The emergence of microneedle (MN) technologies offers a route for a pain free, straightforward and efficient way of transdermal drug delivery, but technological barriers still exist which pose significant challenges for manufacture of MN systems with high volume outputs at low cost. The main aim of this research was to develop new ways for MN manufacture primarily using micro-injection moulding processes with high performance engineering thermoplastics. During the moulding process these polymeric melts will be subjected to extreme stress and temperature gradients and detailed material characterisation combined with in-line monitoring is desirable to optimise the moulding parameters and will help in achieving sharp microneedles with acceptable quality. Hence high shear rheology of these selected materials was performed at wall shear rates carried out in excess of 107 s-1 over a range of temperatures to predict the flow behaviour of polymer melts at such high shear strain rates. This information was fed into injection moulding simulation software tools (Moldflow) to assist the MN production process design. The optimal design was then used to produce a full 3D solid model of the injection mould and mould insert. Furthermore various design of experiments were conducted considering input parameters such as injection pressure, injection speed, melt temperature, filling time and mould cavity temperature. Response variables including product quality and data acquired from the cavity pressure and temperature transducers were used to optimise the manufacturing process. The moulded MNs were geometrically assessed using a range of characterisation techniques such as atomic force microscopy, confocal microscopy and scanning electron microscopy. An attempt to make hollow MNs was performed and encountered many challenges like partial cavity filling and part ejection during processing. Studies were carried out to understand the problem and identified the major problem was in tool design and improvements to the moulding tool design were recommended. Plasma treatment and mechanical abrasion were employed to increase the surface energy of the moulded polymer surfaces with the aim of enhancing protein adsorption. Sample surface structures before and after treatment were studied using AFM and surface energies have been obtained using contact angle measurement and calculated using Owens-Wendt theory. Adsorption performance of bovine serum albumin and release kinetics for each sample set was assessed using a Franz diffusion cell. Results indicate that plasma treatment significantly increases the surface energy and roughness resulting in better adsorption and release of BSA. To assist design-optimisation and to assess performance, a greater understanding of MN penetration behaviour is required. Contact stiffness, failure strength and creep behaviour were measured during compression tests of MN against a steel surface, and in-vitro penetration of MNs into porcine skin. The MN penetration process into porcine skin was imaged using optical coherence tomography. Finally, a finite element model of skin was established to understand the effect of tip geometry on penetration. The output of findings from this research will provide proof of concept level development and understanding of mechanisms of MN penetration and failure, facilitating design improvements for micro-injection moulded polymeric MNs.

The aircraft industry has long been concerned with the increase of drag on airplanes due to fouling of the wings by insects. The present research studied the effects of surface energy and surface roughness on the phenomenon of insect sticking. Aluminum plates of different roughnesses were coated with thin films of polymers with varying surface energies. The coated plates were attached to a custom jig and mounted on top of an automobile for insect collection. Contact angle measurements, x-ray photoelectron spectroscopy and specular reflectance infrared spectroscopy were used to characterize the surfaces before and after the insect impact experiments. Scanning electron microscopy showed the topography of insect residues on the exposed plates. Moments were calculated in order to find a correlation between the parameters studied and the amount of bugs collected on the plates. An effect of surface energy on the sticking of insect residues was demonstrated. / M.S.

This aircraft industry is concerned with the increase of drag on planes due to the sticking of insects on critical airfoil areas. The objectives of the present study were to investigate the effects of surface energy and elasticity on the number of insects sticking onto the polymer coatings on a modified aircraft wing and to determine the mechanism by which insects stick onto surfaces during a high-Velocity impact. Analyses including scanning electron microscopy (SEM), electron spectroscopy for chemical analysis (ESCA) and contact angle measurements of uncoated and polymer-coated aluminum surfaces have been performed. An air-gun was designed to accelerate insects to high speeds and impact them onto modified wing surfaces in a laboratory environment. A direct relation between the number of insects sticking on a sample and its surface energy was obtained. Since the sticky liquid from a burst-open insect will not spread on the low energy surface, it will ball up providing poor adhesion between the insect debris and the surface. The incoming air How can easily blow oH' the insect debris thus reducing the number of insects that remain stuck on the surface. Also a direct relation between the number of insect sticking onto sample surfaces and their moduli of elasticity was obtained. The deceleration of an insect impacting onto an elastomer reduces in proportional to the modulus of elasticity of the material. As a consequence, the rate of change of momentum is lower and the force and pressure exerted on the body of the insect is reduced if it impacts onto a material with a low modulus of elasticity. This lessens the chance of bursting the i insect exoskeleton. / Master of Science

<p>Cilj istraživanja doktorske disertacije je bio ispitivanje mogućnosti primene<br />vlakana od nerđajućeg čelika za koalescenciju kapi mineralnih ulja različite polarnosti<br />pri različitoj permeabilnosti sloja. Pored toga cilj je bio i komparativna analiza efikasnosti separacije ispitivanih ulja vlaknima visoke i niske energije povr&scaron;ine. Postavljena je i modifikovana metoda kinetike upijanja tečnosti za ocenu sklonosti ulja ka odabranim vlaknima od kojih se formira sloj. Po prvi put je primenjena i metoda ve&scaron;tačkih neuronskih mreža za simulaciju koalescentne filtracije.<br />Eksperimentalni program koalescentne filtracije je realizovan na model emulziji<br />dispergovanog ulja u vodi konstantne ulazne koncentracije 500 mg/l,<br />pri konstantnoj temperaturi od 20&deg;C, horizontalnoj orijentaciji toka fluida i<br />prosečnoj veličini kapi ulja od 10 &mu;m. Uticaj geometrije sloja ispitivan je variranjem<br />permeabilnosti u opsegu od 0,1810^-9 m2 do 5,510^-9 m² za konstantnu<br />debljinu sloja od 5 cm. Testirana su tri uzorka mineralnog ulja velikog raspona<br />viskoznosti i polarnosti. Svi ogledi su realizovani pri konstantnoj brzini fluida u intervalu od 10 m/h do 80 m/h. Izlazna koncentracija dispergovane faze<br />odredivana je FTIR spektrofotometrijom.<br />Značajan doprinos u istraživanju fenomena koalescencije u sloju vlakana<br />ogleda se u utvrdivanju mogućnosti primene vlakana nerdajućeg čelika na<br />separaciju kapi mineralnih ulja, razumevanju simultanog uticaja energije<br />povr&scaron;ine, geometrije sloja i prirode uljne faze, kao i uvodenju nove veličine<br />izo-izlazne koncentracije. Test odredivanja kinetike upijanja tečnosti je pokazao<br />da odnos liofilno-liofobne kva&scaron;ljivosti materijala adekvatno opisuje sklonost<br />nekog filtarskog materijala ka separaciji ulja mineralnog porekla. Ovako<br />sveobuhvatna analiza uticaja različitih parametara na efikasnost koalescentne<br />filtracije, data u ovoj disertaciji, nije zabeležena u dostupnim literaturnim navodima.<br />Rezultati doktorske disertacije omogući će skraćivanje vremena i materijalnih<br />tro&scaron;kova neophodnih za projektovanje koalescera, jer smanjuju potreban<br />obim eksperimentalnih istraživanja potrebnih za uspe&scaron;no projektovanje.<br />Odabrani uslovi rada, prvenstveno prečnik vlakana materijala u odnosu na<br />ulaznu veličinu kapi, kao i način njihovog pakovanja, uz obezbedivanje poznate<br />i definisane permeabilnosti, obezbedili su željenu separaciju, čija se efikasnost<br />separacije kapi ispitivanih ulja vlaknima od nerdajućeg čelika kreće u<br />opsegu od 91% do 99% za opseg brzina fluida od 10 m/h do 50 m/h. Kod sloja<br />vlakana od nerdajućeg čelika efikasnija separacija je zapažena pri niskim vrednostima<br />permeabilnosti, dok je kod polimernog materijala obrnut slučaj. Zaključeno je da, u postojećim okolnostima, kod posmatranih materijala dominiraju<br />različiti mehanizmi koalescencije u sloju. Oblik zavisnosti izlazne koncentracije<br />od brzine i permeabilnosti za oba ispitivana materijala, nerdajući čelik i<br />polipropilen, je sličan. Polipropilen ima veći radni opseg brzina u odnosu na<br />nerdajući čelik. Medutim, nerdajući čelik uspe&scaron;nije separi&scaron;e ulje najniže viskoznosti<br />u oblasti niskih vrednosti permeabilnosti i pri niskim radnim brzinama<br />u odnosu na polipropilen. Zadovoljavajući kvalitet separacije se kod polipropilena<br />ostvaruje pri najvi&scaron;oj permeabilnosti i u &scaron;irokom opsegu brzina, dok se<br />kod nerđajućeg čelika najvi&scaron;e vrednosti kritične brzine za ceo opseg ispitivane<br />viskoznosti ostvaruju pri najnižoj permeabilnosti sloja.</p> / <p>The aim of the doctoral thesis was to investigate the possibility of the stainless<br />steel fibers application for the coalescence of mineral oil drops with different<br />polarity varying also the bed permeability. Additional aim was the comparative<br />analysis of the tested oil separation efficiency with fibers that have high<br />and low surface energy. The method for the evaluation of the fiber-liquid wetting<br />kinetic was set up and modified in order to assess the affinity of oil to the<br />selected fiber that was used to form the filtration bed. For the first time, the<br />method of artificial neural networks was applied to simulate the coalescence<br />filtration.<br />Experimental program of coalescence filtration was performed on oil-in-water<br />model emulsion with constant inlet concentration of 500 mg/l, at a constant<br />temperature of 20&deg;C, horizontal fluid flow orientation and average oil drop<br />size of 10 &mu;m. The influence of bed geometry was studied varying bed permeability<br />in the range from 0,1810^-9 m2 to 5,51010^-9 m2 for the constant layer thickness of 5 cm. Three samples of mineral oil that have large range of viscosity<br />and polarity were tested. All experiments were carried out at constant<br />fluid velocity in the range from 10 m/h to 80 m/h. The output dispersed phase<br />concentration was determined by FTIR spectrophotometry.<br />A significant contribution to the research of the coalescence phenomenon in<br />a fiber bed was achieved by determining the possibility to use stainless steel<br />fibers for the separation of mineral oil drops, broadening the apprehension<br />of the simultaneous influence of surface energy, bed geometry and oil phase<br />nature, as well as the introduction of an iso-output concentration as a new<br />parameter. The evaluation of the fiber-liquid wetting kinetic showed that the<br />lipophilic-lyophobic wettability ratio of the material adequately describes the<br />tendency of a filter material for the mineral oil separation. Such comprehensive<br />analysis of the various parameters impact on the efficiency of coalescence<br />filtration, presented in this thesis, was not found in available literature. The results<br />of the doctoral thesis will enable the reduction of time and material cost<br />needed for the design of coalescer, by decreasing the extent of experimental<br />research necessary for successful design.<br />Selected working conditions, primarily the fiber diameter in relation to the input<br />drop size, as well as bed packaging, while ensuring the known and defined<br />bed permeability, provided the desired separation, with the oil drop separation<br />efficiency of tested stainless steel fibers in the range from 91% to 99% for a fluid<br />velocity range from 10 m/h to 50 m/h. When stainless steel was used, more<br />efficient separation was observed for the low bed permeability, whereas for<br />the polymer fibers the reverse order was identified. It was concluded that, in<br />the existing circumstances, different mechanisms of oil drop coalescence dominate<br />for these materials. The dependence of output concentration from the<br />velocity and bed permeability for both tested materials, stainless steel and polypropylene, was similar. Polypropylene has a higher operating velocity range<br />in comparison to stainless steel. However, when compared to polypropylene,<br />stainless steel separates more successfully the oil with the lowest viscosity in<br />the low bed permeability and at low fluid velocity domain. Satisfactory quality<br />of separation with polypropylene is achieved at the highest bed permeability<br />and in a wide fluid velocity range, whereas, with the stainless steel, the highest<br />values of critical velocity, for the entire range of tested viscosity, are realized at<br />the lowest bed permeability.</p>

Neste trabalho investigou-se a influência da adição dos ânions cloreto, fluoreto e sulfato nas propriedades físico-químicas de nanopós de zircônia sintetizada pelo método Pechini. Análises de fluorescência de Raios-X, difração de Raios-X, espectroscopia no infravermelho, área de superfície específica, espectroscopia Raman, microscopia eletrônica de varredura, análise termogravimétrica, calorimetria diferencial por varredura, amplitude sônica eletrocinética e dilatometria foram realizadas para caracterizar os pós sintetizados. Os resultados obtidos mostraram que o tratamento térmico realizado para a obtenção dos pós retirou os ânions cloreto e fluoreto da composição química final da zircônia enquanto o ânion sulfato permaneceu. Mesmo sendo retirados os ânions cloreto e fluoreto influenciaram no processo de cristalização da zircônia modificando o tamanho de cristalito obtido. A permanência do ânion sulfato na composição química da zircônia se deve à maior energia de ligação com o cátion Zr 4+ assim, observou-se uma maior influência deste ânion no processo de cristalização. Isso permitiu a formação de cristalitos menores e a estabilização da fase tetragonal da zircônia. Em todos os casos, as análises mostraram que a influência dos ânions se deu por segregação dos mesmos na superfície da zircônia o que, principalmente no caso do ânion sulfato, tende a reduzir a energia da superfície da zircônia através do aumento da área de superfície específica. Verificou-se também que o ânion sulfato pode ser retirado da superfície da zircônia através da lavagem do pó em meio básico. Esse procedimento permitiu aumentar a área de superfície específica e tende a melhorar sua sinterabilidade. / In this study was investigated the influence of the addition of the chloride, fluoride and sulfate anions in the physico-chemical properties of zirconia nanopowders synthesized by the Pechini method. Analyses of X-ray fluorescence, X-ray diffraction, infrared spectroscopy, specific surface area, Raman spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry, electrokinetic sonic amplitude and dilatometry were performed to characterize the synthesized powders. The results showed that the heat treatment performed to obtain the powders removed the chloride and fluoride anions from the final chemical composition of the zirconium whereas the sulfate anion anion remained. Despite the chloride and fluoride anions removal, they influenced the crystallization process of the zirconium, modifying the size of the crystallite obtained. The permanence of the sulfate anion in the chemical composition of the zirconia is due to the higher binding energy with the Zr 4 + cation, thus it was observed a greater influence of that anion in the crystallization process. That allowed the formation of smaller crystallites and the stabilization of the tetragonal phase of the zirconia. In all of the cases, the analyses showed that the influence of the anions occurred by their segregation on the surface of the zirconia which, particularly in the case of the sulfate anion, tends to reduce the surface energy of the zirconium by increasing the specific surface area. It was also found that the sulfate anion can be removed from the surface of the zirconia by washing the powder in a basic medium. That procedure increased the specific surface area and it tends to improve its sinterability.

As aplicações do ZrO2 dependem das suas fases cristalinas e muitos estudos têm sido realizados sobre suas transições e os aditivos empregados no seu controle. No entanto, os mecanismos atuantes em tais processos são explicados com base exclusivamente cinética desconsiderando a contribuição termodinâmica que os aditivos exercem sobre as energias dos polimorfos e suas superfícies. Neste trabalho, o efeito termodinâmico do MgO sobre as transformações de fases é estudado para pós de ZrO2 preparados por uma rota química derivada do método Pechini. Análises de picnometria, área de superfície específica, difração de raios X, espectroscopias de infravermelho, Raman e de fotoelétrons excitados por raios X, além de amplitude sônica eletrocinética foram empregadas para caracterizar a evolução das fases formadas. Verifica-se que quantidades crescentes de MgO desestabilizam a fase monoclínica e tornam a fase tetragonal estável. A fase cúbica é encontrada para grandes quantidades de MgO. As transformações de fases marcam descontinuidades em características como área de superfície específica devido a alteração de simetria cristalina. O MgO, na forma de periclásio, não foi observado para quantidades inferiores a 40 % molar. Levando-se em conta a baixa solubilidade do MgO no ZrO2 conclui-se que o controle das fases observadas possui pouca contribuição de processos cinéticos associados à formação de defeitos puntiformes. Resultados de XPS mostram que o íon Mg2+ localiza-se tanto na rede cristalina quanto na superfície do ZrO2. A sua segregação é atribuída a um efeito termodinâmico que resulta na diminuição da energia de superfície do ZrO2 promovendo o desenvolvimento de um excesso de superfície, confirmado pelas medidas de área de superfície específica, com a conseqüente diminuição do tamanho de partícula. Tais conclusões implicam que ambos os efeitos termodinâmicos e cinéticos devem ser considerados no controle do polimorfismo do ZrO2. / The applications of ZrO2 depend on its cristalline phases and several studies have been carried out about its transitions and the additives used to control it. However, the active mechanisms in such processes are explained with an exclusively kinetic basis disregarding the thermodynamic contribution that the additives exert over the polimorphs and surface energies. In this work, the thermodynamic effect of MgO on phase transformation is reported for ZrO2 powders prepared by a chemical route derived from Pechini\'s method. Picnometric, specific surface area, X-ray diffraction, infrared, Raman and X-ray photoelectron spectroscopies, besides electrokinetic sonic amplitude experiments were performed to characterize the evolution of the formed phases. It is verified that crescent amounts of MgO desestabilize the monoclinic phase and make stable the tetragonal. The cubic phase is found for large amounts of MgO. The phase transformations appoint descontinuities as the specific surface area due to crystalline simmetry change. The MgO, in the periclase form, wasn?t observed for amounts lower than 40 molar %. Taking into account the low solubility of MgO into ZrO2 it is concluded that the control of the observed phases has a low contribution to kinetic processes associated to point defects formation. XPS data show that Mg2+ ion is located onto the bulk as far as the ZrO2 surface. Its segregation is assigned to a thermodynamic effect resulting in a decrease of ZrO2 surface energy, which promotes the development of a surface excess, upholded by specific surface area measurements, with the consequent decrease of particle size. Such conclusions impose that both thermodynamic and kinetic effects must be considered on the control of ZrO2 polimorphism.

Os avanços na engenharia de materiais têm aumentado a busca por materiais com atividade antimicrobiana para aplicação em áreas da saúde. Neste contexto, a presente pesquisa desenvolveu materiais para revestir bráquetes metálicos utilizados no tratamento ortodôntico. As sínteses de hidroxiuretanos (HU) foram realizadas empregando-se bis(ciclocarbonatos) derivados de epóxidos com segmentos siloxânicos por reação de aminólise. Dois ciclocarbonatos (CC) foram sintetizados, a partir da reação de cicloadição de CO2 ao anel epóxi do 1,3-bis(3-glicidiloxipropil)tetrametildisiloxano e do polidimetilsiloxano diglicidil éter catalisada pelo brometo de hexadeciltrimetilamônio. Os CCs obtidos foram denominados de CCMDMS e CCPDMS. Para aumentar o tamanho dos HUs e, consequentemente proporcionar um ganho nas propriedades mecânicas, realizou-se um processo de extensão pela reação da 3-(aminometil)-3,5,5-trimetilcicloexilamina com os CCs (CC-HUMDMS e CC-HUPDMS). O processo de finalização dos HUs foi realizado através da reação do CC-HUMDS com a 3-trietoxisililpropilamina e, o CC-HUPDMS com a 3-trietoxisililpropilamina e N-aminoetil-3-trimetoxisililpropilamina. Os HUs sintetizados foram chamados de HUMDMS, HUPDMS e HUPDMS2. Para elevar o caráter antibiofilme do HUMDMS, HUPDMS e HUPDMS2 foram incorporadas nanopartículas a suas estruturas por dois métodos. O primeiro, método coloidal, consistiu na redução dos cátions Ag+ em etanol misturados com os HUs, sendo os produtos denominados de HUMDMSCol, HUPDMSCol e HUPDMS2Col. O segundo, método fotoassistido, baseou-se na adição de nanopartículas de óxido de zinco (nanoZnO), nesta etapa, os HUs foram chamados de HUMDMSZnO, HUPDMSZnO e HUPDMS2ZnO, seguido pela imersão em solução aquosa de nitrato de prata e, posterior, redução com luz ultravioleta, os materiais obtidos foram chamados de HUMDMSIrr, HUPDMSIrr e HUPDMS2Irr. Os materiais foram caracterizados quanto à sua estrutura química, para tanto, utilizou-se técnicas espectroscópicas de infravermelho com reflexão total atenuada, ressonânciamagnética nuclear e fotoelétrons excitados por raios-X. A morfologia foi analisada por microscopia de transmissão eletrônica e difração de raios-X, avaliou-se a estabilidade térmica por análise termogravimétrica e a energia superficial por medidas de ângulo de contato. As técnicas de espectroscopia no ultravioleta e visível e espectrometria de emissão atômica com plasma acoplado indutivamente foram utilizadas para observar a banda plasmônica das nanopartículas e a sorção/dessorção de cátions, respectivamente. As nanoAg apresentaram absorção plasmônica em 415 e 440 nm para os métodos coloidal e fotoassistido, respectivamente. O valor de pH satisfatório para sorção de Ag+ foi observado entre 7 e 8, com a seguinte ordem de sorção HUPDMS2 &gt; HUMDMS &gt; HUPDMS. As isotermas de sorção mostraram que o modelo de Sips justifica satisfatoriamente o processo de sorção dos cátions Ag+ pelos HUs. Os materiais foram termicamente estáveis para temperaturas inferiores a 200 °C. A resistência abrasiva dos HUs foi avaliada com base em ensaios de fricção utilizando-se escova e creme dental. Os filmes de HUPDMS apresentaram maior fragilidade, mesmo com aumento da resistência devido adição de nanoZnO. Todos os filmes apresentaram energia superficial inferior a 25 mN/m, indicando assim, resistência à formação de biofilme. A atividade antibiofilme dos materiais híbridos foi testada para as bactérias Escherichia coli, Enterococos feacalis e Estreptococos mutans, bem como, para o fungo Candida albicans. O processo de dessorção dos cátions Ag+ nos filmes com nanoAg potencializou a eficácia contra a formação de biofilme. / Advances in material engineering have increased the search for materials with antimicrobial activity for application in health areas. In this context, the present research developed materials to coat metallic brackets used in orthodontic treatment. The synthesis of hydroxyurethanes (HU) was carried out using bis(cyclocarbonates) derived from epoxides with siloxane segments by aminolysis reaction. Two cyclocarbonates (CC) were synthesized by cycloaddition reaction of CO2 to the epoxy ring of 1,3-bis(3-glycidyloxypropyl) tetramethyldisiloxane and the polydimethylsiloxane diglycidyl ether catalyzed by hexadecyltrimethylammonium bromide. The obtained CCs were called CCMDMS and CCPDMS. To increase the size of the HUs and consequently provide a gain in the mechanical properties, a process of extension was carried out by the reaction of 3-(aminomethyl)-3,5,5-trimethylcyclohexylamine with the CCs (CC-HUMDMS and CC-HUPDMS). The HU-termination process was performed by reacting CC-HUMDS with 3-triethoxysilylpropylamine and CC-HUPDMS with 3-triethoxysilylpropylamine and N-aminoethyl-3-trimethoxysilylpropylamine. The HUs synthesized were called HUMDMS, HUPDMS and HUPDMS2. To raise the antibiofilm character of the HUMDMS, HUPDMS and HUPDMS2 nanoparticles were incorporated into their structures by two methods. The first, colloidal method consisted in the reduction of the Ag+ cations in ethanol mixed with the HUs, the products being called HUMDMSCol, HUPDMSCol and HUPDMS2Col. The second, photo-assisted method was based on the addition of nanoparticles of zinc oxide (nanoZnO), at this stage the HUs were called HUMDMSZnO, HUPDMSZnO and HUPDMS2ZnO, followed by immersion in aqueous solution of silver nitrate and subsequent reduction by ultraviolet light, the obtained materials were called HUMDMSIrr, HUPDMSIrr and HUPDMS2Irr. The materials were characterized in terms of their chemical structure, using infrared spectroscopy techniques with attenuated total reflection, nuclear magnetic resonance and X-ray excited photoelectrons, the morphology was analyzed by transmission electron microscopy and X-ray diffraction, the thermal stability was evaluated by thermogravimetric analysis and the surface energy by contact angle measurements. Ultraviolet and visible spectroscopy techniques and inductively coupled plasma atomic emission spectrometry were used to observe the plasmon band of nanoparticles and cation sorption/desorption, respectively. The nanoAg presented plasmid absorption at 415 and 440 nm for the colloidal and photoassayed methods, respectively. The pH value satisfactory for Ag+ sorption was observed between 7 and 8, with the following sorption order HUPDMS2 &gt; HUMDMS &gt; HUPDMS. The sorption isotherms showed that the Sips model satisfactorily justifies the sorption process of the Ag+ cations by HUs. The materials were thermally stable at temperatures below 200 °C. The abrasive strength of the HUs were evaluated based on friction tests using brush and toothpaste. The films of HUPDMS presented greater fragility, even with increased resistance due to the addition of nanoZnO. All films presented surface energy lower than 25 mN/m, thus indicating resistance to biofilm formation. The antibiofilm activity of the hybrid materials was tested for Escherichia coli, Enterococos feacalis and Streptococcus mutans strains, as well as for Candida albicans fungus. The desorption process of Ag+ cations in films with nanoAg enhanced the antibiofilm efficacy.

La durabilité des verres, leur réactivité ou leur fonctionnalisation peuvent être optimisées en modifiant leur état de surface, ouvrant ainsi la voie à de nouvelles applications. L'objectif de cette thèse est de mieux appréhender les modifications induites à la surface et à la sub-surface des verres d'oxydes, ainsi que l'évolution des micro-défauts existant à leur surface au cours de traitements thermiques. Ces traitements sont réalisés autour de la température de transition vitreuse, mais à des températures où le verre ne se déforme pas. Cette étude met en évidence l'influence cruciale de l'atmosphère de traitement. Elle porte principalement sur le cas du verre « float », en distinguant les faces « air » et « étain ».En s'appuyant sur les spectroscopies SIMS et Infrarouge, l'étude montre que les modifications de la sub-surface du verre dépendent de la teneur en eau de l'atmosphère du four. Alors que la sub-surface, initialement hydratée, est peu modifiée lorsque le taux d'humidité est élevé, les changements les plus significatifs sont observés sous atmosphère sèche. La déshydratation de la sub-surface du verre induit en effet la création d'une couche enrichie en silice par appauvrissement en ions modificateurs.Pour caractériser l'influence de ces modifications sur l'évolution de la morphologie des micro-défauts de surface au cours des traitements thermiques, des micro-fissures sont générées par indentation Vickers puis analysées par microscopies optique et électronique. Deux mécanismes sont mis en évidence : soit une fermeture des fissures dans les premiers instants du traitement sous l'effet de la relaxation des contraintes, soit une sphéroïdisation des fissures par flux visqueux induit par les forces tensions capillaires. Ces mécanismes sont en compétition et dépendent de l'état initial de la sub-surface du verre. En effet, la viscosité de cette sub-surface est fortement dépendante de son taux d'hydratation et peut varier très significativement au cours du traitement thermique. Dans le cas de la face « étain » du verre float, l'influence du caractère oxydant de l'atmosphère est également mis en évidence. / The glass durability, its reactivity or its functionalization can be optimized by surface modification, allowing development of new applications. The aim of this thesis is to better understand the changes induced at the oxide glass surface and sub-surface and the evolution of surface micro-flaws during thermal treatment.These treatments are performed around glass transition temperature, but at temperatures at which the samples are not deformed. The key role of the atmosphere of treatment is especially highlighted. Analyses focused on the float glass both on the “air side” and “tin side”.Based on SIMS and infrared spectroscopies, results show that the sub-surface changes depend on the water content of the furnace atmosphere. While the sub-surface, initially hydrated, is not strongly modified when the humidity level is high, significant changes are induced under dry atmosphere. The dehydration of the sub-surface induces indeed the formation of a silica enriched layer by impoverishment of modified ions.In order to characterize the influence of these changes on the evolution of micro-flaws morphology during thermal treatments, micro-cracks are generated by Vickers indentation and analyzed by optical and electronic microcopies. Two main behaviors are evidenced: either a direct crack closure during the first step of the thermal treatment due to stress relaxation or a crack spheroidization caused by viscous flow driven by capillarity forces. Both mechanisms are in competition and depend on the initial state of the glass sub-surface. The viscosity of this layer is highly dependent on the hydration level and can vary significantly during the treatment. In case of “tin side” of float glass, the effect of oxidant atmosphere is also evidenced.

Esta tese está dividida em duas partes. Na Parte I, blendas de polietileno maleado (M-PE) e butirato acetato de celulose (CAB) (5-50% em massa) e compósitos de polietileno (PE) ou M-PE e 20% em massa de celulose, acetato de celulose (CA), propionato acetato de celulose (CAP) ou CAB foram preparados em um misturador. As estruturas e propriedades das misturas foram estudadas através de ensaios mecânicos, calorimetria exploratória diferencial, microscopia eletrônica de varredura, extração com solvente seletivo seguida de espectroscopia FTIR e difração de raios-X (XRD). As blendas M-PE/CAB e os compósitos PE/polissacarídeo e M-PE/polissacarídeo não apresentaram mudanças significativas nos valores da temperatura de fusão (Tm) quando comparados aos valores de Tm do PE e do M-PE. Dados de XRD mostraram que a adição das cargas não causou mudança na estrutura cristalina do PE ou M-PE, mas aumentou a região amorfa dos materiais, indicado que a miscibilidade ocorre na parte amorfa do PE. Compósitos preparados com M-PE apresentaram tensão no escoamento e elongação superiores do que os preparados com PE, evidenciando o efeito compatibilizante do anidrido maléico. Na parte II, o efeito de dois bons solventes, acetona e acetato de etila, nas características e propriedades superficiais dos filmes finos (50nm&#60;espessura<200nm) e ultrafinos (espessura<6nm) de CA, CAP ou CAB preparados por revestimento rotacional ou adsorção, respectivamente, foram caracterizados por elipsometria, microscopia de força atômica (AFM) e medidas de ângulo de contato. Os resultados foram discutidos baseados na taxa de evaporação do solvente e na energia de interação substrato-solvente. Os efeitos do recozimento e do tipo de éster de celulose na espessura, morfologia e molhabilidade da superfície foram investigados. Após o recozimento, os filmes ultrafinos de ésteres de celulose tornam-se hidrofóbicos, indicando uma reorientação molecular na interface sólido-ar. Os filmes ultrafinos preparados a partir de soluções de acetona são estáveis, enquanto que os preparados a partir de soluções de acetato de etila apresentaram dewetting. A estabilidade dos filmes foi monitorada por AFM e explicada pelos valores da constante de Hamaker, determinados pela primeira vez para estes materiais. A imobilização de lipase sobre os filmes ultrafinos estáveis de CA, CAP e CAB com e sem recozimento foi quantificada para avaliar a possibilidade de aplicação destes filmes como substratos para biomoléculas. A adsorção de lipase sobre os filmes de CA e CAP com recozimento foi mais pronunciada do que nos mesmos filmes sem recozimento. A atividade enzimática da lipase foi avaliada com medidas espectrofotométricas do produto formado a partir da hidrólise do para-nitrofenol dodecanoato. A lipase imobilizada sobre os filmes mais hidrofóbicos apresentou uma atividade maior do que a lipase livre e manteve a atividade alta após três usos. As amostras foram estocadas por até 30 dias. A lipase imobilizada sobre os filmes mais hidrofóbicos manteve 70% da sua atividade, e a lipase imobilizada sobre os filmes mais hidrofílicos manteve apenas 30% da atividade. Estes resultados indicaram que preservação da estrutura conformacional da enzima foi favorecida pela hidrofobicidade do substrato polimérico e interações entre os resíduos polares da lipase e as partes de glucopiranosil dos ésteres de celulose. / This thesis is divided into two parts. In the first part, blends of maleated polyethylene (M-PE) and cellulose acetate butyrate (CAB) (5-50wt%) and composites of polyethylene (PE) or M-PE and 20wt% of cellulose, cellulose acetate (CA) or cellulose acetate propionate (CAP) were prepared in an laboratory mixer. The mixtures structures and properties have been studied by means of tensile testing, differential scanning calorimetry, scanning electron microscopy, X-ray diffraction (XRD) and extraction with a selective solvent followed by Raman spectroscopy. No significant change on the melting temperature (Tm) values obtained for M-PE/CAB blends or PE/polysaccharides or M-PE/polysaccharides composites could be observed, when compared with the Tm values obtained for PE and M-PE. X-ray diffraction showed that the addition of the polysaccharides had no influence on the lattice constants of PE or M-PE, but it increased the PE amorphous region, indicating that the miscibility happens on the amorphous region of the PE. Composites prepared with M-PE presented yield stress and elongation values higher than those prepared with PE, showing the compatibilizer effect of maleic anhydride. In the second part, the effect of two good solvents, acetone and ethyl acetate, on the characteristics and surface properties of thin (30nm&#60;thickness<200nm) and ultrathin (thickness<6nm) cellulose ester films obtained by spin coating or adsorption, respectively, has been investigated by means of ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The results were discussed in the light of solvent evaporation rate and interaction energy between substrate and solvent. The effects of annealing and type of cellulose ester on film thickness, film morphology and surface wettability were also studied. Upon annealing, ultrathin films of cellulose ester became hydrophobic, evidencing molecular re-orientation at the solid-air interface. Ultrathin films prepared from acetone solutions are stable, but the ones prepared from ethyl acetate solutions presented dewetting. Film stability was followed by AFM and explained with basis on the Hamaker constant values, calculated for the first time for CA, CAP and CAB. The adsorption of lipase onto stable ultrathin films of cellulose esters, with and without annealing, was quantified in order to evaluate the possibility of applying such films as support for biomolecules. Lipase adsorption onto annealed CA and CAP films was more pronounced than that onto CA and CAP untreated films. Enzymatic activity was evaluated by the spectrophotometric measurement of the product formed from the hydrolysis of para-nitrophenyl dodecanoate. Lipase immobilized onto more hydrophobic films presented higher activity than free lipase and could be reused three times retaining activity at a high level. The effect of storing time on the activity of immobilized lipase was studied. Lipase immobilized onto more hydrophobic films retained 70% of activity after one month, reaching the same level of activity of free lipase, and lipase immobilized onto more hydrophilic films retained just 30% of activity after 30 days. These results indicated that enzyme preservation was favored by polymeric substrate hydrophobicity and by the interactions between the polar residues of lipase and the glucopyranosyl moieties of cellulose ester.

Thermodynamic analysis of processes in electrolytic fuel cell membrane Michal Pavelka April 12, 2012 Abstract Hydrogen fuel cells1 may become a key technology of 21st century, and it is important to be able to describe their behavior, therefore. In this work we focus on hydrogen fuel cells with a polymer-electrolyte membrane. For the membrane we adopt an existing model2 . We for- mulate the model in the framework of the mixture theory which we develop similarly as has been done in the classical textbook of Mazur and de Groot3 . However, refining the concept of potential energy of a material point, we introduce new terms called internal potential ener- gies which enable us to describe macroscopic consequences of internal forces between water and polymer in the membrane and to describe the influence of gradient of surface tension of water in the membrane. We solve the model in 1D approximation. Consequently, we calculate the influence processes in the membrane have on efficiency of the fuel cell. 1 see for example Larminie, J. and A. Dicks. Fuel Cell Systems Explained. 2nd edition. John Wiley & Sons Ltd., 2003. ISBN 0-470-84857-X. 2 Weber, A. Z. and J. Newman. Transport in Polymer-Electrolyte Membranes I, II, III. J. Electrochem. Soc., 150 (7), A1008-A1015, 2003; 151 (2), A1311-A1325, 2004.; 151 (2), A1326-A1339,...