Studies that involve natural fiber orientation in a matrix were mostly based on regulating shear forces during mixing of fiber and matrix. This study attempts to propose a novel technique for orientating natural fibers like cellulose in a viscous polymer matrix such as polylactic acid (PLA) by applying the concepts of magnetism. Orientation of cellulose fibers in a PLA was achieved by modifying the cellulose fibers with a ferromagnetic entity and subjecting to a magnetic field. Chemically modified cellulose fibers (CLF) were oriented in dilute polylactic acid by subjecting the fiber and matrix to a magnetic field of ≈ 4T (Tesla). CLF and Microcrystalline cellulose (MCC) were oxidized with Hydrogen peroxide and further reacted with activated Ferrous sulphate heptahydrate (FeSO4.7H2O) in order to form Cellulose-Fe complexes. Chemically modified CLF was characterized by spectroscopic, thermal and morphological methods. The results from X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR spectroscopy) agree that coordination bonds were formed between deprotonated and/or oxidized hydroxyl groups of cellulose and Fe2+ ions. Powder X-ray diffraction (PXRD) was used to compare the crystallinity of unmodified and modified samples of CLF. Thermal properties of modified cellulose were studied using thermogravimetric analysis (TGA) and a differential scanning calorimeter (DSC). Scanning electron microscopy (SEM) results showed that there was minimal morphological change occurred to cellulose after treatment. It was also observed that the electrical conductivity of cellulose modified with Fe 2+ was higher than that of unmodified samples. The modified CLF was then mixed with polylactic acid diluted with dichloromethane and the fibers in the matrix suspension were subjected to a magnetic field of ≈ 4T. The suspension was allowed to solvent cast inside a glass vial in the magnetic field. Morphological examination of the fiber matrix composites using confocal microscopy showed that CLF were successfully oriented along the flux direction of the magnetic field.

Studies that involve natural fiber orientation in a matrix were mostly based on regulating shear forces during mixing of fiber and matrix. This study attempts to propose a novel technique for orientating natural fibers like cellulose in a viscous polymer matrix such as polylactic acid (PLA) by applying the concepts of magnetism. Orientation of cellulose fibers in a PLA was achieved by modifying the cellulose fibers with a ferromagnetic entity and subjecting to a magnetic field. Chemically modified cellulose fibers (CLF) were oriented in dilute polylactic acid by subjecting the fiber and matrix to a magnetic field of ≈ 4T (Tesla). CLF and Microcrystalline cellulose (MCC) were oxidized with Hydrogen peroxide and further reacted with activated Ferrous sulphate heptahydrate (FeSO4.7H2O) in order to form Cellulose-Fe complexes. Chemically modified CLF was characterized by spectroscopic, thermal and morphological methods. The results from X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR spectroscopy) agree that coordination bonds were formed between deprotonated and/or oxidized hydroxyl groups of cellulose and Fe2+ ions. Powder X-ray diffraction (PXRD) was used to compare the crystallinity of unmodified and modified samples of CLF. Thermal properties of modified cellulose were studied using thermogravimetric analysis (TGA) and a differential scanning calorimeter (DSC). Scanning electron microscopy (SEM) results showed that there was minimal morphological change occurred to cellulose after treatment. It was also observed that the electrical conductivity of cellulose modified with Fe 2+ was higher than that of unmodified samples. The modified CLF was then mixed with polylactic acid diluted with dichloromethane and the fibers in the matrix suspension were subjected to a magnetic field of ≈ 4T. The suspension was allowed to solvent cast inside a glass vial in the magnetic field. Morphological examination of the fiber matrix composites using confocal microscopy showed that CLF were successfully oriented along the flux direction of the magnetic field.

Biologiškai skaidžių atliekų kompostavimui didelę įtaką turi anglies ir azoto santykis, priklausantis nuo kompostuojamų medžiagų rūšies. Kokybiškam kompostui pagaminti būtinos trys pagrindinės fazės: temperatūros kilimo, aukštos temperatūros ir temperatūros kritimo. Oro temperatūra buvo palanki kompostavimo procesui – vidutinė mėnesio temperatūra buvo aukštesnė arba artima daugemiačiams vidurkiams, o kritulių kiekis kompostavimo metu buvo permainingas. Komposto temperatūra priklausė nuo kompostavimo procesui būdingos fazės ir matavimo vietos – aukščiausia temperatūra (nuo 63 iki 82oC) nustatyta termofilinio proceso metu aukščiausios komposto vietos giliuosiuose sluoksniuose. Rūgštingumas komposto krūvoje kito nuo neutralaus (pH 7) kompostavimo pradžioje, termofilinės kompostavimo fazės metu tapo šarminės reakcijos (pH 8,0–8,3), temperatūros kritimo fazėje komposto rūgštingumas mažėjo iki neutralių reikšmių (pH 7,0–7,1). Optimalus kompostavimui drėgnumas (50–60%) buvo pasiektas trečią kompostavimo savaitę. Kompostavimo aikštelėse gaminant kompostą po atviru dangumi būtina atsižvelgti į meteorologines sąlygas, kurias vertinant galima parinkti tinkamą komposto krūvos vartymo dažnumą bei dirbtinio laistymo poreikį. / The carbon to nitrogen ratio, depending on the type of compostable materials, has a great impact on the composting of biodegradable waste. The three main phases necessary for obtaining the high-quality compost: temperature rise, high temperature and temperature drop. The air temperature was favourable to the composting process – the average monthly temperature was above or close to the multi-annual average, and the rainfall has been erratic during composting. The compost temperature depended on the phase and the measurement location characterized by the composting process – the highest temperature (from 63 to 82 °C) was determined during the thermophilic process in the deep layers of the highest composting place. The acidity of the compost pile varied from neutral (pH 7) at the beginning of composting, became alkaline (pH 8,0–8,3) during the thermophilic composting phase, the compost acidity decreased to neutral values (pH 7,0–7,1) during the temperature drop phase. The optimum composting humidity (50–60%) was achieved on the third week of composting. When the compost is produced in the open air composting sites, it is necessary to take account of the meteorological conditions. According to these evaluated conditions, the proper moving procedure frequency and the need for artificial irrigation can be selected for the compost pile.

Pharmaceuticals in the aquatic environment is an emerging issue and the risks they pose are mostly unknown. They are used in large amounts throughout the world and can enter the environment, as the active metabolite or unmetabolised, through excretion by people and improper disposal. As these drugs are designed to have specific biological effects in a specific organism (as well as sometimes having other non-specific side effects), their potential to cause effects within the environment is great. Clofibric acid (the major metabolite of the lipid lowering drug, Clofibrate) is non-biodegradable, highly motile, very persistent and frequently detected at μg/I levels in the environment. I studied possible effects of clofibric acid in fish, using different experimental approaches and endpoints. The studies involve two different species, and for one of these species, fish at different stages of development. The chapters within this thesis have presented the first evidence (albeit preliminary) of clofibric acid having effects on both adult and embryo fish. When fathead minnow embryos were exposed to clofibric acid, the effects seen included changes in the eggshell, time to hatch, hatchability, mortality and viability. Adult fathead minnow were similarly exposed and significant effects on specific parameters were also observed. These included effects on lipid metabolism, steroidogenesis and spermatogenesis - thought to be via cholesterol transport - as well as significant effects on the expression of several genes involved in lipid metabolism and detoxification. Exposure of juvenile (sexually undifferentiated) bream also found significant differences in some endpoints. Other results suggested, less pronounced effects of clofibric acid on some other parameters. The results from this research show that there are effects of clofibric acid in pathways which were not only unexpected in fish (for example, steroidogenesis, spermatogenesis and gene expression), but also at concentrations below those previously shown to have any biological effects on fish. These effects indicate that clofibric acid may potentially have an impact on fish fecundity, and even more worryingly, on human health for those people prescribed it.

Thesis (M.S.)--University of Alabama at Birmingham, 2008. / Description based on contents viewed Feb. 5, 2008; title from title screen. Includes bibliographical references (p. 65-68).

Thesis (M.Sc.(Chemical Engineering))--University of Pretoria, 2007. / Abstract in English. Includes bibliographical references (leaves 74-80).

La recherche sur les matériaux diélectriques souples et biodégradable a été augmenté considérablement en raison de l'augmentation des exigences concernant l'énergie et les questions environnementales. Les composites polymériques, avec constante diélectrique élevée ont ainsi, été préférés par rapport aux composites à base de céramique pour les périphériques de stockage de l'énergie. L'objectif de cette thèse est de fabriquer une électrode biodégradable matériaux à base de nano-fibrilles de cellulose natives et oxydés (CNF) et de graphène pour améliorer le stockage diélectrique ainsi que les applications de stockage de charge électrochimique. La présente méthode de réduction, induite par les UV sur l'oxyde de graphène (GO) dans des matrices de cellulose, est une alternative prometteuse aux traitements à base de solvant en évitant la détérioration des propriétés des matériaux et l'utilisation de solvants organiques. Cette méthode pourrait être étendue à d’autres matériaux composites polymères. / The research on biodegradable and flexible dielectric materials has been increased widely because of increasing requirements about energy and environmental issues. Polymeric composites with high dielectric constant have, thus, been demanded increasingly compared to ceramic based composites for energy storage devices. The objective of this thesis is to fabricate a biodegradable electrode materials based on pristine and oxidized cellulose nanofibrils (CNF) with different graphene based fillers for enhanced dielectric storage as well as electrochemical charge storage applications. The presented dry method of UV induced reduction of graphene oxide (GO) in cellulose matrices are promising alternatives to solvent based treatments avoiding the deterioration of material properties and the use of organic solvents. This method could be extended to alternative polymer composite materials. In contrast to previous reports, the dielectric properties mainly focussed on the higher frequency regions to provide real, intrinsic material properties and obtained significant enhancement than reported studies. This approach gives a new insight to the exact performance of materials on dielectric charge storage applications. The current study gives more insight for the development of flexible, lightweight and biodegradable electrode materials for energy storage device applications.

Charles University Faculty of Pharmacy in Hradci Králové Department of Pharmaceutical Technology Consultant: PharmDr. Ondřej Holas, PhD. Student: Petra Staňková Title of Thesis: Pharmaceutical applications of polyesters as drug nanocarriers Nanoparticles are nowadays intensively studied and perspective type of a drug carrier. Its potential is based on a possibility of targeted drug delivery and controlled drug release. The theoretical part is about nanoparticles types, polymers derived from α-hydroxyacids (PLA, PGA, PLGA). Focus is given on methods of nanoparticles preparation: dispersion of preformed polymers or the polymerization of monomers. The modification of particles surface and practical use of nanomedicine in healthcare are described in other chapters. The research in experimental part is focused on the influence of different types of PLGA and their weighing on the size, polydispersity, nanoparticles zeta potential and encapsulation efficiency of rhodamine B. Nanoparticles were prepared by nanoprecipitation method or by solvent evaporation method. The Zetasiser ZS 90 device was used to measure the size of the nanoparticles and to measure zeta potential. The result of the research shows the most suitable weighing for creation of nanoparticles is 25 mg. The samples of this weighing show a...

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nos últimos 20-30 anos polímeros biodegradáveis vêm sendo estudados e desenvolvidos e atualmente já são comercializados. Contudo, o custo, a processabilidade e algumas propriedades ainda dificultam a penetração desses polímeros no mercado e a competição com as chamadas commodities. Não são poucos os autores que se dedicam a desenvolver aditivos e formulações para superar essas limitações. Desta forma, esta Tese se dedicou ao desenvolvimento de compósitos de Ecobras, fabricado pela Basf e comercializado pela Corn Products, utilizando como carga mineral resíduo da extração da bauxita, no município de Santa Luzia/PB, o qual consiste em sua totalidade de vermiculita. Esta vermiculita foi quimicamente modificada com sais de alquil fosfônio para melhorar a compatibilidade com a matriz polimérica e também espaçar as camadas de aluminossilicato. De fato, a modificação com o brometo de hexadecil tributil fosfônio resultou na esfoliação da vermiculita tornando-a potencialmente apropriada para a obtenção de nanocompósitos. A preparação dos compósitos foi realizada pelo método de intercalação no estado fundido e foram comparadas a utilização da câmara interna de mistura e da mini extrusora de dupla rosca, sendo esta última mais eficaz na dispersão da vermiculita, conforme revelado pela microscopia eletrônica de varredura, difração de raios-X e reometria de placas. O grau de dispersão também foi influenciado pela estrutura química do modificador da vermiculita e pelo teor dessa carga incorporada à matriz. Teores mais elevados levaram a formação de aglomerados, enquanto a modificação da carga implicou na formação de micro e nanocompósitos. Ainda houve alterações das propriedades térmicas com aumento dos valores da temperatura de transição vítrea, de cristalização e fusão, embora o grau de cristalinidade tenha sido mantido. Nitidamente, foram obtidos materiais mais rígidos, com maior módulo e menor capacidade de deformação. Cerca de 58% de perda de massa foi observada para os micro e nanocompósitos obtidos após 17 semanas de enterro em solo simulado para avaliação da biodegradabilidade, valor bem próximo ao Ecobras puro. De modo geral, a incorporação das diferentes vermiculitas retardou nas primeiras semanas a biodegradação, provavelmente em função de modificações na estrutura cristalina, conforme sugerido pelos maiores valores de temperatura de fusão observados durante o acompanhamento do processo de biodegradação. No entanto, após 7 semanas os perfis de biodegradação dos micro e nanocompósitos se aproximaram bastante do Ecobras puro. Desta forma, foi possível nesta Tese obter um nanocompósito de Ecobras com vermiculita modificada com brometo de hexadecil fosfônio utilizando ferramentas comuns de processamento no estado fundido com biodegradabilidade próxima ao polímero de partida, porém mais rígido e menos deformável / In the last 20-30 years biodegradable polymers have been studied and developed and currently are already commercialized. However, cost, processability and some properties still avoid the penetration of such polymers on the market and the competition with the so-called commodity. There are few authors who are dedicated to developing additives and formulations to overcome these limitations. Thus, this thesis is devoted to the development of Ecobras composites, blend of PBAT and starch manufactured by BASF and commercialized by Corn Products, using as mineral filler a residue of bauxite extraction from Santa Luzia / PB, which consists entirely of vermiculite. The vermiculite was chemically modified with alkyl phosphonium salts to improve compatibility with the polymer matrix, and also to increase the space between aluminosilicate layers. In fact, its modification with hexadecyl tributyl phosphonium bromide promoted the exfoliation of vermiculite making it potentially suitable for obtaining a nanocomposite. The preparation of the composites was performed by the melt intercalation technique. Internal mixing chamber and a twin screw mini-extruder were compared as processing tool, the latter was more effective in dispersing the vermiculite, as revealed by scanning electron microscopy, X-ray diffraction and plate rheometry. The degree of dispersion was also influenced by the amount and chemical structure of the vermiculite. Higher filler levels led to formation of agglomerates, while filler modification led to formation of micro and nanocomposites. There were changes in the thermal properties with increasing temperature values of glass transition, crystallization and melting, although the degree of crystallinity has been retained. Clearly, stiffer materials were obtained, with a higher modulus and low strain capacity. About 58% of weight loss was observed for micro and nanocomposites after 17 weeks of burial in simulated soil for evaluation of biodegradability, very close to pure Ecobras value. Generally, the incorporation of different vermiculite delayed biodegradation in the first weeks, probably due to changes in crystalline structure as suggested by the higher melting temperature values observed during the monitoring of the biodegradation process. However, after seven weeks of the micro and nanocomposites biodegradation profiles approached quite to pure Ecobras. Thus, it was possible in this work obtain a Ecobras nanocomposite with hexadecyl tetrabutyl phosphonium bromide modified vermiculite prepared by melt intercalation technique using common processing tools and with biodegradability close the starting polymer, but more rigid and less deformable

Foram desenvolvidas embalagens biodegradáveis ativas tipo espuma, obtidas a partir de fécula de mandioca, capazes de aumentar a vida-de-prateleira de frutas minimamente processadas. Para tanto, agentes ativos que evitam a proliferação de fungos, a perda de peso e, também, forneçam uma indicação visual (mudança de cor da embalagem) da qualidade do produto embalado, foram adicionados às embalagens de fonte renovável. As espumas foram obtidas pelos processos de extrusão e termoprensagem de uma massa de fécula, gel (fécula suspensa em água) e aditivos (plastificantes e/ou agentes ativos). As formulações de espumas variaram quanto: ao tipo e concentrações de plastificantes (glicerol e polietilenoglicol PEG 300); às quantidades de sólido (fécula de mandioca em pó); aos diferentes tratamentos da fécula (modificações química por acetilação e físicas irradiação e pré-gelatinização); à procedência da fécula (da Bahia e do Paraná); ao reaproveitamento de espumas descartadas; às diferentes concentrações de agentes ativos (ácido l-ascórbico, cloreto de cálcio, sorbato de potássio e permanganato de potássio) e quanto à adição de corantes naturais (extratos de beterraba e repolho roxo). Foram avaliadas, principalmente, as propriedades mecânicas e de barreira das diferentes formulações de espumas de fécula de mandioca. Os resultados indicaram que quanto maior a concentração de fécula mais resistente é a espuma. As espumas contendo o plastificante PEG 300 se mostraram bastante flexíveis, apresentaram boa resistência à ruptura e absorveram pouca água. A pré-gelatinização da fécula proporcionou melhores propriedades mecânicas e de barreira para as espumas em relação aos outros tratamentos dados à fécula de mandioca. Já a adição de agentes ativos à massa não proporcionou tais melhoras às embalagens. As espumas de fécula de mandioca produzidas pelo processo de extrusão seguido de termoprensagem foram mais resistentes à ruptura do que as produzidas somente por termoprensagem. / Active biodegradable packaging foams type were developed, obtained from cassava starch, to increase the shelf-life of minimally processed fruits. For this, active agents that prevent the proliferation of fungi, weight loss and, still, provide a visual indication (change of packaging color) of the packaged product quality, were added to the renewable packaging. The foams were obtained by extrusion and thermopressing processes of a mixture of starch, gel (starch suspended in water) and additives (plasticizers and/or active agents). The foams formulations varied as: the type and concentrations of plasticizers (glycerol and polyethylene glycol PEG 300); the concentrations of solid (cassava starch powder); the different treatments of starch (chemical, for acetylation, and physical modifications radiation and pre-gelatinization); the starch suppliers (from Bahia and Paraná); the reuse of discarded foams; the different active agents (l-ascorbic acid, calcium chloride, potassium sorbate and potassium permanganate) and the addition of natural dyes (beet and cabbage extracts). It was evaluated, mainly, the mechanical and barrier properties of the different formulations of cassava starch foams. The results indicated that the higher starch concentration more resistant become the foam. The foams containing the plasticizer PEG 300 proved to be very flexible, had good tensile strength and absorbed less water. The pre-gelatinization of starch provided better mechanical and barrier properties to foams in comparison with other treatments of cassava starch. The addition of active agents to the mix did not provide such improvements to packaging. The cassava starch foams produced by extrusion followed by thermopressing were more resistant to breakage than those produced only by thermopressing.