived from the linearized analysis. The flexure of the wet-bulb temperature surface is explored, and it is shown how evaporation trajectories cross ridges and valleys, so that ridges and valleys of the surface do not coincide with separation boundaries. Finally, the assumption of gas-phase limited mass transfer is relaxed, by employing a model that includes diffusion in the liquid phase. A finite-volume method is used to solve the system of partial differential equations that results. The evaporation trajectories for the distributed model reduce to those of the lumped (gas-phase limited) model as the diffusivity in the liquid increases; under the same gas-phase conditions the permissible terminal compositions of the distributed and lumped models are the same.

Propondo um modelo para acompanhamento do processo Composicional

Silva, Alexandre Reche. Propondo um modelo para acompanhamento do processo Composicional. Ictus - Periódico do PPGMUS/UFBA, v. 11, n. 1, p. 11-28, Salvador, BA, 2010.

Comprendre et maîtriser le passage de type I à type II de puits quantiques d'In(x)Ga(1-x)As(y)Sb(1-y) sur substrat de GaSb

Les antimoniures sont des semi-conducteurs III-V prometteurs pour le développement de dispositifs optoélectroniques puisqu'ils ont une grande mobilité d'électrons, une large gamme spectrale d'émission ou de détection et offrent la possibilité de former des hétérostructures confinées dont la recombinaison est de type I, II ou III. Bien qu'il existe plusieurs publications sur la fabrication de dispositifs utilisant un alliage d'In(x)Ga(1-x)As(y)Sb(1-y) qui émet ou détecte à une certaine longueur d'onde, les détails, à savoir comment sont déterminés les compositions et surtout les alignements de bande, sont rarement explicites. Très peu d'études fondamentales sur l'incorporation d'indium et d'arsenic sous forme de tétramères lors de l'épitaxie par jets moléculaires existent, et les méthodes afin de déterminer l'alignement des bandes des binaires qui composent ces alliages donnent des résultats variables. Un modèle a été construit et a permis de prédire l'alignement des bandes énergétiques des alliages d'In(x)Ga(1-x)As(y)Sb(1-y) avec celles du GaSb pour l'ensemble des compositions possibles. Ce modèle tient compte des effets thermiques, des contraintes élastiques et peut aussi inclure le confinement pour des puits quantiques. De cette manière, il est possible de prédire la transition de type de recombinaison en fonction de la composition. Il est aussi montré que l'indium ségrègue en surface lors de la croissance par épitaxie par jets moléculaires d'In(x)Ga(1-x)Sb sur GaSb, ce qui avait déjà été observé pour ce type de matériau. Il est possible d'éliminer le gradient de composition à cette interface en mouillant la surface d'indium avant la croissance de l'alliage. L'épaisseur d'indium en surface dépend de la température et peut être évaluée par un modèle simple simulant la ségrégation. Dans le cas d'un puits quantique, il y aura une seconde interface GaSb sur In(x)Ga(1-x)Sb où l'indium de surface ira s'incorporer. La croissance de quelques monocouches de GaSb à basse température immédiatement après la croissance de l'alliage permet d'incorporer rapidement ces atomes d'indium et de garder la seconde interface abrupte. Lorsque la composition d'indium ne change plus dans la couche, cette composition correspond au rapport de flux d'atomes d'indium sur celui des éléments III. L'arsenic, dont la source fournit principalement des tétramères, ne s'incorpore pas de la même manière. Les tétramères occupent deux sites en surface et doivent interagir par paire afin de créer des dimères d'arsenic. Ces derniers pourront alors être incorporés dans l'alliage. Un modèle de cinétique de surface a été élaboré afin de rendre compte de la diminution d'incorporation d'arsenic en augmentant le rapport V/III pour une composition nominale d'arsenic fixe dans l'In(x)Ga(1-x)As(y)Sb(1-y). Ce résultat s'explique par le fait que les réactions de deuxième ordre dans la décomposition des tétramères d'arsenic ralentissent considérablement la réaction d'incorporation et permettent à l'antimoine d'occuper majoritairement la surface. Cette observation montre qu'il est préférable d'utiliser une source de dimères d'arsenic, plutôt que de tétramères, afin de mieux contrôler la composition d'arsenic dans la couche. Des puits quantiques d'In(x)Ga(1-x)As(y)Sb(1-y) sur GaSb ont été fabriqués et caractérisés optiquement afin d'observer le passage de recombinaison de type I à type II. Cependant, celui-ci n'a pas pu être observé puisque les spectres étaient dominés par un niveau énergétique dans le GaSb dont la source n'a pu être identifiée. Un problème dans la source de gallium pourrait être à l'origine de ce défaut et la résolution de ce problème est essentielle à la continuité de ces travaux.

Diario, pour piano seul, de Heber Schuenemann - du déchiffrage de l'oeuvre à son interprétation: démarche et réflexions d'une pianiste

Cette thèse porte sur la recherche-création ayant menée à l’apprentissage et l’exécution publique de Diário, œuvre pour piano du compositeur brésilien Heber Schuenemann (né en 1971). Dans ce cycle, qui comprend 23 courtes pièces, le compositeur explore la notion de « hasard », propre à la musique aléatoire. Il utilise également des techniques de composition s’apparentant au sérialisme et au minimalisme. Après avoir présenté les principales caractéristiques des courants musicaux propres à l’œuvre, la chercheuse-pianiste procède à une analyse de l’œuvre, décrivant la structure et les techniques de composition de chaque pièce. Par la suite, elle décrit sa propre démarche d’interprète – du déchiffrage de l’œuvre à sa prestation publique et à son enregistrement en studio – et elle commente son expérience à la lumière de la littérature pertinente. Sont abordées, notamment, les difficultés inhérentes au déchiffrage d’une œuvre atonale et les diverses étapes menant à l’identification de ses éléments structuraux; les difficultés relatives à la technique pianistique; l’importance du regroupement d’unités et de l’acquisition d’automatismes corporels; la définition de l’image artistique. Des pistes pédagogiques favorisant l’enseignement et l’apprentissage de l’œuvre sont également présentées.

Propondo um modelo para acompanhamento do processo Composicional

Silva, Alexandre Reche. Propondo um modelo para acompanhamento do processo Composicional. Ictus - Periódico do PPGMUS/UFBA, v. 11, n. 1, p. 11-28, Salvador, BA, 2010.

Fauna edáfica sob modelos em estágio inicial de restauração de floresta subtropical

The goal of this study was to compare areas under different forest restoration technologies in relation to abundance, richness, diversity and composition of the present fauna in the litter and soil. The treatments evaluated were: natural regeneration (RN); high diversity tree plantations (L) and nucleation (N). An area of secondary forest was included in the study as a reference of soil conditions. The experimental design was in randomized block with four replications. Samples were collected for extraction of mesofauna (October/2012; July and October/2013) and macrofauna (June and October/2013) in six points of each plot, totaling 24 samples per treatment. For collecting soil macrofauna was used TSBF method. The mesofauna was collected with a metal cylinder and extracted by Berlese-Tüllgren funnel. Litter and soil were collected separately at each point and the fauna was identified level of class/taxonomic order. The springtails were classified using morphotypes. In total, considering the mesofauna, macrofauna and three times collected were accounted 28618 organisms. In relation soil mesofauna, the evaluated technologies did not differ, after three years of restoration, in relation to total abundance of organisms and community composition. The Shannon diversity index (H), in soil mesofauna, followed a human impact gradient. This index was higher in natural regeneration, which not was undergone technical interventions and showed higher moisture in the soil. The tree planting technology, under the control of volunteer plants in total area, showed lower H index. In the case of litter mesofauna, the technologies did not differ in relation the mean richness, total abundance of organisms and community composition. Considering edaphic macrofauna, technologies did not differ in relation to the abundance and richness, and in the evaluation of June/2013, RN showed higher H index and differed in relation to the community composition of other technologies. In October/2013 evaluation, the differences between the technologies in relation to H index were narrower and these did not differ in terms of composition of soil macrofauna community. In litter macrofauna, in June/2013, the RN presented greater richness and H index when compared to other technologies and in evaluation October/2013 technologies did not differ in relation to community composition, richness and mean abundance of organisms. In the case of springtails, technologies after three years in the restoration process, did not differ in relation to the abundance, richness and composition of Collembola community for different morphotypes. The secondary forest, in relation to forest restoration technologies, presented greater abundance of saprophages, predators and greater diversity of morphotypes of springtails. From these results it, we recommended to natural regeneration by to have the lowest cost of deployment, followed by nucleation and online planting. The animals should be monitored over time, in the restoration technologies, as well as the physical and chemical characteristics of the soil, in order to understand the possible changes in the composition and diversity of organisms.

Incorporação de resíduos cerâmicos vidrados em argamassas bastardas: estudo de propriedades físicas e mecânicas

Dissertação de Natureza Científica para obtenção do grau de Mestre em Engenharia Civil Perfil de Edificações

An?lisis de los problemas en la argumentaci?n escrita en espa?ol de estudiantes de tercer semestre de la licenciatura en lenguas extranjeras de la Universidad del Valle [recurso electr?nico]

This study identifies and analyzes the problems of academic and argumentative writing in third semester students of the Bachelor of Foreign Languages at the Universidad del Valle, in order to determine which are the most common difficulties arisen in the process of writing. Formal aspects of language and rhetorical elements will be analyzed in the written productions of students. This is a qualitative ethnographic study that aims to determine how the relationship between the pedagogical intervention, classroom interactions and classroom activities in the course of Composition II, help to overcome these difficulties. The research shows that students have many difficulties in the academic writing as the use of an appropriate lexical, cohesion between paragraphs of a text, use of punctuation, citation and conjugation of verbs. In relation to the construction of the argument, it was found problems in students? texts: students fail in prevailing an argumentative sequence, there is not an approach and continuation of a thesis throughout the text, there is no consistency between the thesis and the arguments developed throughout the production, problems in the use of rebuttals and backings in the argumentation. In addition to these, and although they are not the most common problems, interference of words from a foreign language (English or French) and orality marks were found in the students? argumentative essays. Finally, this work demonstrates that educational intervention and classroom interactions help to improve the different versions of the written productions, though, some problems remain unsolved at the end of the intervention.

Operatory kompozycji i miary Carlesona w teorii przestrzeni Hardy’ego-Orlicza na obszarach

Wydział Matematyki i Informatyki: Zakład Teorii Interpolacji i Aproksymacji

Comprendre et maîtriser le passage de type I à type II de puits quantiques d'In(x)Ga(1-x)As(y)Sb(1-y) sur substrat de GaSb

Les antimoniures sont des semi-conducteurs III-V prometteurs pour le développement de dispositifs optoélectroniques puisqu'ils ont une grande mobilité d'électrons, une large gamme spectrale d'émission ou de détection et offrent la possibilité de former des hétérostructures confinées dont la recombinaison est de type I, II ou III. Bien qu'il existe plusieurs publications sur la fabrication de dispositifs utilisant un alliage d'In(x)Ga(1-x)As(y)Sb(1-y) qui émet ou détecte à une certaine longueur d'onde, les détails, à savoir comment sont déterminés les compositions et surtout les alignements de bande, sont rarement explicites. Très peu d'études fondamentales sur l'incorporation d'indium et d'arsenic sous forme de tétramères lors de l'épitaxie par jets moléculaires existent, et les méthodes afin de déterminer l'alignement des bandes des binaires qui composent ces alliages donnent des résultats variables. Un modèle a été construit et a permis de prédire l'alignement des bandes énergétiques des alliages d'In(x)Ga(1-x)As(y)Sb(1-y) avec celles du GaSb pour l'ensemble des compositions possibles. Ce modèle tient compte des effets thermiques, des contraintes élastiques et peut aussi inclure le confinement pour des puits quantiques. De cette manière, il est possible de prédire la transition de type de recombinaison en fonction de la composition. Il est aussi montré que l'indium ségrègue en surface lors de la croissance par épitaxie par jets moléculaires d'In(x)Ga(1-x)Sb sur GaSb, ce qui avait déjà été observé pour ce type de matériau. Il est possible d'éliminer le gradient de composition à cette interface en mouillant la surface d'indium avant la croissance de l'alliage. L'épaisseur d'indium en surface dépend de la température et peut être évaluée par un modèle simple simulant la ségrégation. Dans le cas d'un puits quantique, il y aura une seconde interface GaSb sur In(x)Ga(1-x)Sb où l'indium de surface ira s'incorporer. La croissance de quelques monocouches de GaSb à basse température immédiatement après la croissance de l'alliage permet d'incorporer rapidement ces atomes d'indium et de garder la seconde interface abrupte. Lorsque la composition d'indium ne change plus dans la couche, cette composition correspond au rapport de flux d'atomes d'indium sur celui des éléments III. L'arsenic, dont la source fournit principalement des tétramères, ne s'incorpore pas de la même manière. Les tétramères occupent deux sites en surface et doivent interagir par paire afin de créer des dimères d'arsenic. Ces derniers pourront alors être incorporés dans l'alliage. Un modèle de cinétique de surface a été élaboré afin de rendre compte de la diminution d'incorporation d'arsenic en augmentant le rapport V/III pour une composition nominale d'arsenic fixe dans l'In(x)Ga(1-x)As(y)Sb(1-y). Ce résultat s'explique par le fait que les réactions de deuxième ordre dans la décomposition des tétramères d'arsenic ralentissent considérablement la réaction d'incorporation et permettent à l'antimoine d'occuper majoritairement la surface. Cette observation montre qu'il est préférable d'utiliser une source de dimères d'arsenic, plutôt que de tétramères, afin de mieux contrôler la composition d'arsenic dans la couche. Des puits quantiques d'In(x)Ga(1-x)As(y)Sb(1-y) sur GaSb ont été fabriqués et caractérisés optiquement afin d'observer le passage de recombinaison de type I à type II. Cependant, celui-ci n'a pas pu être observé puisque les spectres étaient dominés par un niveau énergétique dans le GaSb dont la source n'a pu être identifiée. Un problème dans la source de gallium pourrait être à l'origine de ce défaut et la résolution de ce problème est essentielle à la continuité de ces travaux.