O maior consumo de concentrados de hemácias está relacionado a pacientes que enfrentam procedimentos cirúrgicos. A solicitação de reserva de concentrados de hemácias para cirurgia em quantidades muito além do necessário sobrecarrega a Agência Transfusional, configura desperdício de recursos humanos, danos ao erário e prejuízo ao paciente, haja vista que muitos hemocomponentes são reservados para cirurgias, mas poucos são utilizados. A dificuldade no transporte e armazenamento dos hemocomponentes em condições adequadas fora da Agência Transfusional é fato que agrava essa situação e aumenta o desperdício, pois muitos hemocomponentes são solicitados, não são utilizados e retornam ao Serviço de Hemoterapia sem condições de serem reintegrados ao estoque. Tendo em vista que o Hospital de Base do Distrito Federal é a unidade hospitalar com o maior quantitativo em solicitação de reservas de concentrados de hemácias, e por ser recomendável que cada Serviço de Hemoterapia desenvolva seu protocolo específico e personalizado, o objetivo desse estudo é criar um manual de reserva de concentrados de hemácias para procedimentos invasivos, com o quantitativo de hemocomponentes a serem reservados para cada tipo de cirurgia, visando promover o uso racional do sangue no referido hospital. Para isso foi realizado um levantamento dos dados de cirurgias realizadas no Hospital de Base do Distrito Federal nos meses de fevereiro a julho de 2015. Em cada cirurgia foi analisado se houve solicitação e utilização de reserva de hemocomponentes. Com os dados obtidos foi calculado o índice de pacientes transfundidos para cada tipo de cirurgia, sendo confeccionado o manual, que consiste em um quadro com a conduta hemoterápica a ser adotada em cada tipo de cirurgia, se nenhuma, ou realização de tipagem e pesquisa de anticorpos irregulares, ou realização de prova de compatibilidade e reserva de concentrado de hemácias. Foi calculada a quantia aproximada de recursos com insumos que seria economizada caso fosse adotada a conduta sugerida no ano estudado. Para que o manual seja efetivamente aplicado tanto no momento de realizar a solicitação da reserva quanto no momento de preparar a reserva, deve haver uma sistemática de implantação do manual no ambiente hospitalar, com orientações quanto ao correto preenchimento do tipo de cirurgia no mapa cirúrgico e na requisição de reserva ao Banco de sangue. É importante a reavaliação periódica e comparação das solicitações de reservas de concentrados de hemácias para cirurgias eletivas com o cenário do ano anterior. O sucesso na implementação deste manual depende da compreensão e colaboração de uma equipe multidisciplinar de cirurgiões, anestesistas e colaboradores da Agência Transfusional. / Optimizing blood ordering and transfusion has been largely discussed because of patient\'s safety and money constraints. The highest use of red blood cells in a hospital is related to surgical procedures. The preoperative blood order in quantities much higher than necessary, overloads the Blood bank, which configures wasted human resources, wasted public resources and can cause injury to the patient. In most hospitals many blood components are reserved for surgeries, but few are used. The difficulty in transporting and storing the blood components in suitable conditions outside the Blood bank aggravates this situation and increases the costs. Many blood components are requested but not used and return to the blood transfusion service without conditions to be reintegrated into the stock. Considering that Hospital de Base of the Federal District Brazil is the one with the highest quantity of preoperative crossmatching orders in our state, the purpose of this study was to create a maximum blood ordering schedule (MBOS) for elective surgeries. MBOS has been established since 1977 and should be based on recommendation that each hospital may develop for its specific needs. This MBOS should recommend the maximum packed red blood cell quantity to be reserved for each type of surgery, aiming to promote the rational use of blood in the hospitals. For that, a survey of the data of surgeries performed at the Hospital de Base was carried out from February to July 2015. For each surgery, we analyzed if there was a request and use of a packed red blood cell. With the data obtained, the index of patients transfused for each type of surgery was calculated, and the manual was elaborated, consisting of a chart with hemotherapy decision to be adopted in each type of surgery. The manual included 3 types of recommendations for blood bank staff: none, type and screen only, or crossmatch units of packed red blood cells. The approximate amount of resources that would be saved if the suggested strategy were adopted in 2015 were also calculated. The idea is to have a systematic implementation of the manual in the hospital considering the moment of ordering blood products and the moment of adopting the strategy proposed at the blood bank. Some improvements are needed such as guidelines with suggestions including the complete and accurate filling of the surgical map (exact type of surgery) and implementation of a better blood ordering system with more information about patients and surgeries. This kind of manual most be reviewed periodically since surgical procedures can change over time with new techniques been included in the therapeutic strategies. The success in implementing this manual depends on the consent and collaboration of a multidisciplinary team including surgeons, anesthesiologists, and blood bank staff.

Neste trabalho apresentamos uma descrição geométrica do grupo de tranças no disco Bpnq e sua apresentação em termos de geradores e relatores no famoso teorema da apresentação de Artin. Mostraremos também que o grupo de tranças puras PBpnq, grupo que possui a permutação trivial das cordas, é bi-ordenável, ou seja, exibiremos uma ordenação para PBpnq que será invariante pela multiplicação em ambos os lados. Esse processo é dado a partir da combinação da técnica de pentear Artin e a expansão Magnus para grupos livres. / In this work, we present a geometric description of the braids groups of the disk Bpnq and its presentation in terms of generators and relations in the famous theorem of Artin\'s presentation. We also show that groups of pure braids, denoted by PBpnq, groups that have the trivial permutation of the strings, are bi-orderable, that is, we will present the explicit construction of a strict total ordering of pure braids PBpnq which is invariant under multiplying on both sides. This process is given from the combination of the techniques of combing Artin and Magnus expansion to free groups.

O Zoneamento Ecológico-Econômico (ZEE) corresponde a instrumento da Política Nacional do Meio Ambiente (PNMA) regulamentado pelo Decreto nº 4.297 de 10 de julho de 2002, busca integrar e promover sinergias entre variados aspectos de políticas de ordenamento territorial e está entre aquelas que mais possibilitam impactar as formas de uso e ocupação do território e uso dos recursos naturais, destinando-se a subsidiar a formulação e implementação de programas, planos, políticas e projetos, públicos e privados. As diretrizes e recomendações do ZEE são resultantes da leitura e interação entre potencialidades, vulnerabilidades e dinâmicas territoriais. Compete à União executar os projetos em escala nacional e regional, complementarmente os estados da federação também possuem a prerrogativa em executá-lo com o objetivo de efetivar ações de planejamento, gestão e ordenamento territorial. De maneira geral, o ZEE possui o objetivo de viabilizar o desenvolvimento sustentável a partir da compatibilização do crescimento econômico, avanços sociais e conservação ambiental, partindo da caracterização e o diagnóstico dos componentes dos meios físico e biótico, socioeconômico e aspectos jurídicos e institucionais, além de estabelecer cenários exploratórios para a proposição de estratégias e diretrizes para cada unidade territorial delimitada (zonas), denotando, particularidades ambientais, sociais, econômicas e culturais existentes, além de vulnerabilidades e potencialidades distintas sobre território. As diretrizes metodológicas e a regulamentação legal que estabelecem critérios para a elaboração do ZEE apresentam uma lacuna ao não definir diretamente em seu arcabouço metodológico indicadores de avaliação e monitoramento tanto das etapas de construção, quanto dos diagnósticos executados. Assim, propõem-se a adoção de indicadores geoambientais para compor o escopo do ZEE, os quais serão inseridos no âmbito das etapas de desenvolvimento dos projetos. Os indicadores de avaliação atuam desde a fase de planejamento até a de implementação do ZEE, ponderando as transições entre as etapas e aferindo resultados das normatizações de diretrizes. Os indicadores de monitoramento permitem o acompanhamento de mudanças e alterações sazonais ou pontuais a partir de um marco ordenador, permitindo a mensuração das transformações quanto à dinâmica socioespacial em relação às alternâncias nas categorias de uso e ocupação das terras (atividades produtivas, conservação, expansão urbana, etc.) e avanços sociais. Deste modo, fundamentou-se a proposta de dezoito indicadores geoambientais de monitoramento e sete indicadores geoambientais de avaliação ao escopo metodológico e institucional do ZEE no país, indicadores classificados de acordo com as áreas temáticas ambiental, econômica, social e normativa. / The Ecologic-Economic Zoning (EEZ) is a policy instrument of the National Policy for the Environment (NPE), regulated by the Decreto (Decree) nº 4.297 from July 10th, 2002. It aims to integrate and promote synergy between several aspects of territorial planning policies. It is among the most efficient tools for land use and occupation planning, as well as managing natural resources, seeking to provide a mutual ground for both the planning and implementation of public and private policies, programs and plans. The evaluation and recommendations from the EEZ are a result of understanding and visualizing potentials, vulnerabilities and territorial dynamics. It is a federal responsibility to execute projects in national and regional scales, however, states are also eligible to execute them towards effective actions in territorial planning, management and ordering. Overall, the EEZ aims to promote sustainable economic development through economic growth, social advance and environmental conservation. By the study and diagnosis of the physical, biological and socioeconomic environment, as well as juridical and institutional aspects, it establishes potential scenarios for the proposition of strategies and guidelines for each defined territorial unit (zones). In this process, environmental, social, economic and cultural characteristics will be considered, as well as potentials and vulnerabilities. The methodological guidelines and legal regulations which set the criteria for the preparation of the EEZ present a gap when not directly defining indicators for the evaluation and monitoring during the many stages of the intended diagnosis. In this context, the use of geo-environmental indicators is proposed in the EEZ objectives, which will be inserted during the different stages of project development. They are valuable tools in all EEZ stages, from planning to implementation, better defining transitions between project stages and evaluating results from guidelines. These indicators allow monitoring of seasonal and smaller-scale changes from a regulating date, improving the monitoring of socio-spatial dynamics in the transitions between land use and land cover categories (productive activities, conservation, urban expansion, etc.) and social advances. Eighteen geo-environmental indicators and seven evaluation indicators have been proposed as part of the methodological set of the EEZ in Brazil, classified in environmental, economic, social and normative areas.

O maior consumo de concentrados de hemácias está relacionado a pacientes que enfrentam procedimentos cirúrgicos. A solicitação de reserva de concentrados de hemácias para cirurgia em quantidades muito além do necessário sobrecarrega a Agência Transfusional, configura desperdício de recursos humanos, danos ao erário e prejuízo ao paciente, haja vista que muitos hemocomponentes são reservados para cirurgias, mas poucos são utilizados. A dificuldade no transporte e armazenamento dos hemocomponentes em condições adequadas fora da Agência Transfusional é fato que agrava essa situação e aumenta o desperdício, pois muitos hemocomponentes são solicitados, não são utilizados e retornam ao Serviço de Hemoterapia sem condições de serem reintegrados ao estoque. Tendo em vista que o Hospital de Base do Distrito Federal é a unidade hospitalar com o maior quantitativo em solicitação de reservas de concentrados de hemácias, e por ser recomendável que cada Serviço de Hemoterapia desenvolva seu protocolo específico e personalizado, o objetivo desse estudo é criar um manual de reserva de concentrados de hemácias para procedimentos invasivos, com o quantitativo de hemocomponentes a serem reservados para cada tipo de cirurgia, visando promover o uso racional do sangue no referido hospital. Para isso foi realizado um levantamento dos dados de cirurgias realizadas no Hospital de Base do Distrito Federal nos meses de fevereiro a julho de 2015. Em cada cirurgia foi analisado se houve solicitação e utilização de reserva de hemocomponentes. Com os dados obtidos foi calculado o índice de pacientes transfundidos para cada tipo de cirurgia, sendo confeccionado o manual, que consiste em um quadro com a conduta hemoterápica a ser adotada em cada tipo de cirurgia, se nenhuma, ou realização de tipagem e pesquisa de anticorpos irregulares, ou realização de prova de compatibilidade e reserva de concentrado de hemácias. Foi calculada a quantia aproximada de recursos com insumos que seria economizada caso fosse adotada a conduta sugerida no ano estudado. Para que o manual seja efetivamente aplicado tanto no momento de realizar a solicitação da reserva quanto no momento de preparar a reserva, deve haver uma sistemática de implantação do manual no ambiente hospitalar, com orientações quanto ao correto preenchimento do tipo de cirurgia no mapa cirúrgico e na requisição de reserva ao Banco de sangue. É importante a reavaliação periódica e comparação das solicitações de reservas de concentrados de hemácias para cirurgias eletivas com o cenário do ano anterior. O sucesso na implementação deste manual depende da compreensão e colaboração de uma equipe multidisciplinar de cirurgiões, anestesistas e colaboradores da Agência Transfusional. / Optimizing blood ordering and transfusion has been largely discussed because of patient\'s safety and money constraints. The highest use of red blood cells in a hospital is related to surgical procedures. The preoperative blood order in quantities much higher than necessary, overloads the Blood bank, which configures wasted human resources, wasted public resources and can cause injury to the patient. In most hospitals many blood components are reserved for surgeries, but few are used. The difficulty in transporting and storing the blood components in suitable conditions outside the Blood bank aggravates this situation and increases the costs. Many blood components are requested but not used and return to the blood transfusion service without conditions to be reintegrated into the stock. Considering that Hospital de Base of the Federal District Brazil is the one with the highest quantity of preoperative crossmatching orders in our state, the purpose of this study was to create a maximum blood ordering schedule (MBOS) for elective surgeries. MBOS has been established since 1977 and should be based on recommendation that each hospital may develop for its specific needs. This MBOS should recommend the maximum packed red blood cell quantity to be reserved for each type of surgery, aiming to promote the rational use of blood in the hospitals. For that, a survey of the data of surgeries performed at the Hospital de Base was carried out from February to July 2015. For each surgery, we analyzed if there was a request and use of a packed red blood cell. With the data obtained, the index of patients transfused for each type of surgery was calculated, and the manual was elaborated, consisting of a chart with hemotherapy decision to be adopted in each type of surgery. The manual included 3 types of recommendations for blood bank staff: none, type and screen only, or crossmatch units of packed red blood cells. The approximate amount of resources that would be saved if the suggested strategy were adopted in 2015 were also calculated. The idea is to have a systematic implementation of the manual in the hospital considering the moment of ordering blood products and the moment of adopting the strategy proposed at the blood bank. Some improvements are needed such as guidelines with suggestions including the complete and accurate filling of the surgical map (exact type of surgery) and implementation of a better blood ordering system with more information about patients and surgeries. This kind of manual most be reviewed periodically since surgical procedures can change over time with new techniques been included in the therapeutic strategies. The success in implementing this manual depends on the consent and collaboration of a multidisciplinary team including surgeons, anesthesiologists, and blood bank staff.

Made available in DSpace on 2016-04-26T20:23:05Z (GMT). No. of bitstreams: 1 Rachel Leticia Curcio Ximenes.pdf: 1148855 bytes, checksum: 2c3d9315073556cf66d5fbf8578f9856 (MD5) Previous issue date: 2014-08-25 / This dissertation in inserted in a controversy around rationality in frames developed to deal with the application of legal principals proportionality. As a first approach, proportionality is a possible manner by which the applicant interpreter in legal rights solves conflicts among legal principals by deciding which one of them will have precedence upon one another regarding phatic circumstances e legal ones in a concrete case. Proportionality is not unanimity as it has its own thought, being either controversy. Differences involves since its ideal thinking in legal principals all the way to duty rules up to the form of solving conflicts among them. In these analyses, it is necessary to take into account the need of a relationship between proportionality and fundamental Law. In the development of this research it has been used compared Law aiming in demonstrating proportionality not assumed in the same examination in all nations, either when it comes to its origin and structure. It has been also used the analysis in the Supreme Court in Brazil aiming in identifying differences and the act of questioning the use of proportionality by its ministers. Thus, it has been analyzed proportionality on Legislative Parliament. Finally, such study aims in showing authors who sustain proportionality, how do they bring its contents and how it can be brought up on legal decisioning. In other words, its argumentation consists of demonstrating what the critics are all about in a subjective way and not being controlled upon fails in Law as it is possible to deconstruct legal decisions and doctrinaire opinions in a way to identify reasons why differences may enable rational control in making use of proportionality / Esta dissertação insere-se na polêmica acerca da racionalidade de uma das formas desenvolvidas para lidar com a aplicação de princípios jurídicos a proporcionalidade. Como primeira aproximação, a proporcionalidade é uma possível maneira pela qual o intérpreteaplicador do direito resolve conflitos entre princípios jurídicos, decidindo qual deles terá precedência sobre o outro diante das circunstâncias fáticas e jurídicas do caso concreto. Ocorre que a proporcionalidade não é uma unanimidade, eis que possui sua própria racionalidade, racionalidade esta controversa. As divergências envolvem desde a própria conceituação de princípios jurídicos como normas de dever-ser até a forma de resolver conflitos entre eles. Nessa análise, há que se levar em conta ainda a necessária relação entre proporcionalidade e direitos fundamentais. No desenvolvimento da pesquisa foi utilizado o direito comparado, com o objetivo de demonstrar que a proporcionalidade não assume a mesma feição em todas as nações, seja no tocante à sua origem, seja no tocante à sua estrutura. Por conseguinte foi também utilizada a análise de julgados do Supremo Tribunal Federal brasileiro, a fim de identificar as divergências e questionar o uso da proporcionalidade pelos ministros. E por fim analisou-se a proporcionalidade sob a perspectiva do Poder Legislativo. Desse modo, a dissertação busca mostrar onde os autores que criticam e sustentam a proporcionalidade divergem, e como isso pode ser trazido também para a seara da decisão judicial. Em outras palavras, seu argumento consiste na demonstração de que a crítica à proporcionalidade como forma subjetiva e não controlável de aplicação do direito falha, porque é possível desconstruir as decisões judiciais e as posições doutrinárias, de maneira a identificar as razões para as divergências e possibilitar o controle racional do uso da proporcionalidade

Orientador: Erotilde Goreti Pezatti / Banca: Aryon Dall'Igna Rodrigues / Banca: Wilmar da Rocha D'Angelis / Banca: Cristina Martins Fargetti / Banca: Niminon Suzel Pinheiro / Resumo: Os índios Kaingáng do Oeste Paulista, após o processo de pacificação, foram levados a viver em aldeias, demarcadas pelo Governo e administradas pelo SPI - Serviço de Proteção ao índio (hoje FUNAI). A primeira aldeia que surgiu desse processo foi a de Icatu, localizada a 8 km da cidade Braúna, no Oeste Paulista. Os professores Kaingáng de Icatu atualmente demonstram a preocupação com o ensino da língua, já que, segundo eles, a fala e a escrita do Kaingáng do Sul não correspondem com a do Kaingáng de São Paulo e que há diferenças entre as duas variedades. Para verificar se as observações dos Kaingáng paulistas têm fundamento, propusemo-nos em descrever o dialeto Kaingáng paulista da aldeia Icatu, comparando-o com o dialeto Kaingáng do Sul. A hipótese é a de que a divergência entre as duas variedades do Kaingáng se deve ao contato do Kaingáng de Icatu com a língua terena, também falada nessa aldeia, e, principalmente, com o português, atualmente a primeira língua. Para tanto, investigamos a ordenação e as categorias Tempo, Modo e Aspecto (TAM), diferenciando aspectos morfossintáticos mais visíveis entre as duas variedades. Para averiguarmos a ordenação e a categorização do TAM no Kaingáng do Sul, utilizamos os trabalhos de Wiesemann (1967, 1971, 2002), D'Angelis (2004, 2005) e Gonçalves (2007, 2009a, 2009b, 2010a, 2010b). E, para mostramos os aspectos relacionados à sintaxe do Kaingáng paulista, embasamo-nos em Cavalcanti (1987), D'Angelis e Silva (2000), D'Angelis (2002a, 2002b, 2006a, 2006b, 2008a, 2008b). O corpus analisado compõe-se de sentenças e narrativas produzidas por professores Kaingáng da aldeia paulista de Icatu, com a ajuda de uma das falantes mais velhas. Ao compararmos o dialeto paulista de Icatu com o do Sul, notamos que, apesar de sua obsolescência e sua ortografia distanciada da ortografia do dialeto do Sul, a morfossintaxe... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The Kaingáng Indians from the western region of the State of São Paulo, after undergoing a pacification process, were taken to live in villages lined off by the government and managed by the Indian Protection Service [SPI - Serviço de Proteção ao Índio] (currently, FUNAI). Located 8 km away from the city of Braúna, in western São Paulo State, Icatu is the first village built out of this process. Currently, Kaingáng teachers from Icatu show concern about teaching the language, since, according to them, the spoken and written aspects of the Kaingáng from the South do not correspond to those of the Kaingáng from São Paulo. They also claim that there are differences between these two varieties. In order to verify that those claims about the Kaingáng from São Paulo are accurate, we endeavored in describing the Kaingáng dialect from São Paulo State, specifically from Icatu, comparing it to the Kaingáng dialect from the South. Our hypothesis suggests that the differences between both varieties of the Kaingáng are explained by the contact of the Kaingáng people from Icatu with the Terena language, also spoken in this village, and, mainly, with the Portuguese language, currently their first language. So, we investigated both the order and the Time, Mode and Aspect categories [TAM - Tempo, Modo, Aspecto], differentiating the most visible morphosyntactic aspects between the two varieties. In order to verify the order and the TAM categories in the Kaingáng from the South, we used written materials from Wiesemann (1967, 1971, 2002), D'Angelis (2004, 2005) and Gonçalves (2007, 2009a, 2009b, 2010a, 2010b). Also, in order to show the syntax-related aspects of the Kaingáng from São Paulo, we based our study on Cavalcanti (1987), D'Angelis e Silva (2000), D'Angelis (2002a, 2002b, 2006a, 2006b, 2008a, 2008b). The analyzed corpus is comprised of sentences and narratives put together... (Complete abstract click electronic access below) / Doutor

Les Hydroxydes Doubles Lamellaires (HDL) sont des matériaux en couches à forte potentialité pour de nombreux domaines d’applications, cependant, leur caractère d’isolants électriques limite les possibilités d’applications en électrochimie. Il est donc intéressant de chercher des moyens d’améliorer leurs propriétés conductrices. Dans ce but, trois approches ont été envisagées : - l’insertion de cations de métaux de transition 3d dans les feuillets, - l’intercalation de médiateurs redox entre les feuillets ou - l’ajout de percolant électronique dans le système afin d’obtenir des HDL « électroactifs ». Même si les combinaisons possibles de cations divalents et trivalents dans le feuillet HDL sont nombreuses, toutes les études ont été centrées sur le rôle d’un élément principalement, le cobalt. La composition chimique des matériaux ainsi que leurs propriétés physico-chimiques en termes de morphologie et de structure globale et locale ont été étudiées par le couplage de différentes techniques d’analyse (DRX, IRTF, MEB, ATG, XAS, PDF, XPS) avant de réaliser la caractérisation des propriétés électrochimiques par voltammétrie cyclique et spectroscopie d’impédance électrochimique. Ces analyses ont alors montré les potentialités applicatives de certaines compositions des matériaux HDL choisis. Les propriétés capacitives des phases CoIICoIII-CO3 ont été étudiées pour une utilisation en tant que matériaux d’électrodes de supercondensateurs alors que la présence d’un médiateur redox ainsi que les propriétés d’immobilisation d’enzymes de la phase hybride Co2Al-ABTS ont permis d’élaborer des bioélectrodes potentiellement adaptables dans une biopile. / Layered Double Hydroxides (LDH) are lamellar materials with strong potentiality for numerous fields of application, however, their insulating electric character limits the possibilities for electrochemical applications. It is thus necessary to investigate for ways to improve their conductive properties. In this purpose, three approaches were envisaged: - insertion of cations of 3d transition metals into the lamellar sheets, - insertion of redox mediators between the layers or - addition of electronic percolants in the system to obtain “electroactive” LDH. Even if the possibilities of combination of divalent and trivalent metal cations within the LDH layer are tunable, all the studies were centered on the role of an element mainly, the cobalt. The chemical compositions of materials as well as their physico-chemical properties, in terms of morphology and global and local structure, were then studied by coupling various analytical techniques before realizing the characterization of the electrochemical properties by cyclic voltammetry and electrochemical impedance spectroscopy. These analyses then showed the application potentialities of certain type of LDH materials. The capacitive properties of CoIICoIII-CO3 phases were studied as supercapacitor electrode materials while the presence of a redox mediator as well as the immobilization properties for enzymes of the hybrid phase Co2Al-ABTS allowed constructing bioelectrodes potentially applicable in biofuel cell.

Dans le domaine des polymères, l'auto-organisation de la matière a été largement étudiée dans les dernières années et beaucoup de progrès dans le domaine des films ordonnés, générés par l'auto-assemblage de copolymères à blocs, ont été réalisés. Ce progrès est motivé par le fait que les films auto-assemblés possèdent des applications en biologie, photonique, adhésion. Le sujet initial de thèse est la fabrication des films structurés en nid d’abeilles formés par un bloc de copolymère contenant une partie hydrophobe ( à peu près 90%) et une partie hydrophile (10%) qui peuvent s’auto-organiser en nid d’abeilles. Les films de polymères préparés seront ultérieurement à la base d’une étude de complexation avec des métaux. Ceci sert à décontaminer les eaux usées des métaux ou pesticides. Durant ces années de thèse, une méthodologie d’analyse de surface est détaillée pour comprendre la topographie de ces films ainsi que la chimie de surface de ces derniers. Pour cette raison, divers techniques d’analyses sont utilisées pour décrire vigoureusement la surface de ces films afin d’optimiser ces films pour complexer les contaminants à origine industrielle.Une des techniques d’analyse de surface, i.e. TOF-SIMS (Time Of Flight-Secondary Ion Mass Spectroscopy), a prouvé être un outil efficace pour caractériser chimiquement la composition élémentaire et moléculaire de l’extrême surface et en profondeur. Cette technique était la technique de base de ces études. Elle la permis de décrire les empreintes spectrales ainsi que la distribution en surface et en profondeur de chaque polymère dans les films élaborés en nid d’abeilles. / Since its introduction in 1994, the preparation of ordered porous polymer films by the breath figure “BF” method has received a considerable interest. Self-organized porous polymer films, with pores ordered into a hexagonal pattern, can be elaborated by a fast solvent evaporation method under a humid atmosphere, also called “Breath Figure” approach. The honeycomb films have found a panel of perspective applications ranging from materials with optical properties, biomaterial sensors, and scaffold for tissue engineering or highly hydrophobic surfaces. The main objective of this PhD thesis project is the fabrication of sensitive hierarchically self-organized bio inspired films based on organic compound trapping block copolymers. It is worth noting that one of the advantages of using block copolymer structure is that the first block confers the hydrophobic character, required for the elaboration and stability of HC structure, and the second block could provide an additional functionality such as hydrophilicity, stimuli-responsive character or trapping of targeted molecules (especially metals).During this thesis, a methodology of surface analysis is performed in order to understand the topography of these films as well as its surface chemistry. For this reason, various analytical techniques are used to describe the surface of these films vigorously in order to optimize these films to complex industrial contaminants.One of the techniques of surface analysis, i.e. TOF-SIMS (Time of Flight-Secondary Ion Mass Spectroscopy), has proved to be an effective tool for chemical characterization of the surface and in depth. This technique was the basic technique of our studies. It allowed the description of spectral finger prints as well as the distribution on the surface and in depth of each polymer in the structured films.

A escolha por fazer ou por comprar é um problema clássico enfrentado pelas empresas. Essa decisão diz respeito à opção de fazer internamente, optar por uma gestão hibrida (interna e externa ao mesmo tempo) ou terceirizar uma atividade. Por envolver diversos critérios, muitos responsáveis por ela utilizam métodos de decisão multicritério para que se obtenha melhores resultados. O objetivo deste trabalho consiste em desenvolver uma estrutura para a tomada de decisão de fazer ou comprar e utilizar métodos de decisão multicritério para conferir maior confiabilidade à essa decisão. Para isso, os objetivos específicos são: (1) realizar uma pesquisa bibliográfica sobre o tema (decisão de fazer ou comprar auxiliada por métodos de decisão multicritério), (2) propor um processo estruturado de decisão para o problema de fazer ou comprar, (3) propor métodos adequados aos propósitos de categorização ou ordenação nas diferentes etapas do processo, incluindo métodos que contemplem a possibilidade de decisão em grupo e (4) realizar um estudo comparativo de métodos de decisão multicritério para a decisão sobre Fazer ou Comprar. Os objetivos desse trabalho foram plenamente alcançados trazendo contribuições como: uma revisão bibliográfica sistemática sobre métodos de decisão multicritério para o problema de fazer ou comprar; uma estrutura de decisão para dar suporte à decisão de fazer ou comprar; a aplicação de métodos ainda não utilizados para o problema de fazer ou comprar; aplicação de métodos que suportem a problemática da decisão em grupo e; a comparação entre dois métodos para o propósito de categorização e duas para o propósito de ordenação. / The make or buy decision is a classical decision problem in operations management and it is difficult to make because of its very nature (multiple criteria). To better contend with these challenges, many decision makers choose Multi-Criteria Decision Making (MCDM) techniques to support their decisions. The aim of this work is to develop a methodology to support the make or buy decision and the use of the multi-criteria decision methods in this context. The specific objectives are: (1) to conduct a literature research about multi-criteria decision making techniques to support the make or buy decision; (2) to propose a structured decision framework to the make or buy problem; (3) to propose appropriate methods for categorization or ordering at different stages of the process, including methods that support group decisions and; (4) to perform a comparative study of multi-criteria decision-making methods for the make or buy problem. The objectives of this work were fully achieved by bringing contributions such as: a systematic literature review on multi-criteria decision-making methods for the make or buy problem; A decision framework to support the make or buy decision; The application of methods that were not found in the systematic literature review for the problem of make or buy problem; Application of methods that support the group decision problem and; The comparison between two techniques for categorization purposes and two for ordering purposes.

L'exfoliation en phase liquide du graphite est l'une des méthodes les plus prometteuses pour augmenter la production et la disponibilité commerciale du graphène. Le processus d'exfoliation peut être décrit, de manière conceptuelle, en quatre étapes: le contact du graphite avec le liquide, l'intercalation du solvant entre les feuillets de graphène, la dispersion du matériau à deux dimension et sa stabilisation en phase liquide. Comme les liquides ioniques peuvent être facilement obtenus avec différentes structures moléculaires et donc des propriétés physicochimiques modulables, ils ont été utilisés dans cette thèse comme milieux liquides pour l'exfoliation du graphite. Notre objectif est d'optimiser l'exfoliation du graphite à travers la compréhension des mécanismes moléculaires et des interactions impliquées dans chaque étape du processus. Les énergies interfaciale graphite-liquide ont été calculées à partir de tensions de surface et d'angles de contact mesurées entre des liquides ioniques et du graphite pour déterminer l'affinité de différents liquides à la surface du graphite. Afin d'étudier cette interface liquide - solide, des simulations en dynamique moléculaire ont été menées pour analyser l'organisation des liquides ioniques à la surface du graphite. De même, l'énergie libre nécessaire pour créer des cavités au sein du liquide ionique a été calculée.Des simulations moléculaires ont également été réalisées pour modéliser l'exfoliation d'un feuillet de graphène à partir de graphite en apportant une vue microscopique de l'intercalation des molécules de solvant. L'énergie nécessaire à l'exfoliation a pu être calculée en présence de différents liquides. Des composés polyaromatiques ont été considérés comme des modèles pour le graphène car ils peuvent être facilement obtenus purs, sans variabilité de structure, défauts ou groupes fonctionnels non contrôlés. Les enthalpies de dissolution du naphtalène, anthracène et pyrène dans différents liquides ioniques ont été mesurées par calorimétrie en solution et liées à leur solubilité. L'organisation des ions autour de ces composés modèles a été étudiée par simulation moléculaire et spectroscopie Infra-Rouge.Après l'exfoliation, les échantillons de graphène en suspension dans différents liquides ioniques ont été caractérisés expérimentalement en termes de taille de feuillets (microscopie électronique à transmission et microscopie à force atomique), nombre de couches de graphène (microscopie à force atomique, spectroscopie Raman), concentration totale (spectroscopie UV-visible) et pureté du matériau exfolié (spectroscopie de photoélectrons~X). Vingt liquides ioniques différents à base de cations imidazolium, pyrrolidinium et ammonium et d'anions bis (trifluorométhylsulfonyl)imide, triflate, dicyanamide, tricyanométhanide et méthylsulfate ont été testés. Les interactions moléculaires permettant d'établir de règles de conception pour les liquides ioniques capables d'exfolier les matériaux carbonés ont été identifiées. Le cation pyrrolidinium a montré des résultats prometteurs dans toutes les étapes du processus d'exfoliation, par rapport au cation imidazolium ou ammonium. La sélection d'un grand anion flexible a réduit l'énergie interfaciale avec le graphite, dispersé les nanocarbones en augmentant l'entropie du système et stabilisé le graphite exfolié en plus grande quantité. Un petit anion tel que le triflate semble être favorable à l'obtention de graphène, même si la taille des couches et leur quantité sont réduites. Un liquide ionique ayant une partie apolaire importante facilitera l'insertion et la dispersion du nanomatériau de carbone. Pour la stabilisation du graphite, les interactions alkyle-π et π- π sont décisives. / The liquid-phase exfoliation of graphite is one of the most promising methods to increase production and commercial availability of graphene. The exfoliation process can be conceptually described in four steps: the contact of the graphite with liquid, the intercalation of the solvent between layers, the dispersion of the two dimensional material, and its stabilization in the liquid-phase. Because ionic liquids can be easily obtained with chosen molecular structures and tunable physicochemical properties, they were used in this study as liquid media for the exfoliation of graphite. Our aim is to optimize the exfoliation of graphite through the understanding of the molecular mechanisms and of the interactions involved in each step of the process.The liquid-graphite interfacial energies from measured surface tensions and contact angles, between ionic liquids and pristine graphite surface, were used to determine the affinity of different liquids at the surface of graphite. In order to investigate this interface, molecular dynamics simulations were conducted to analyse the ordering of ionic liquids at the surface of graphite. The free energies necessary to create cavities inside the bulk ionic liquid have also been studied.Molecular simulations were also used to study the exfoliation of one graphene layer from a stack of graphite and hence provide a microscopic view of the intercalation of solvent molecules. The energies involved in the process have been calculated.Polyaromatic compounds were regarded as models for graphene as they can be easily obtained pure, without structure variability, defects or uncontrolled functional groups. Enthalpies of dissolution of polyaromatic hydrocarbons (naphthalene, anthracene and pyrene) in different ionic liquids were measured by solution calorimetry and related with their solubility. The ordering of the ions around this model compounds were studied by molecular simulation and spectroscopy Infra-Red.After exfoliation, samples of suspended graphene in different ionic liquids have been characterized experimentally in terms of flake size (using transmission electron microscopy and atomic force microscopy), number of layers (atomic force microscopy, spectroscopy Raman), total concentration (UV-visible spectroscopy) and purity of the exfoliated material (X-ray photoelectron spectrometry).Twenty different ionic liquids based on imidazolium, pyrrolidinium and ammonium cations and on bis(trifluoromethylsulfonyl)imide, triflate, dicyanamide, tricyanomethanide, and methyl sulfate have been tested. The molecular interactions have been identified thus allowing the establishment of design rules for ionic liquids capable of exfoliating carbon materials. The pyrrolidinium cation has shown promising results in all the steps of exfoliation process, compared to the imidazolium or ammonium cation. Selecting a large and flexible anion reduced the interfacial energy with graphite, dispersed the nanocarbons by increasing the entropy of the system and stabilized the exfoliated graphite in larger quantity. A small anion such as triflate appears to be favorable for obtaining graphene, whereas the size of the layers and their quantity is reduced. An ionic liquid having an important apolar portion will facilitate the insertion and dispersion of graphene layers. For the stabilization of graphite, the alkyl-π et π -π interactions are decisive.