The challenge of demolding during the cast molding process of silicone hydrogel contact lenses can be addressed with the application of hydrophobic coatings on the surface of lens mold. In particular, the adhesion between silicone hydrogel and silicate substrates was minimized by applying silane modification on the surface of silicate substrates. Peel tests were conducted to measure the adhesive strengths between silicone hydrogel and surface modified glass substrates. Water contact angle measurement and X-ray photoelectron spectroscopy (XPS) were utilized to characterize the surface properties of silane treated glass substrates.Silicone hydrogel was obtained by curing macromer mixture under UV for 6 minutes, with UV intensity of 95.0 mW/cm2. The obtained silicone hydrogel had a modulus of 0.87±0.09 MPa, within the same range of commercial contact lenses. And the hydrogel with a UV curing time of 6 minutes was unable to be peeled off from clean glass substrates. The effects of silane type and concentration on coating effectiveness were investigated and the most effective types of silane were found to be triethoxyphenylsilane (TEPhS) and octyltriethoxysilane (OTES), with an optimal concentration of 5 wt%. The peel strength between silicone hydrogel and silicate substrates was reduced to below 15.5 N/m with the application of TEPhS and OTES coatings. However, these silane coatings were not durable enough. Silane coupling agents need to be reapplied before each curing process of silicone hydrogel. / Thesis / Master of Applied Science (MASc)

<p>The interactions of microgel based adhesives with cellulose were studied by peel test of cellulose laminates and tensile test of handsheets. The objective of this project was to create design rules for microgel based adhesives so as to improve the wet paper strength. Colloidal microgel based adhesives were formed by coating carboxylated poly(Nisopropylacrylamide) (PNIPAM) microgels with polyvinylamine (PVAm). The characterization of the microgel base adhesives were performed by electrophoretic mobilities, dynamic light scattering, and potentiometric titration. The microgel based adhesives were pH sensitive and their swelling behaviour was related to the composition of PVAm in the microgels. The maximum amount of PVAm binding to microgels depends on the location of charges in the microgels and the molecular weight of PVAm. The binding process of PVAm to microgels was monitored by quartz crystal microbalance measurements. It is proposed that the binding of PVAm to microgels is controlled by the rate of initial attachment of PVAm and the rate of reconfiguration of PVAm on the microgels. The microgel based adhesives were laminated between oxidized cellulose films and the wet adhesion of microgel based adhesives with cellulose was studied by a 90° peel test. The wet delamination force was measured as a function of PVAm content, PVAm molecular weight, coverage of adhesives on cellulose films, size of adhesives, stiffness of adhesives and the roughness of cellulose films. The wet adhesion of microgel based adhesives with cellulose increased with PVAm content in the microgels, and decreased with microgel stiffness. The molecular weight of PVAm did not influence the performance of adhesives. The effect of microgel size on wet adhesion with cellulose was related to the roughness of cellulose films. Larger microgels did fill the voids between rough cellulose films to create more contact area with these films resulting in higher wet adhesion. By contrast, for smooth cellulose films, the size of microgels didn’t affect the wet adhesion. Finally, this basic research was extended to a practical situation. The microgel based adhesives were added to unbeaten, bleached softwood pulp to prepare handsheets and their ability to enhance wet paper strength was evaluated by tensile test. The wet paper strength increased with PVAm content of the microgels. For linear PVAm, high molecular weight PVAm was more effective as a wet strength adhesive while for PVAm coated microgels, the molecular weight was not significant for wet paper strength. With the aid of PVAm coating, solid carboxylated polystyrene particles improved the wet paper strength. However the wet strength of paper treated with PVAm coated microgels was larger than that treated with PVAm coated polystyrene by a factor of 2.</p> / Doctor of Philosophy (PhD)

When bonds between copper and printed circuit board laminates are subjected to impulsive forces, the need arises to characterize fracture energies corresponding to related, high-speed failure events. Work (or energy) is required to create new surface area—with associated dissipation events—during fracture, and this energy (for a given material system) is dependent on the speed of crack propagation, the locus of failure, and the temperature of the bond when it is broken. Since the 90° peel test has been widely employed in quasi-static fracture testing of film adhesion for printed circuit board applications, this test was first used as a basis to which other test results could be compared. A test fixture was designed and built for quasi-static peel testing that accommodated peeling at different angles and temperatures. A similar test was then desirable for the direct comparison of dynamic fracture events to those quasi-static results. The “loop peel test” was thus developed to mimic the common 90° peel test and to quantify the time- and temperature-dependent fracture energies of peel specimens during low-velocity impact. This test has been successfully used to determine the apparent critical strain energy release rate of copper/epoxy bonds for low-velocity impact conditions (1-10 m/s), for a case of near-interfacial failure. The falling wedge test has also been adapted to estimate the apparent critical strain energy release rate at similar fracture conditions. Four types of printed circuit boards have been analyzed with the above impact test methods as well as with their corresponding quasi-static tests, and the fracture energies measured with the impact tests have been compared to those obtained using quasi-static tests. Fracture energies of the material systems considered were dependent on time (speed of fracture), temperature, and the amount of moisture migration, as determined via humidity conditioning parameters. / Master of Science

The transformation of the rangelands of the South Island of New Zealand during the pastoral era fits into the wider international context of European expansion into the 'new' world. European settlers displaced native peoples, introduced 'old' world animals and plants, and imposed a capitalist system that converted local resources into international commodities. In New Zealand the orthodox explanation of the pastoral impact on the rangelands claims that pastoralists introduced an unsustainable system of land use to the region. The pastoralists� indiscriminate burning practices and overstocking with sheep opened up the country to invasion by rabbits. Burning and overgrazing by sheep and rabbits stripped the natural fertility of the soils and left the country depleted, eroded, and overwhelmed by pests and weeds. This thesis sets out to test those claims. It explores burning, the stocking of the rangelands with sheep and the impact of rabbits in detail. It also examines other land management practices, as well as sheep breeding, to see what impact they had on the landscape. The timeframe is set between 1841, when formal British settlement was established in the South Island, and 1912, by which time most of the great estates and stations had been broken up into smaller runs and farms. The thesis uses station diaries, memoirs, contemporary newspapers and farming journals to assess what happened on the ground during the pastoral era. In particular, the thesis uses Mt Peel Station as a case study to examine the intensification in land use that took place between 1841 and 1912, in order to explain the transformation of the landscape and to answer the questions: what happened, how did it happened and why did it happened as it did? These sources illustrate that the pastoral era was characterised by innovation. Pastoralists had access to technical and scientific information from around the world. Some conducted their own experiments to improve the productivity of the land and their stock. There was also a learning process involved in adapting their methods to fit the local rangeland environments. They were not simply rapacious capitalists out to strip the wealth from the land for their own personal gain; indeed, many pastoralists set out to establish viable and sustainable enterprises. The thesis argues that the rangelands consisted of a variety of landscapes and climates. Differences in resource endowments had a considerable influence in shaping the environmental outcomes on different stations. Aridity and rabbits were two key factors in the depletion of the vegetation and the degradation of the landscape in the rangelands. Runs in semi-arid districts that were overwhelmed by rabbits suffered long-term damage. In districts where rainfall was more reliable stations that had been overrun by rabbits recovered remarkably quickly. Stations like Mt Peel, that were largely unaffected by the first rabbit plague, were able to maintain and even increase their productivity up to the time they were subdivided. The orthodox analysis of the transformation of the rangelands in the pastoral era does not account for these differences in outcomes.

The transformation of the rangelands of the South Island of New Zealand during the pastoral era fits into the wider international context of European expansion into the 'new' world. European settlers displaced native peoples, introduced 'old' world animals and plants, and imposed a capitalist system that converted local resources into international commodities. In New Zealand the orthodox explanation of the pastoral impact on the rangelands claims that pastoralists introduced an unsustainable system of land use to the region. The pastoralists� indiscriminate burning practices and overstocking with sheep opened up the country to invasion by rabbits. Burning and overgrazing by sheep and rabbits stripped the natural fertility of the soils and left the country depleted, eroded, and overwhelmed by pests and weeds. This thesis sets out to test those claims. It explores burning, the stocking of the rangelands with sheep and the impact of rabbits in detail. It also examines other land management practices, as well as sheep breeding, to see what impact they had on the landscape. The timeframe is set between 1841, when formal British settlement was established in the South Island, and 1912, by which time most of the great estates and stations had been broken up into smaller runs and farms. The thesis uses station diaries, memoirs, contemporary newspapers and farming journals to assess what happened on the ground during the pastoral era. In particular, the thesis uses Mt Peel Station as a case study to examine the intensification in land use that took place between 1841 and 1912, in order to explain the transformation of the landscape and to answer the questions: what happened, how did it happened and why did it happened as it did? These sources illustrate that the pastoral era was characterised by innovation. Pastoralists had access to technical and scientific information from around the world. Some conducted their own experiments to improve the productivity of the land and their stock. There was also a learning process involved in adapting their methods to fit the local rangeland environments. They were not simply rapacious capitalists out to strip the wealth from the land for their own personal gain; indeed, many pastoralists set out to establish viable and sustainable enterprises. The thesis argues that the rangelands consisted of a variety of landscapes and climates. Differences in resource endowments had a considerable influence in shaping the environmental outcomes on different stations. Aridity and rabbits were two key factors in the depletion of the vegetation and the degradation of the landscape in the rangelands. Runs in semi-arid districts that were overwhelmed by rabbits suffered long-term damage. In districts where rainfall was more reliable stations that had been overrun by rabbits recovered remarkably quickly. Stations like Mt Peel, that were largely unaffected by the first rabbit plague, were able to maintain and even increase their productivity up to the time they were subdivided. The orthodox analysis of the transformation of the rangelands in the pastoral era does not account for these differences in outcomes.

Made available in DSpace on 2017-07-21T20:42:46Z (GMT). No. of bitstreams: 1 Danielle M Ferreira Madeira.pdf: 2830948 bytes, checksum: b0683133449a7aa9574bf79758c203d4 (MD5) Previous issue date: 2013-02-27 / The objective of this work was to study the surface adhesion of polyethylene on the liquid paper board. By using surface characterization, the chemical and physical interactions between the paper board and polyethylene were studied. Paper board samples were laminated with low density polyethylene with an extruder, in order to evaluate the adhesion forces of the following samples: 1) Paper board coating with different latex composition; 2) paper board bottom layer (brown side) with surface sizing (starch) and, 3) paper board bottom layer (brown side) without surface sizing (starch). It was also evaluated in the extruded samples treated with flame the polyethylene adhesion. The following analyses were used in other to characterize the paper board surface: 1) Contact angle analysis for surface energy determination, 2) Confocal laser scanning microscopy for surface roughness analysis and, 3) FTIR spectroscopy Attenuated Total Reflectance (ATR) to evaluate differences in the functional groups. The characterization results were correlated with the increase of polyethylene adhesion forces on the paper board surface. It was observed that flame treatment on the paper board surface increased the surface tension, thus increasing the adhesion forces of the polyethylene. In comparison to the styrene-butadiene latex, the styrene acrylic latex, which contains polar groups in its composition, improved the adhesion forces of the polyethylene with the paper board top layer (white side). For the paper board bottom layer (brown side) with no surface sizing, the polyethylene adhesion was superior when compared to the sized paper board. It can be explained by the increase on the surface smoothness of the paper which may interfere on the polyethylene adhesion. The flame treatment may have caused the oxidation of functional groups on the surface of the paper board, resulting in the surface tension increase and, consequently, increasing the polyethylene adhesion. The surface tension has shown to be an excellent indicator for polyethylene adhesion due to its linear correlation with polyethylene adhesion forces. On the other hand, it has not been observed difference on surface roughness on the studied samples. The FTIR-ATR technique has not been sensitive for the detection of chemical differences among the samples treated with and without flame. However, this technique can be used to verify the latex composition in the paper board coating. The Peel Test Method (180º) which is used to evaluate the adhesion force, presents more reliable results than the manual delamination test that depends on the analyst. / O objetivo deste trabalho foi estudar a adesão de polietileno à superfície do papel cartão utilizado na produção da embalagem Longa Vida. Através de técnicas de caracterização de superfície foram verificadas as interações químicas e físicas existentes entre o papel cartão e o polietileno. Amostras de papel cartão foram laminadas com polietileno de baixa densidade em uma extrusora para avaliar a força de adesão nas seguintes amostras: 1) “coating” do papel cartão com diferentes látex na composição da tinta de revestimento. 2) base do papel cartão (lado marrom) com colagem superficial com amido. 3) base do papel cartão (lado marrom) sem colagem superficial com amido. Nas amostras extrusadas também foi avaliada a adesão de polietileno quando a superfície do papel cartão foi tratada com chama. Análise do ângulo de contato para obtenção da energia superficial, microscopia confocal a laser, para verificar efeitos na rugosidade superficial, e análise de infravermelho (ATR – reflectância total atenuada), para avaliar diferenças dos grupos funcionais, foram também utilizadas para a caracterização da superfície do papel cartão. O resultado da caracterização foi correlacionado com aumento das forças de adesão de polietileno à superfície do papel cartão. Para os casos estudados, observou-se que o tratamento de superfície feito com chama no papel cartão aumentou a energia superficial, elevando assim a força de adesão ao polietileno. O uso de látex estireno-acrílico, que apresenta grupos polares na composição, também propiciou melhor adesão de polietileno na cobertura (lado branco do papel cartão) comparado ao látex estireno-butadieno. Para a base do papel cartão (lado marrom) sem a colagem superficial, a adesão de polietileno se mostrou superior à condição com colagem, pois esta gera maior nivelamento da superfície, deixando a base do papel cartão mais lisa, dificultando assim a adesão de polietileno. Os tratamentos de superfície com chama podem ter causado a oxidação da superfície do papel cartão, gerando assim um aumento de grupos polares na superfície, aumentando a energia superficial da mesma e, consequentemente, melhorado a adesão de polietileno. A energia superficial pode ser vista como um excelente indicativo para adesão de polietileno, pois se verificou uma correlação linear onde quanto maior a energia superficial do papel cartão, maior a força de adesão ao polietileno. Por outro lado, a rugosidade superficial não mostrou diferenças entre as amostras estudadas. A técnica de infravermelho (ATR) não foi sensível para detectar diferenças químicas entre os tratamentos com e sem chama. No entanto, esta técnica pode ser utilizada para verificar a composição, quanto ao tipo de látex, usado na tinta de revestimento do papel cartão. O método Peel Test em 1800, usado para avaliar a força de adesão, apresenta resultados mais confiáveis do que somente a avaliação através da delaminação manual, que depende muito do analista e sua percepção.

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This thesis deals with numerical simulation of a peel test with an Aluminium foil and Low Density Poly-Ethylene (LDPE) laminate. This work investigates the effects of the substrate thickness and studies the influences of interfacial strength and fracture energy of the cohesive zone between the Aluminium and LDPE. This study evaluates the proper guidelines for defining cohesive properties. A numerical cohesive zone model was created in ABAQUS. Continuum tensile tests were performed to extract LDPE material properties. The aluminium properties were found in literature. After acquiring material parameters, the simulation continued with studying the effects of changing interfacial strength, geometric parameters and fracture energy. The results were obtained in the form of root rotations and the force displacement response was studied carefully. It was validated by comparison to the traction separation curve.

O presente trabalho teve como objetivo o aproveitamento do hidrolisado de cascas de mandioca para produção de pigmentos carotenoides. Para isso, foi realizado o isolamento de leveduras provenientes da Região Amazônica, caracterização das cascas de mandioca e obtenção dos hidrolisados por via ácida (HA) e enzimática (HE). Por fim, foram avaliados o efeito da relação C:N e da luminosidade sobre a produção de carotenoides pelas leveduras previamente selecionadas nos hidrolisados. Os extratos carotenogênicos foram caracterizados quanto ao potencial anti-oxidante e antimicrobiano, sendo ainda avaliado o uso da biomassa seca como agente pigmentante em um material polimérico. Foram isoladas sete colônias pigmentadas (4 do solo, 2 de água e 1 de fruto), as quais foram identificadas como pertencentes ao gênero Rhodotorula. Com relação as cascas de mandioca, o principal componente em % m/m foi o amido (71,0), seguido da lignina (13,0), glucana (4,6), xilana (2,4), cinzas (2,6) e extrativos (4,6). Na melhor condição de hidrólise ácida (1% H2SO4, 10% sólidos, 120 min), foi obtido 48 g/L de glicose, o que correspondeu a uma eficiência de 67%. Já para a hidrólise enzimática (3000 U Termamyl 2X, 240 U AMG XXL, 14% sólidos, 65 min) obtevese 80,8 g/L de glicose, correspondendo a uma eficiência de 79,5%. Nas condições de cultivo empregando HA ou HE contendo cerca de 50,0 g/L de glicose sem qualquer suplementação (pH inicial 6,0, temperatura de 30ºC, agitação de 200rpm e na presença de luminosidade) foi possível selecionar a cepa Rh S2 no HA e a Rh RNA no HE, as quais apresentaram, respectivamente (12,7 g/L e 7,6 mg/L) e (22,8 g/L e 11,2 mg/L) de biomassa e carotenoides totais. O maior potencial antioxidante foi obtido com a cepa Rh S2 que apresentou cerca de 30% de redução do radical DPPH sendo que ambos extratos apresentaram ação anti-microbiana frente à Escherichia coli e Aspergillus fumigatus. Quanto as propriedades mecânicas do compósito formulado com a biomassa seca da cepa Rh S2, ficou demonstrada a possibilidade do uso desta biomassa como agente pigmentante em resinas poliméricas. Estes resultados revelam o grande potencial das leveduras selecionadas para a produção de carotenoides a partir de um subproduto da agroindústria, ressaltando ainda suas importantes propriedades biológicas e de pigmentação, as quais poderão ser exploradas em diferentes aplicações. / The present work had as objective the utilization of the hydrolyzate of cassava peels for the production of carotenoid pigments. For this, the yeast from the Amazon region was isolated, characterizing the cassava peels and acid hydrolysates (HA) and enzymatic (HE). Finally, the effect of the C: N ratio and the luminosity on carotenoid production by the selected yeasts in the hydrolysates were evaluated. Carotenogens extracts are characterized as antioxidant and antimicrobial potential, and the use of dry biomass as a pigment agent in a polymeric material is also evaluated. Seven pigmented colonies (4 soil, 2 water and 1 fruit) were isolated, as were the communities as individuals belonging to the genus Rhodotorula. Compared with cassava peels, the main component in% by weight of starch (71.0), followed by lignin (13.0), glucan (4.6), xylan (2.4), ashes (26) and extractives (4.6). The acid hydrolysis condition (1% H2 SO4, 10% solids, 120 min) was 48 g/L glucose, corresponding to an efficiency of 67%. Already for an enzymatic hydration (3000 U Termamyl 2X, 240 U AMG XXL, 14% solids, 65 min), 80.8 g/L of glucose was obtained, corresponding to an efficiency of 79.5%. In the ingestion conditions using HA or HE of about 50.0 g/L of glucose without any supplement (initial pH 6.0, temperature of 30 ° C, agitation of the presence light) it was possible to select the strain Rh S2 in HA and Rh RNA is not HE, as it is today (12.7 g/L and 7.6 mg/L) and (22.8 g/L and 11.2 mg/L) biomass and total carotenoids. The highest antioxidante potential was obtained with the Rh S2 protein which had about 30% reduction of the DPPH radical, with both extracts being moved against the microbiota against Escherichia coli and Aspergillus fumigatus. Regarding the mechanical properties of the compound formulated with a dry biomass of the strain Rh S2, the possibility of the use of this biomass as pigment agent in polymer resins has been demonstrated. This research was useful to increase the potential of selected yeasts for the production of carotenoids from a by-product of agroindustry, highlighting their historical and pigmentation characteristics, such as the ports explored in different applications.