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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
111

Desenvolvimento de sistema de esterilização por plasma: eficácia inerente e comparativa com óxido de etileno / Development of a plasma sterilization system: inherent and comparative efficacy with ethylene oxide

Juliano de Morais Ferreira Silva 10 August 2006 (has links)
Estudos envolvendo o emprego de novas técnicas de esterilização têm apresentado nítido crescimento nos últimos anos como alternativa aos processos convencionais. A grande possibilidade consiste no emprego do plasma como agente de esterilização. Essa tecnologia tem considerável potencial para desenvolver o meio mais eficiente e seguro de esterilização de artigos termossensíveis com ênfase para a indústria farmacêutica e médica e até mesmo em outras áreas industriais. O objetivo deste trabalho foi investigar a influência de alguns parâmetros de processos por plasma e correlacionar sua eficácia com processos por óxido de etileno. Neste trabalho, estudos foram realizados empregando tecnologia de esterilização por plasma usando reator Reactive Ion Etching (RIE). Os valores aplicados de potências de rádio-frequência, a 13,56 MHz foram 25 W, 50 W, 100 W e 150 W. Os gases testados foram oxigênio puro e misturas de oxigênio e peróxido de hidrogênio (190/10, 180/20 e 160/40 sccm) e fluxo constante de 200 sccm, pressão de 0,100 torr e temperatura abaixo de 60°C. Esterilizador por óxido de etileno foi empregado a 450 mg/L (Oxyfume 2002®), 55°C, 60% de umidade e -0,65 e 0,60 kgf/cm2 de pressão. Os indicadores biológicos empregados foram constituídos de esporos de Bacillus subtilis var. niger ATCC 9372, inoculados em lamínulas de vidro de 18 x 18 mm e discos de papel de 13 mm de diâmetro em uma carga de 2,0 x 107 UFC/suporte. Os tempos de exposição aos processos por plasma foram de 3 a 120 minutos. Reduções progressivas da contagem inicial de microrganismos foram observadas nos valores D: 215,91,55,55,9,19 e 2,91 minutos para processos por plasma com oxigênio puro, a 25 W, 50 W, 100 W e 150 W, respectivamente. Misturas de oxigênio e peróxido de hidrogênio apresentaram os seguintes valores D: 190/10 sccm (6,41 min), 180/20 sccm (6,47 min) e 160/40 sccm (4,02 min), a 100 W e 190/10 sccm (1,47 min), 180/20 sccm (3,11 min) e 160/40 sccm (1,94 min), a 150 W. Processos empregando óxido de etileno apresentaram valor D de 2,86 minutos. Análises por Microscopia Eletrônica de Varredura demonstraram danos causados ao córtex dos esporos. Sistema empregando plasma como principal agente de esterilização apresentou-se efetivo em desafios com indicadores biológicos. Os processos por plasma provaram ser a mais apropriada tecnologia de esterilização de materias termossensíveis e com grande potencial para substituir os métodos convencionais de esterilização em futuro próximo. / Studies involving new sterilization techniques have increased in the past few years as alternatives to conventional processes. The great possibility consists in the use of plasma as sterilization agent. This technology has the enormous potential to develop a more efficient and safer means of sterilization at thermo-sensitive matters, focusing the pharmaceutical and medical industry - even though it can be applied to other industrial areas. The aim of the present study was to investigate the influence at some parameters of plasma processes and correlate the effectiveness plasma with ethylene oxide sterilizer. In this work, studies were performed taking into account a plasma sterilization technology using a Reactive Ion Etching (RIE) reactor. Power was applied at 13.56 MHz using a 6 inch diameter electrode. The gases tested were pure oxygen and oxygen-hydrogen peroxide mixtures (190/10, 180/20, and 160/40 sccm), and gas flow held constant 200 sccm, pressure at 0.100 torr and radio-frequency power at 25 W, 50 W, 100 W, and 150 W and temperature below 60°C. Ethylene oxide sterilizer were performed using 450 mg/L (Oxyfume 2002®) at 55°C, 60% humidity and -0.65 and 0.60 kgf/cm2 pressure. The biological indicator used was Bacillus subtilis var. niger ATCC 9372, witch was inoculated in glass carries (18 x 18 mm) and paper discs (13 mm diameter) in a load of 2.0 x 107 CFU/support. The exposition times were 3 to 120 minutes. Progressive reductions of the initial microbial count could be observed in the D values witch were 215.91, 55.55, 9.19, and 2.91 minutes for pure oxygen plasma at 25 W, 50 W, 100 W and 150 W, respectively. Oxygen-hydrogen peroxide mixtures plasma showed D values: 190/10 sccm (6.41 min), 180/20 sccm (6.47 min) and 160/40 sccm (4.02 min) at 100 W and 190/10 sccm (1.47 min), 180/20 sccm (3.11 min) and 160/40 sccm (1.94 min) at 150 W. Ethylene oxide processes showed D value to 2.86 minutes. Scanning Electron Microscopy analyses showed some damage on the spore cortex. Processes using plasma as main sterilization agent are presented effective in challenge with biological indicators. The plasma proved to be the most appropriate sterilization technology in thermosensitive matters and to have a great potential to replace conventional sterilization methods in the near future.
112

Ultra-large sheet formation by 1D to 2D hierarchical self-assembly of a “rod–coil” graft copolymer with a polyphenylene backbone

Huang, Yinjuan, Yuan, Rui, Xu, Fugui, Mai, Yiyong, Feng, Xinliang, Yan , Deyue 17 July 2017 (has links) (PDF)
This communication reports a unique ultra-large sheet formation through hierarchical self-assembly of a rod–coil graft copolymer containing a rigid polyphenylene backbone and flexible poly(ethylene oxide) (PEO) side chains. The hierarchical self-assembly process involved a distinctive morphological transition of 1D helical to 2D superstructures. The graft copolymer offers a new chance for the challenging bottom-up fabrication of ultra-large self-assembled nanosheets in solution, as well as a novel system for fundamental studies on 2D self-assembly of polymers.
113

Synthesis of silica-polymer hybrid particles via controlled radical polymerization in aqueous dispersed media / Synthèse de particules hybrides silice-polymère par polyméristaion radicalaire contrôlée en milieu aqueux dispersé

Qiao, Xiaoguang 20 December 2013 (has links)
Des polymères à base de méthacrylate de poly(oxyde d'éthylène) (PEOMA) avec des chaînes pendantes PEO (Mn = 300 ou 950 g mol-1) ou des copolymères de PEOMA300 et d'acide méthacrylique (AMA) ont été synthétisés par polymérisation radicalaire contrôlée par les nitroxydes en utilisant une alkoxyamine (BlocBuilder®) comme amorceur en présence de SG1 et d'une faible quantité de styrène. Les copolymères à base de PEOMA300 et d'AMA sont thermo- et pH-sensibles. Les deux types de macroalkoxyamines ont été utilisés pour amorcer la copolymérisation en émulsion du méthacrylate de n-butyle et du styrène et former, par auto-assemblage induit par la polymérisation, des particules composées de copolymères à blocs amphiphiles, en absence ou présence de particules de silice. En absence de silice, des particules stabilisées de façon stérique ou électrostérique ont été formées. La polymérisation présente les caractéristiques d'une polymérisation contrôlée avec néanmoins la formation d'une faible proportion de chaînes mortes. L'effet du pH, de la force ionique et de la nature ou de la concentration des macroalkoxyamines sur la cinétique de polymérisation et la morphologie des particules a été étudié, et des sphères, des vésicules ou des nanofibres ont été obtenues. Les macroalkoxyamines à base de PEO s'adsorbent sur la silice via la formation de liaisons hydrogène entre les chaînes PEO et les groupes silanol. La synthèse de copolymères à blocs en surface de la silice a conduit à la formation de particules hybrides de différentes morphologies (bonhomme de neige, multipodes, framboise, coeur-écorce, têtard, mille pattes) liées à la taille de la silice, au pH et à la nature du macroamorceur / Water-soluble brush-type polymers composed of poly(ethylene)oxide methacrylate (PEOMA) units with PEO side groups of various chain lengths (Mn = 300 and 950 g mol-1) or of PEOMA300 with methacrylic acid (MAA) were synthesized by nitroxide-mediated polymerization using an alkoxyamine initiator (BlocBuilder®) and SG1 nitroxide in the presence of a low amount of styrene. The PEOMA300-MAA based copolymers showed a dual temperature/pH response. The two series of macroalkoxyamines were used in aqueous emulsion copolymerization of nbutyl methacrylate and styrene leading to the formation of particles composed of amphiphilic block copolymers through polymerization-induced self-assembly, in both the absence and presence of silica. The experiments performed in the absence of silica particles resulted in the formation of sterically or electrosterically stabilized latexes. The polymerization exhibited all the features of a controlled system with however the presence of a small proportion of dead chains. The effect of pH value, ionic strength and type and concentration of the macroalkoxyamine initiator on polymerization kinetics and latex morphologies was investigated. Depending on the reaction conditions, spherical particles, vesicles or nanofibers were successfully prepared. The PEO-based macroalkoxyamines were shown to adsorb on the silica surface via hydrogen bond interaction between PEO and the silanol groups. This enabled block copolymers to be generated in situ on the silica surface leading to hybrid particles with snowman, raspberry, daisy, core-shell, “tadpole-” and “centipede-” like morphologies depending on the silica particle size, pH value and type of macroinitiator
114

Ultra-large sheet formation by 1D to 2D hierarchical self-assembly of a “rod–coil” graft copolymer with a polyphenylene backbone

Huang, Yinjuan, Yuan, Rui, Xu, Fugui, Mai, Yiyong, Feng, Xinliang, Yan, Deyue 17 July 2017 (has links)
This communication reports a unique ultra-large sheet formation through hierarchical self-assembly of a rod–coil graft copolymer containing a rigid polyphenylene backbone and flexible poly(ethylene oxide) (PEO) side chains. The hierarchical self-assembly process involved a distinctive morphological transition of 1D helical to 2D superstructures. The graft copolymer offers a new chance for the challenging bottom-up fabrication of ultra-large self-assembled nanosheets in solution, as well as a novel system for fundamental studies on 2D self-assembly of polymers.
115

Multidimensional Mass Spectrometry Studies on Amphiphilic Polymer Blends and Cross-Linked Networks

O'Neill, Jason Michael 08 July 2021 (has links)
No description available.
116

Phytochemical Modification of Biodegradable/Biocompatible Polymer Blends with Improved Immunological Responses

Buddhiranon, Sasiwimon 06 December 2012 (has links)
No description available.
117

Aplicação da proteína verde fluorescente (GFPuv) como indicador biológico na validação da autoclavação de soluções parenterais e da esterilização por óxido de etileno de itens termolábeis. Comparação com esporos de Bacillus subtilis / Application of fluorescent green protein, GFPuv, as a biologic indicator in the validation of autoclaving of parenteral solutions and ethylene oxide sterilization of thermolabile items. comparison with Bacillus subtilis spores

Ishii, Marina 04 October 2006 (has links)
A Proteína Verde Fluorescente recombinante, GFPuv, é um sistema marcador atrativo pois, sua presença pode ser visualizada através da intensidade de fluorescência emitida, sem o uso de substratos ou meios complexos. Sendo uma molécula estável à presença de substâncias orgânicas, temperaturas acima de 70°C e ampla faixa de pH, é um potencial Indicador Biológico (IH) para diversas aplicações. A estabilidade térmica da GFPuv, foi avaliada pela medida da perda de intensidade de fluorescência, expressa em valores D (min), tempo de exposição necessário para redução de 90% da intensidade de fluorescência inicial da GFPuv. GFPuv (3,5-9,0 µg/mL), expressa por E. coli e isolada por extração de Partição em Três Fases (TPP) e purificação por Cromatografia de Interação Hidrofóbica (IDC), foi diluída nas soluções parenterais preparadas em tampão (10 mM cada: Tris-EDTA, pH 8; Fosfato, pH 6 e 7, e Acetato, pH 5) e em água para injeção, WFI; pH = 6,70±0,40), e expostas a temperaturas de 25°C e ao intervalo entre 80°C e 100°C. A 95°C, os valores D para a GFPuv em soluções de 1,5% a 50% de glicose variaram de: (i) 1,63 (±0,23) min em acetato pH 5; (ii) 2,64 ± 0,26 min em WFI; (iii) 2,50 ± 0,18 min em fosfato pH 6; (iv) 3,24 ± 0,28 min em fosfato pH 7 e, (v) 2,89 ± 0,44 min em Tris-EDTA pH 8. Cloreto de sódio associado aos tampões proporcionou influência positiva na estabilidade da GFPuv, sendo que em soluções de Tris-EDTA, a adição de 15-20% de NaCl dobrou a estabilidade térmica da GFPuv (valores D de 65,79 min e 18,12 min a 80 °C e 85°C) em relação à solução sem cloreto de sódio. Nos processos de esterilização por óxido de etileno (45°C-60°C), a GFPuv pode ser utilizada como IB para monitorar a distribuição de gás dentro da câmara, pois, apresentou variação na concentração remanescente de até 80%, após processamento, estabelecendo áreas distintas dentro da câmara. No tratamento em autoclave, a GFPuv em solução apresentou resistência térmica em solução de fosfato pH 7,0 (valor F = 2,53 min (± 0,12)). Quando expressa por esporos de Bacillus subtilis, a intensidade de fluorescência emitida por esporos sobreviventes se manteve. A estabilidade térmica da GFPuv atestou sua potencialidade como indicador biológico fluorescente da garantia da eficácia de tratamento de soluções e materiais expostos ao calor. / The recombinant Green Fluorescent Protein, GFPuv is an attractive system marker due to its ability to emit fluorescence when exposed to ultraviolet light, without use of substrates or complex environment. Being a stable molecule even in the presence of organic substances, temperatures above 70°C and wide range of pH, it is a potential Biological Indicator, BI, for many applications, including thermal processes. GFPuv thermal stability was evaluated by the loss of fluorescence intensity expressed in decimal reduction time (D-value, min), the exposure time required to reduce 90% of the GFPuv initial fluorescence intensity. GFPuv (3.5-9.0 µg/mL), expressed by E. coli and isolated by Three Phases Partitioning, TPP extraction with Hidrophobic Interaction Chromatography, HIC, was diluted in buffered solutions (each 10 mM: Tris-EDTA, pH 8; phosphate, pH 6 and 7, and acetate, pH 5) and in water for injection, WFI; pH = 6.70 (± 0.40), and exposed to temperatures of 25°C and between 80°C and 95°C. At 95°C, the D-value for GFPuv in 1.5%-50% glucose, ranged from: (i) 1.63 ± 0.23 min in acetate pH 5; (ii) 2.64 ± 0.26 min in WFI; (iii) 2.50 ± 0.18 min in phosphate, pH 6; (iv) 3.24 ± 0.28 min in phosphate, pH 7, (v) 2.89 ± 0.44 min in Tris-EDTA, pH 8. Sodium cloride provided a positive influence over GFPuv stability. In Tris-EDTA solutions, the addition of 15% and 20% of NaCl doubled the thermal stability of GFPuv (D = 65.79 min and D = 18.12 min at 80°C, and 85°C, respectively, in relation to the solutions without NaCl. For ethylene oxide sterilization processes (45°C-60°C), GFPuv can be used as biological indicator to monitor gas distribution into the chamber. After processing, the protein concentration varied by 80%, showing distinct areas into the chamber. In autoclave, GFPuv in solution showed thermal resistance in phosphate pH 7.0 solution (F-value = 2.53 (± 0.12) min. When expressed by Bacillus subtilis spores, the fluorescence intensity was kept constant after thermal processing. The thermal stability of GFPuv provides the basis for its potential utility as a fluorescent biological indicator to assess the efficacy of the treatment of liquids and materials exposed to steam.
118

Aplicação da proteína verde fluorescente (GFPuv) como indicador biológico na validação da autoclavação de soluções parenterais e da esterilização por óxido de etileno de itens termolábeis. Comparação com esporos de Bacillus subtilis / Application of fluorescent green protein, GFPuv, as a biologic indicator in the validation of autoclaving of parenteral solutions and ethylene oxide sterilization of thermolabile items. comparison with Bacillus subtilis spores

Marina Ishii 04 October 2006 (has links)
A Proteína Verde Fluorescente recombinante, GFPuv, é um sistema marcador atrativo pois, sua presença pode ser visualizada através da intensidade de fluorescência emitida, sem o uso de substratos ou meios complexos. Sendo uma molécula estável à presença de substâncias orgânicas, temperaturas acima de 70°C e ampla faixa de pH, é um potencial Indicador Biológico (IH) para diversas aplicações. A estabilidade térmica da GFPuv, foi avaliada pela medida da perda de intensidade de fluorescência, expressa em valores D (min), tempo de exposição necessário para redução de 90% da intensidade de fluorescência inicial da GFPuv. GFPuv (3,5-9,0 µg/mL), expressa por E. coli e isolada por extração de Partição em Três Fases (TPP) e purificação por Cromatografia de Interação Hidrofóbica (IDC), foi diluída nas soluções parenterais preparadas em tampão (10 mM cada: Tris-EDTA, pH 8; Fosfato, pH 6 e 7, e Acetato, pH 5) e em água para injeção, WFI; pH = 6,70±0,40), e expostas a temperaturas de 25°C e ao intervalo entre 80°C e 100°C. A 95°C, os valores D para a GFPuv em soluções de 1,5% a 50% de glicose variaram de: (i) 1,63 (±0,23) min em acetato pH 5; (ii) 2,64 ± 0,26 min em WFI; (iii) 2,50 ± 0,18 min em fosfato pH 6; (iv) 3,24 ± 0,28 min em fosfato pH 7 e, (v) 2,89 ± 0,44 min em Tris-EDTA pH 8. Cloreto de sódio associado aos tampões proporcionou influência positiva na estabilidade da GFPuv, sendo que em soluções de Tris-EDTA, a adição de 15-20% de NaCl dobrou a estabilidade térmica da GFPuv (valores D de 65,79 min e 18,12 min a 80 °C e 85°C) em relação à solução sem cloreto de sódio. Nos processos de esterilização por óxido de etileno (45°C-60°C), a GFPuv pode ser utilizada como IB para monitorar a distribuição de gás dentro da câmara, pois, apresentou variação na concentração remanescente de até 80%, após processamento, estabelecendo áreas distintas dentro da câmara. No tratamento em autoclave, a GFPuv em solução apresentou resistência térmica em solução de fosfato pH 7,0 (valor F = 2,53 min (± 0,12)). Quando expressa por esporos de Bacillus subtilis, a intensidade de fluorescência emitida por esporos sobreviventes se manteve. A estabilidade térmica da GFPuv atestou sua potencialidade como indicador biológico fluorescente da garantia da eficácia de tratamento de soluções e materiais expostos ao calor. / The recombinant Green Fluorescent Protein, GFPuv is an attractive system marker due to its ability to emit fluorescence when exposed to ultraviolet light, without use of substrates or complex environment. Being a stable molecule even in the presence of organic substances, temperatures above 70°C and wide range of pH, it is a potential Biological Indicator, BI, for many applications, including thermal processes. GFPuv thermal stability was evaluated by the loss of fluorescence intensity expressed in decimal reduction time (D-value, min), the exposure time required to reduce 90% of the GFPuv initial fluorescence intensity. GFPuv (3.5-9.0 µg/mL), expressed by E. coli and isolated by Three Phases Partitioning, TPP extraction with Hidrophobic Interaction Chromatography, HIC, was diluted in buffered solutions (each 10 mM: Tris-EDTA, pH 8; phosphate, pH 6 and 7, and acetate, pH 5) and in water for injection, WFI; pH = 6.70 (± 0.40), and exposed to temperatures of 25°C and between 80°C and 95°C. At 95°C, the D-value for GFPuv in 1.5%-50% glucose, ranged from: (i) 1.63 ± 0.23 min in acetate pH 5; (ii) 2.64 ± 0.26 min in WFI; (iii) 2.50 ± 0.18 min in phosphate, pH 6; (iv) 3.24 ± 0.28 min in phosphate, pH 7, (v) 2.89 ± 0.44 min in Tris-EDTA, pH 8. Sodium cloride provided a positive influence over GFPuv stability. In Tris-EDTA solutions, the addition of 15% and 20% of NaCl doubled the thermal stability of GFPuv (D = 65.79 min and D = 18.12 min at 80°C, and 85°C, respectively, in relation to the solutions without NaCl. For ethylene oxide sterilization processes (45°C-60°C), GFPuv can be used as biological indicator to monitor gas distribution into the chamber. After processing, the protein concentration varied by 80%, showing distinct areas into the chamber. In autoclave, GFPuv in solution showed thermal resistance in phosphate pH 7.0 solution (F-value = 2.53 (± 0.12) min. When expressed by Bacillus subtilis spores, the fluorescence intensity was kept constant after thermal processing. The thermal stability of GFPuv provides the basis for its potential utility as a fluorescent biological indicator to assess the efficacy of the treatment of liquids and materials exposed to steam.
119

Microscopy techniques for studying polymer-polymer blends

Mattsson, Sandra January 2019 (has links)
Semiconductors are used in many electronic applications, for example diodes, solar cells and transistors. Typically, semiconductors are inorganic materials, such as silicon and gallium arsenide, but lately more research and development has been devoted to organic semiconductors, for example semiconducting polymers. One of the reasons is that polymers can be customized, to a greater extent than inorganic semiconductors, to create a material with desired properties. Often, two polymers are blended to obtain the desired function, but two polymers do not usually result in an even blend. Instead they tend to separate from each other to varying degrees. The morphology of the blend affects the material properties, for example how efficiently it can convert electricity to light. In this project, thin films consisting of polymer blends were examined using microscopy techniques for the purpose of increasing our understanding of the morphology of such blends. One goal was to investigate whether a technique called correlative light and electron microscopy can be useful for examining the morphology of these films. In correlative light and electron microscopy, a light microscope and an electron microscope are used in the same location in order to be able to correlate the information from the two microscopes. The second goal was to learn about the morphology of the thin films using various microscopy techniques. The polymers used were Super Yellow and poly(ethylene oxide) with large molecular weight. Super Yellow is a semiconducting and light-emitting polymer while poly(ethylene oxide) is an isolating and non-emitting polymer that can crystallize. In the blend films, large, seemingly crystalline structures appeared. The structures could be up to 1 mm in the lateral direction, while the films were only approximately 170 nm thick. These structures could grow after the films had dried and their shapes were similar to those of poly(ethylene oxide) crystals. Consequently, there is reason to believe that it is the poly(ethylene oxide) that makes up the seemingly crystalline structures, but the structures also emitted more light than the rest of the film, and Raman spectroscopy showed that there was Super Yellow in the same location as the crystals. Among the microscopy techniques used, phase contrast microscopy was particularly interesting. This method visualizes differences in optical path length and was useful for studying polymer blends when the polymers have different indices of refraction. Correlating light and electron microscopy showed that there was a pronounced topographical difference between the seemingly crystalline regions and the rest of the thin film. Light microscopy has a limited resolution due to diffraction, but as long as the resolution of the light microscope is sufficient for seeing phase separation, correlative light and electron microscopy turned out to be a good method for studying the morphology of thin films of polymer blends. / Halvledare är viktiga för många elektroniska ändamål eftersom de kan användas till exempelvis dioder, solceller och transistorer. Traditionellt används inorganiska halvledande material som kisel eller galliumarsenid, men på senare tid har allt mer forskning och utveckling inriktat sig mot organiska (kolbaserade) halvledare, såsom halvledande polymerer, bland annat eftersom det i högre utsträckning går att skräddarsy de organiska materialen så att de får önskvärda egenskaper. Ofta blandas två polymerer med varandra för att skapa ett material med nya egenskaper som är önskvärda, men två polymerer brukar inte blandas jämnt utan tenderar att separera från varandra i olika utsträckning. Hur blandningen ser ut (morfologin) påverkar materialets egenskaper, till exempel hur effektivt det omvandlar ström till ljus. Med syfte att öka förståelsen för hur morfologin ser ut hos en blandning av två polymerer, har detta projekt gått ut på att undersöka tunna filmer av polymer-blandningar med hjälp av mikroskopiska tekniker. Ett delmål var att ta reda på om en teknik som heter korrelativ ljus- och elektronmikroskopi är en bra metod för att undersöka morfologin hos dessa filmer. Vid korrelativ ljus- och elektronmikroskopi används både ett ljusmikroskop och ett elektronmikroskop på samma plats för att kunna korrelera informationen som de båda mikroskopen ger. Det andra delmålet var att undersöka vad de olika mikroskopi-teknikerna kan säga om morfologin hos de tunna filmerna. De polymerer som använts är Super Yellow och poly(etylenoxid) med hög molekylmassa. Super Yellow är en oordnad halvledande och ljusemitterande polymer medan poly(etylenoxid) är en isolerande och icke-emitterande polymer som kan kristallisera. I de blandade filmerna uppstod stora kristall-liknande strukturer som kunde vara upp emot 1 mm breda trots att filmerna bara var ungefär 170 nm tunna. Dessa strukturer kunde växa fram efter det att filmerna redan hade torkat och påminde i form om kristaller som kan bildas av poly(etylenoxid). Det finns alltså skäl att tro att det är poly(etylenoxid) som kristalliserats, men de kristall-liknande strukturerna visade sig emittera mer ljus än vad resten av filmen gjorde, och Raman-spektroskopi visade att det även fanns Super Yellow på samma plats som kristallerna. Bland de mikroskopitekniker som testades utmärker sig faskontrastmikroskopi, som visar skillnader i den optiska vägskillnaden (det vill säga faktisk vägskillnad multiplicerat med brytningsindex). Det visade sig vara en intressant teknik för att studera polymerblandningar när de båda polymererna har olika brytningsindex. Genom att korrelera ljus- och elektronmikroskopi visade det sig att det fanns en tydlig skillnad i struktur mellan de kristall-liknande områdena och resten av den tunna filmen. Ljusmikroskopi har begränsad upplösning på grund av ett fenomen som heter diffraktion, men så länge som ljusmikroskopets upplösning är tillräcklig för att se fasseparation visade det sig att korrelativ ljus- och elektronmikroskopi är en bra metod för att studera morfologin hos tunna filmer av polymerblandningar.
120

Morphology and Thermal Behavior of Single Crystals of Polystyrene-Poly(ethylene oxide) Block Copolymers / Morphologies et réorganisation par traitement thermique des monocristaux de copolymères à block de polystyrène-block-Poly(oxyde d'éthylène)

Hamie, Houssam 26 April 2010 (has links)
Dans le travail actuel, nous avons entrepris une étude structurale des monocristaux de polystyrène-polyoxyde d'éthylène (PS-b-PEO) pour élucider l'influence de la conformation du bloc de PS sur la cristallisation à partir d'une solution diluée. Nous avons également étudié le comportement des monocristaux lors d'une chauffe. Il est à noter que l'intérêt dans ces systèmes a été récemment réapparu en vue d'utilisation des monocristaux de copolymères pour générer des brosses amorphes uniformes. Lors de la cristallisation du PEO le bloc amorphe, c. à d. le PS, est rejeté du cristal et s'accumule donc sur des surfaces basales des lamelles cristallines. Puisque l'épaisseur cristalline qui résulte d'un processus de cristallisation isotherme a une valeur bien définie, la densité de greffage de PS en est aussi. Ainsi en changeant l'épaisseur du cristal nous pouvons générer des brosses de PS ayant des densités de greffage très variées. Dans notre étude, nous avons employé une combinaison des techniques d'analyse qui sont opérationnelles dans l'espace directe et réciproque telles que l'AFM et le SAXS/WAXS. Les expériences AFM ont été réalisées sur des monocristaux isolés tandis que les mesures SAXS/WAXS ont été faites sur des gâteux de monocristaux orientés qui ont été préparés par sédimentation lente à partir d'une solution diluée. L'interprétation des résultants SAXS se base sur le modèle à deux phases où les épaisseurs des régions cristallines (Lc) et amorphes (La) peuvent être déterminées en suivant les approches conventionnelles de la fonction de corrélation ou la fonction de distribution des interfaces. / In the present work, we have undertaken a structural study of PS-b-PEO single crystals to elucidate the influence of the state of the PS block on crystallization from dilute solution and on subsequent thermal annealing at elevated temperature. It is noteworthy that the interest in these systems has been recently renewed in the perspective of using them as a model of grafted amorphous brushes with variable grafting density. Indeed, during crystallization of PEO, the amorphous block, i.e. PS, is rejected from the crystal accumulating on its basal surfaces. Since the crystal thickness formed during isothermal crystallization is a sharply selected value, the grafting density of the resulting PS brush is also well defined. Therefore by varying the crystal thickness one can obtain the PS brushes with grafting density varying in a broad range.In our study, a combination of reciprocal and direct-space techniques such as SAXS/WAXS and AFM was employed. While AFM experiments were performed on isolated single crystals, the SAXS investigation was carried out on oriented mats of single crystals slowly sedimented from the "mother" solution. In this case, the one-dimensional two-phase system model was used for the data interpretation where the thickness of the amorphous (La) and crystalline (Lc) layers are conventionally determined following the correlation fonction and interface distribution fonction approaches.

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