Preparação, caracterização e avaliação de nanocompósitos de PBAT/amido de milho e vermiculita organofilizada

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

Corrosão de aços inoxidáveis empregando mapas de impedância

Os aços inoxidáveis correspondem a aços com diferenças de composição e microestrutura. Desta forma, o comportamento em corrosão é consequentemente diferente. Para avaliar este aspecto, aços com PREN variando de aproximadamente 11 a 35% foram analisados por curvas de polarização. A motivação principal desse trabalho foi avaliar o comportamento de cada aço inoxidável com uso de diferentes técnicas (impedância eletroquímica e circuitos elétricos equivalentes) e também na nova técnica de mapas de impedância, da influência do PREN na corrosão em meio de 3,5% NaCl a 25C. A partir dessas curvas, os potenciais de pites e de densidade de corrente de corrosão foram obtidos. Além disto, foram empregados mapas de diagrama de impedância eletroquímica para visualizar o efeito do potencial aplicado, desde o potencial catódico até além do potencial de pite desses aços. Pôde-se observar que o módulo de impedância se reduz abruptamente quando surge o pite. Ademais, há uma alteração do ângulo característico para frequências da ordem de 1 kHz. Para dois aços inoxidáveis, UNS S30400 e UNS S31600, foram utilizados os diagramas de impedância obtidos dos mapas e estimados a evolução dos parâmetros relacionados a um circuito elétrico equivalente para potenciais aplicados.

Caracterização mecânica e tribológica de dois glazeadores disponíveis comercialmente e uma composição experimental

O objetivo desse estudo, in vitro, foi avaliar através de testes mecânicos e tribológicos, a aplicação de dois glazeadores disponíveis comercialmente e uma composição experimental como material de cobertura em restaurações de resina composta com relação à rugosidade superficial, à dureza e à resistência ao desgaste. Foram confeccionados 24 corpos de prova (CP) do compósito Z350XT (3M/ESPE) e divididos em 4 grupos. O grupo controle (GC) não recebeu selamento, o grupo Biscover LV (GB) recebeu aplicação do Biscover LV (Bisco), o grupo Natural Glaze (GN) recebeu aplicação do Natural Glaze (Nova DFL) e o grupo Experimental (GE) recebeu aplicação de um glazeador experimental contendo nanopartículas (1% em peso). Posteriormente, os CP foram submetidos à análise da rugosidade superficial utilizando um perfilômetro e avaliação da dureza através de um nanoindentador, que fornece também o módulo elástico do material. Em seguida, os CP foram submetidos ao teste de desgaste linear alternado, durante 15.000 ciclos, com carga de 5N, em água destilada. A profundidade máxima de desgaste foi avaliada através de um perfilômetro. A análise dos dados relativos à rugosidade superficial (m) foi realizada utilizando ANOVA/Duncan (p-valor = 0,000). As médias e desvio padrão foram: GC-0,12(0,01); GB-0,06(0,01); GN-0,13(0,02); GE-0,13(0,01). A análise da dureza (GPa) e módulo elástico (GPa) foram avaliados aplicando o teste não-paramétrico de Kruskal-Wallis. As médias e desvio padrão para dureza foram: GC-1,10(0,24); GB-0,31(0,004); GN-0,08(0,004); GE-0,12(0,008) para carga de 1,25mN; GC-1,08(0,139); GB-0,32(0,004); GN-0,08(0,003); GE-0,13(0,006) para carga de 2,5mN; GC-1,10(0,101); GB-0,33(0,003); GN-0,09(0,002); GE-0,13(0,056) para carga de 5,0mN. As médias e desvio padrão para módulo elástico foram: GC-17,71(1,666); GB-5,44(0,084); GN-3,484(0,114); GE-4,55(0,178) para carga de 1,25mN; GC-17,5(1,449); GB-5,18(0,065); GN-3,38(0,078); GE-4,55(0,12) para carga de 2,5mN; GC-17,69(1,793); GB-5,04(0,041); GN-3,63(0,066); GE-4,85(0,104) para carga de 5,0mN. A análise dos dados relativos à profundidade de desgaste (m) foi realizada utilizando ANOVA/Dunnett (p-valor = 0,000). As médias e desvio padrão foram: GC-12,51(0,89); GB-0,59(0,07); GN-1,41(0,12); GE-1,84(0,18). A partir dos resultados apresentados pode-se concluir que apenas o Biscover LV foi capaz de reduzir a rugosidade superficial da resina composta testada. Os demais, Natural Glaze e Experimental, não alteraram a rugosidade superficial e foram estatisticamente semelhantes entre si e com o grupo controle. Todos os glazeadores testados reduziram a dureza e o módulo elástico da resina composta quando comparados com o grupo controle, diferindo entre si, apresentando uma ordem crescente de dureza e módulo elástico (Natural Glaze < Experimental < Biscover < Controle). Todos os glazeadores testados foram capazes de reduzir o desgaste da resina composta, quando comparados com o grupo controle, diferindo entre si, apresentado uma ordem crescente de desgaste (Biscover < Natural Glaze < Experimental < Controle).

A model for the erosive wear of rubber at oblique impact angles

A model has been developed to predict the erosive wear behaviour of elastomers under conditions of glancing impact by small hard particles. Previous work has shown the erosive wear mechanism of elastomers under these conditions to be similar in nature to that of abrasive wear by a sharp blade. The model presented here was developed from the model of Southern and Thomas for sliding abrasion, by combining their treatment of the growth of surface cracks with a model for particle impact in which the force - displacement relationship for an idealized flat-ended punch on a semi-infinite elastic solid was assumed. In this way an expression for the erosive wear rate was developed, and compared with experimental measurements of wear rate for natural rubber, styrene - butadiene rubber and a highly crosslinked polybutadiene rubber. Good qualitative agreement was found between the predictions of the model and the experimental measurements. The variation of erosion rate with impact velocity, impact angle, particle size, elastic modulus of the material, coefficient of friction and fatigue properties were all well accounted for. Quantitative agreement was less good, and the effects of erosive particle shape could not be accounted for. The reasons for these discrepancies are discussed. © 1992 IOP Publishing Ltd.

The use of timber in wind turbines.

The advantages of timber in wind turbine blade construction are discussed, and its properties emphasized. The use of timber/epoxy construction enables a high technical specification to be achieved. Tables are given for specific compressive strengths, fatigue strengths and flexural modulus for wind epoxy and glass reinforced polyester composites. Cost ratios are also discussed for the two materials and the cost advantage for wood is emphasized. (A.J.)

Measurement of the Mechanical Properties of Filtercakes

In order to improve drilling mud design to cater for specific well situations, a more comprehensive knowledge and understanding of filter cake failure is needed. This paper describes experimental techniques aimed at directly probing the mechanical properties of filter cakes, without having to take into account artefacts due to fluid flow in the substrate. The use of rheometers allows us to determine shear yield stress and dynamic shear modulii of cakes grown on filter paper. A new scraping technique measures the strength and moisture profiles of typical filter cakes with a 0.1 mm resolution. This technique also allows us to probe the adhesion between the filter cake and its rock substrate. In addition, œdometer drained consolidation and unloading of a filter cake give us compression parameters useful for Cam Clay modelling. These independent measurements give similar results as to the elastic modulus of different filter cakes, showing an order of magnitude difference between water based and oil based cakes. We find that these standard cakes behave predominantly as purely elastic materials, with a sharp transition into plastic flow, allowing for the determination of a well-defined yield stress. The effect ofsolids loading on a given type of mud is also studied.

Variability of nanoindentation responses of bone and artificial bone-like composites

Nanoindentation is a popular technique for measuring the intrinsic mechanical response of bone and has been used to measure a single-valued elastic modulus. However, bone is a composite material with 20-80 nm hydroxyapatite plates embedded in a collagen matrix, and modern instrumentation allows for measurements at these small length scales. The present study examines the indentation response of bone and artificial gelatin-apatite nanocomposite materials across three orders of magnitude of lengthscale, from nanometers to micrometers, to isolate the composite phase contributions to the overall response. The load-displacement responses were variable and deviated from the quadratic response of homogeneous materials at small depths. The distribution of apparent elastic modulus values narrowed substantially with increasing indentation load. Indentation of particulate nanocomposites was simulated using finite element analysis. Modeling results replicated the convergence in effective modulus seen in the experiments. It appears that the apatite particles are acting as the continuous ("matrix") phase in bone and nanocomposites. Copyright © 2004 by ASME.

Laser micromachining of sputtered DLC films

DLC films with different thicknesses (from 100 nm to 1.9 μm) were deposited using sputtering of graphite target in pure argon atmosphere without substrate heating. Film microstructures (sp2/sp3 ratio) and mechanical properties (modulus, hardness, stress) were characterized as a function of film thickness. A thin layer of aluminum about 60 nm was deposited on the DLC film surface. Laser micromachining of Al/DLC layer was performed to form microcantilever structures, which were released using a reactive ion etching system with SF6 plasma. Due to the intrinsic stress in DLC films and bimorph Al/DLC structure, the microcantilevers bent up with different curvatures. For DLC film of 100 nm thick, the cantilever even formed microtubes. The relationship between the bimorph beam bending and DLC film properties (such as stress, modulus, etc.) were discussed in details. © 2005 Elsevier B.V. All rights reserved.

SU8 bio-chemical sensor microarrays

Microfabricated cantilevers have recently attracted considerable attention as novel label-free chemical and biological biosensors which translate surface reactions into nanomechanical bending motion. However these studies have primarily focused on commercially available silicon cantilevers and relatively little work has been performed on cantilevers fabricated from other materials. Polymeric materials, offer significant advantages over silicon by virtue of the low Young's modulus, ease of microfabrication and reduced cost. In this paper, we report a non-vacuum fabrication process to produce arrays of SU8 cantilevers and demonstrate their application as chemical sensors using in situ reference cantilevers. © 2006 Elsevier B.V. All rights reserved.

Mineralization and nanomechanical properties in Articular Calcified Cartilage (ACC)

The contribution of the relative volumes of mineral and collagen to the nanomechanical behavior of articular calcified cartilage is explored using nanoindentation, quantitative backscattered electron imaging, and finite element analysis. Elastic modulus generally increases with mineral volume fraction. In highly mineralized tissues, the mineral occupation of water space significantly increases modulus with addition of little mineral. Mineral and organic phases were modeled using Hashin-Shtrikman composite bounds, calculated as a function of mineral volume fraction. Modulus values fall between the Hashin-Shtrikman bounds, indicating some intermediate degree of mineral phase connectivity. Such connectivity in ACC is greater than that achieved in bone and results from uniform collagen orientation and large volume of water space available for mineral occupation.

Viscoelastic properties of bone as a function of hydration state determined by nanoindentation

Spherical indentation creep testing was used to examine the effect of hydration state on bone mechanical properties. Analysis of creep data was based on the elastic-viscoelastic correspondence principle and utilized a direct solution for the finite loading-rate experimental conditions. The zero-time shear modulus was computed from the creep compliance function and compared to the indentation modulus obtained via conventional indentation analysis, based on an elastic unloading response. The method was validated using a well-known polymer material under three different loading conditions. The method was applied to bone samples prepared with different water content by partial exchange with ethanol, where 70% ethanol was considered as the baseline condition. A hydration increase was associated with a 43% decrease in stiffness, while a hydration decrease resulted in a 20% increase in bone tissue stiffness.

Nanoindentation measurements of bone viscoelasticity as a function of hydration state

Bone is an anisotropic material, and its mechanical properties are determined by its microstructure as well as its composition. Mechanical properties of bone are a consequence of the proportions of, and the interactions between, mineral, collagen and water. Water plays an important role in maintaining the mechanical integrity of the composite, but the manner in which water interacts within the ultrastructure is unclear. Dentine being an isotropic two-dimensional structure presents a homogenous composite to examine the dehydration effects. Nanoindentation methods for determining the viscoelastic properties have recently been developed and are a subject of great interest. Here, one method based on elastic-viscoelastic correspondence for 'ramp and hold' creep testing (Oyen, J. Mater. Res., 2005) has been used to analyze viscoelastic behavior of polymeric and biological materials. The method of 'ramp and hold' allows the shear modulus at time zero to be determined from fitting of the displacement during the maximum load hold. Changes in the viscoelastic properties of bone and dentine were examined as the material was systematically dehydrated in a series of water:solvent mixes. Samples of equine dentine were sectioned and cryo-polished. Shear modulus was obtained by nanoindentation using spherical indenters with a maximum load hold of 120s. Samples were tested in different solvent concentrations sequentially, 70% ethanol to 50% ethanol, 70 % ethanol to 100% ethanol, 70% ethanol to 70% methanol to 100% methanol, and 70% ethanol to 100% acetone, after storage in each condition for 24h. By selectively removing and then replacing water from the composite, insights in to the ultrastructure of the tissue can be gained from the corresponding changes in the experimentally determined moduli, as well as an understanding of the complete reversibility of the dehydration process. © 2006 Materials Research Society.

Fabrication and mechanical property of carbon nanotube/metal composites

Carbon nanotubes (CNTs) are known to exhibit extraordinary mechanical properties such as high tensile strength, the highest Young modulus etc. These, combining with their large aspect ratio, make CNTs an excellent additive candidate to complement or substitute traditional carbon black or glass fiber fillers for the development of nano-reinforced composites. CNTs have thus far been used as additives in polymers, ceramics and metals to be pursued on practical applications of their composites. © 2010 IEEE.

Development of a universal stress sensor for graphene and carbon fibres

Carbon fibres are a significant volume fraction of modern structural airframes. Embedded into polymer matrices, they provide significant strength and stiffness gains by unit weight compared with competing structural materials. Here we use the Raman G peak to assess the response of carbon fibres to the application of strain, with reference to the response of graphene itself. Our data highlight the predominance of the in-plane graphene properties in all graphitic structures examined. A universal master plot relating the G peak strain sensitivity to tensile modulus of all types of carbon fibres, as well as graphene, is presented. We derive a universal value of - average - phonon shift rate with axial stress of around -5ω0 -1 (cm -1 Mpa-1), where ω0 is the G peak position at zero stress for both graphene and carbon fibre with annular morphology. The use of this for stress measurements in a variety of applications is discussed. © 2011 Macmillan Publishers Limited. All rights reserved.

Load-displacement behavior during sharp indentation of viscous-elastic-plastic materials

A constitutive equation is developed for geometrically-similar sharp indentation of a material capable of elastic, viscous, and plastic deformation. The equation is based on a series of elements consisting of a quadratic (reversible) spring, a quadratic (time-dependent, reversible) dashpot, and a quadratic (time-independent, irreversible) slider-essentially modifying a model for an elastic-perfectly plastic material by incorporating a creeping component. Load-displacement solutions to the constitutive equation are obtained for load-controlled indentation during constant loading-rate testing. A characteristic of the responses is the appearance of a forward-displacing "nose" during unloading of load-controlled systems (e.g., magnetic-coil-driven "nanoindentation" systems). Even in the absence of this nose, and the associated initial negative unloading tangent, load-displacement traces (and hence inferred modulus and hardness values) are significantly perturbed on the addition of the viscous component. The viscous-elastic-plastic (VEP) model shows promise for obtaining material properties (elastic modulus, hardness, time-dependence) of time-dependent materials during indentation experiments.