This thesis describes a fundamental study of the miscibility and the nature of the interface between components of core-shell polymer blends using the technique of Fluorescence Resonance Energy Transfer (FRET) coupled with data analysis that involves Monte-Carlo simulations. Our aim in this study was to develop a fundamental methodology to quantitatively determine the width of the interface between the two components in binary polymer blends. At the current state of the art, data analysis of FRET experiments requires translational symmetry. In the system under study, uniform core-shell structures satisfy this criterion. Thus, in this work our focus was directed toward the study of a blend system with a core-shell structure. For this FRET study, I have identified a number of potential donor and acceptor dye pairs that fluoresce in the visible range of the spectrum and can be chemically attached to polymers. Among them, I selected, as the donor and the acceptor, a pair of naphthalimide dyes that have not previously been used for FRET experiments. Model experiments showed that while the fluorescence decay profile of the donor chromophore was exponential in solution, it was not exponential in polystyrene (PS) or poly(methyl methacrylate) (PMMA) films. Thus, I carried out refinements to existing FRET theory to interpret the data generated by using these dyes. Also, I derived a new model to predict the fluorescence intensity of non-exponential decaying donor dyes in core-shell systems. I selected a model system composed of a PS core surrounded by a PMMA shell. The PS core particles were prepared by miniemulsion polymerization to obtain cross-linked PS particles with a narrow size distribution. Seeded emulsion polymerization under starved-fed condition was employed to synthesize monodisperse dye-labeled core-shell particles. The extent of miscibility and the nature of interface between the core and the shell polymers were retrieved from a combined study by Monte-Carlo simulations and analysis of the donor fluorescence intensity decays. Agreement between the retrieved interface thickness and the literature data on PS-PMMA validates the methodology developed here for the use of such donor dyes in FRET studies on polymer blends.

Polycarbonate (PC) is a glassy engineering thermoplastic that has been used for decades because of its superior mechanical properties such as high toughness and stiffness, and for its general thermal stability. However, the industrial demand for higher performance polymers with faster processing times has caused PC to be gradually replaced by different engineered polymer blends, such as polycarbonate/acyrlonitrile-butadiene-styrene (PC/ABS). Blends combine the advantages of the individual components but because they are a relatively new class of materials, their time-dependent behaviour is less well understood. The goal of the present work is to characterize two primary time-dependent processes in a commercial 75:25 PC:ABS blend that are known to affect the long-term mechanical properties of the individual components. The first is physical aging which is a result of non-equilibrium fast cooling of glassy or amorphous polymers. Physical aging is associated with structural relaxation due to enthalpic and volumetric recovery. The second process is hygrothermal conditioning which is the combined application of thermal aging and moisture absorption. Three sets of characterization tests were conducted using Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared spectroscopy (FTIR). The enthalpic relaxation results determined from DSC data for aging at nine different combinations of time and temperature showed that aging experiments are best conducted at temperatures between 80 and 90°C. This range is below the glass temperature of the ABS component. The activation energy for enthalpic relaxation for the unaged blend was found to fall between energies for PC and ABS relaxations, but not according to the rule-of-mixtures. The present study attempted to adopt the Tool–Narayanaswamy-Moynihan (TNM) phenomenological model to predict relaxation kinetics but was found to be complicated by multiple endothermic peaks. It was then concluded that the TNM model, although very useful for single polymer systems, is unsuitable for blends. A semi-empirical model was applied instead to fit the experimental data which provided a reasonable estimate of the relaxation behaviour. Aging at 80°C for the period investigated did not reach equilibrium and it is expected that aging times of upwards of 2 years will be necessary to minimize the errors associated with the data fitting to provide a better fit of the model. The FTIR studies revealed that thermal aging at 80°C in dry atmosphere results in oxidation of the butadiene component. However, the addition of moisture to the aging process appears to prevent, or at least impede, oxidation from occurring. The presence of moisture seems to trigger hydrogen bonding, which saturates regardless of the moisture content after approximately 80 days. The initial rate of moisture diffusion in PC/ABS appeared to depend predominantly on temperature while the ambient moisture concentration tends to only affect the final equilibrium content in the blend.

Polycarbonate (PC) is a glassy engineering thermoplastic that has been used for decades because of its superior mechanical properties such as high toughness and stiffness, and for its general thermal stability. However, the industrial demand for higher performance polymers with faster processing times has caused PC to be gradually replaced by different engineered polymer blends, such as polycarbonate/acyrlonitrile-butadiene-styrene (PC/ABS). Blends combine the advantages of the individual components but because they are a relatively new class of materials, their time-dependent behaviour is less well understood. The goal of the present work is to characterize two primary time-dependent processes in a commercial 75:25 PC:ABS blend that are known to affect the long-term mechanical properties of the individual components. The first is physical aging which is a result of non-equilibrium fast cooling of glassy or amorphous polymers. Physical aging is associated with structural relaxation due to enthalpic and volumetric recovery. The second process is hygrothermal conditioning which is the combined application of thermal aging and moisture absorption. Three sets of characterization tests were conducted using Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared spectroscopy (FTIR). The enthalpic relaxation results determined from DSC data for aging at nine different combinations of time and temperature showed that aging experiments are best conducted at temperatures between 80 and 90°C. This range is below the glass temperature of the ABS component. The activation energy for enthalpic relaxation for the unaged blend was found to fall between energies for PC and ABS relaxations, but not according to the rule-of-mixtures. The present study attempted to adopt the Tool–Narayanaswamy-Moynihan (TNM) phenomenological model to predict relaxation kinetics but was found to be complicated by multiple endothermic peaks. It was then concluded that the TNM model, although very useful for single polymer systems, is unsuitable for blends. A semi-empirical model was applied instead to fit the experimental data which provided a reasonable estimate of the relaxation behaviour. Aging at 80°C for the period investigated did not reach equilibrium and it is expected that aging times of upwards of 2 years will be necessary to minimize the errors associated with the data fitting to provide a better fit of the model. The FTIR studies revealed that thermal aging at 80°C in dry atmosphere results in oxidation of the butadiene component. However, the addition of moisture to the aging process appears to prevent, or at least impede, oxidation from occurring. The presence of moisture seems to trigger hydrogen bonding, which saturates regardless of the moisture content after approximately 80 days. The initial rate of moisture diffusion in PC/ABS appeared to depend predominantly on temperature while the ambient moisture concentration tends to only affect the final equilibrium content in the blend.

University, Diss., 2004--Münster (Westfalen).

Techn. University, Diss., 2004--Dresden.

Made available in DSpace on 2014-06-11T19:32:54Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-04-30Bitstream added on 2014-06-13T19:03:39Z : No. of bitstreams: 1 goncalves_spc_dr_rcla.pdf: 5626530 bytes, checksum: 213f4e6ddace53c7f1d5646655814102 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Neste trabalho, estudou-se a biodegradação dos filmes de PHB-V, PCL, PP e das blendas de PCL/PHB-V (4:1) e PP/PHB-V (4:1) em solo. Os filmes poliméricos foram preparados por compressão a quente e analisados através das análises de infravermelho com transformada de Fourier (FTIR), microscopia eletrônica de varredura (MEV), calorímetria exploratória diferencial (DSC), termogravimetria (TG) e difração de raio-X (DRX), para investigar os processos de biodegradação por um período de 120 dias. A atividade microbiana foi monitorada durante todo o período de experimento, bem como vários parâmetros: pH, temperatura, umidade, matéria orgânica, quantidade de CO2 e quantificação de microrganismos. Após os diferentes tempos do ensaio em solo, os filmes poliméricos apresentaram alterações quanto a sua estrutura molecular e morfologia em diferentes intensidades. Os processos de biodegradação observados nos diferentes filmes poliméricos, ocorreram via erosão superficial. O filme de PHB-V, foi o mais suscetível ao ataque microbiano, sendo completamente decomposto em 30 dias. O grau de cristalinidade de PHB-V permaneceu inalterado, pois a biodegradação ocorreu simultaneamente nas fases amorfa e cristalina. Para os filmes de PCL a biodegradação ocorreu tanto na fase amorfa como na interface do polímero. Os filmes de PP, após a biodegradação apresentaram uma ordenação na estrutura cristalina, denominada como “quemi-cristalização”. A biodegradação das blendas de PCL/PHB-V (4:1) e PP/PHB-V (4:1) ocorreu na interfase dos dois componentes da blenda, indicando que a imiscibilidade/morfologia são fatores que influenciam significativamente no processo de degradação. / In this works, we studied the biodegradation of the films of PHB-V, PCL, PP and the blends of PCL / PHB-V (4:1) and PP / PHB-V (4:1) in soil. The polymer films were prepared by melt-pressing and was evaluated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetry (TGA) and X-ray diffraction (XRD), and investigated with respect to their microbial degradation in soil after 120 days. Microbial activity was monitored during the whole experiment, and various parameters: pH, temperature, moisture, organic matter, amount of CO2 and quantification of microorganisms. After different times of the test in soil, the polymer films showed changes in their molecular structure and morphology in different intensities. The processes of biodegradation observed in various polymer films, occurred via surface erosion. The film of PHB-V was the most susceptible to microbial attack and was completely decomposed in 30 days. The degree of crystallinity of PHB-V remained unchanged since the degradation occurred in both crystalline and amorphous phases. For films of PCL biodegradation occurred in both the amorphous phase as the interface of the polymer. The films of PP after biodegradation underwent an arrangement of the crystalline structure, known as chemi-crystallization. The biodegradation of the blends of PCL / PHB-V (4:1) and PP / PHB-V (4:1) occurred in the interphase of the two components of the blends, indicating that the immiscibility/morphology are factors that significantly influence the process of degradation.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第14104号 / 工博第2968号 / 新制||工||1440(附属図書館) / 26392 / UT51-2008-L159 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 金谷 利治, 教授 伊藤 紳三郎, 教授 瀧川 敏算 / 学位規則第4条第1項該当

In this study, highly ionic conductive solid polymer electrolytes have been prepared by blending high molecular weight polyethylene oxide (PEO: MW 35,000 and 100,000) and bis(trifluoromethane)sulfonamide lithium (LiTFSI) salt. The ionic conductivities were determined for several compositions of the blends at different temperatures. A maximum ionic conductivity of 9.45 x 10-6 S cm-1 at 25 °C has been obtained for the blends containing PEO-35,000/LiTFSI at an ethylene oxide to lithium salt ratio (EO/Li+) of 5, whereas a maximum ionic conductivity 7.7 x 10-6 S cm-1 at 25 °C was observed for the PEO-100,000/LiTFSI blend at EO/Li+ mole ratio of 5. For all the blends, increasing the temperature resulted in enhanced ionic conductivity. Furthermore, addition of tris(pentafluorophenyl)borane (TPFB) increased the conductivities at 25 oC. The overall conclusion of the study is that using LiTFSI and the TPFB in the blends results in ionic conductivities suitable for use in Li-air and/or Li-ion batteries.

Made available in DSpace on 2016-08-29T15:35:38Z (GMT). No. of bitstreams: 1 tese_8657_Fabrício Carlos Tozzi.pdf: 2062578 bytes, checksum: affe975e528cc53bc578480c06857f6c (MD5) Previous issue date: 2015-03-26 / O Brasil não é um grande produtor de óleos leves e, além disso, as refinarias brasileiras ainda não processam integralmente os óleos pesados, logo uma alternativa seria a mistura de óleos leves, ou de características mais leves, com óleos pesados, o que levaria à formação de um novo óleo com característica relativamente leve. O nome deste processo é blending e estas misturas são denominadas de blends. Quando se prepara um blend, há a formação de um novo óleo com características diferenciadas, quando comparado a matriz original (óleo ou blend), logo é importante avaliar o impacto dessa mistura nas novas propriedades físico-químicas produzidas. Neste trabalho, foram utilizados quatro petróleos, sendo dois óleos offshore designados de A e B (Gravidade API = 26,4 e 18,3) e dois onshore designados de C e D (Gravidade API = 12,2 e 19,6, respectivamente) sendo a maior parte classificados como pesados, que foram usados para produção de 68 blends. Estes foram analisados e os novos valores encontrados para as propriedades físico-químicas dos blends como NAT, enxofre total, ponto de fluidez, Gravidade API e viscosidade foram avaliadas e comparadas aos óleos originais. Entre os 68 blends produzidos, 13 blends apresentaram, simultaneamente, uma melhora nos valores para NAT, S total, ponto de fluidez e Gravidade API. Vale destacar que dois blends (nomeados de B30 e B34) apresentaram os melhores resultados para o NAT, S total, viscosidade cinemática e Gravidade API. Como a composição química utilizada na preparação destes blends foram diferenciadas, houve também a necessidade de se verificar a influência da concentração dos óleos A, B, C e D nestes resultados dos blends. É possível verificar uma importante contribuição do óleo A nestes resultados encontrados. Portanto, é possível concluir que quando não há uma grande produção de óleos leves, a mistura destes com os óleos pesados possibilita a formação de misturas com características de óleo relativamente mais leve, otimizando assim, as etapas de produção, processamento e refino.

Orientador: Marco-Aurelio De Paoli / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-06T23:19:24Z (GMT). No. of bitstreams: 1 Waldman_WalterRuggeri_D.pdf: 3716743 bytes, checksum: 268e7c9de8037c6859995d6e15f2f375 (MD5) Previous issue date: 2006 / Doutorado / Quimica Inorganica / Doutor em Ciências