Preparation and characterisation of biodegradable starch-based nanocomposite materials

Different formulations of biodegradable starch-polyester blend nanocomposite materials have been film blown on a pilot scale film blowing tower. The physical properties of different films have been examined by thermal and mechanical analysis and X-ray diffraction. The results show that the addition of an organoclay (from 0 to 5 wt%) significantly improves both the processing and tensile properties over the original starch blends. Wide angle X-ray diffraction (WAXD) results indicate that the best results were obtained for 30wt% starch blends, and the level of delamination depends on the ratio of starch to polyester and amount of organoclay added. The crystallisation temperature of the nanocomposite blends is significantly lower than the base blend. This is probably due to the platelets inhibiting order, and hence crystallisation, of the starch and polyester. The mechanical and thermal properties of the blends are also sensitive to the way the clay particles are dispersed. (C) 2003 Society of Chemical Industry.

Water sorption into poly[(2-hydroxyethyl methacrylate)-co-(1-vinyl-2-pyrrolidone]at 310 K

Poly(2-hydroxyethyl methacrylate) and copolymers of 2-hydroxyethyl methacrylate (HEMA) and 1-vinyl-2-pyrrolidone (VP) in the form of cylindrical samples (approximate to8mm x 20mm) have been prepared and the sorption of water into these cylinders has been studied by the mass-uptake methods and by magnetic-resonance imaging. The equilibrium water contents for the cylinders were found to vary systematically with the copolymer composition. Diffusion of water into the cylinders was found to follow Fickian behaviour for cylinders with high HEMA contents, with the diffusion coefficients obtained from mass-uptake studies dependent on the copolymer composition, varying from 1.7 x 10(-11) m(2) s(-1) for poly(HEMA) to 2.0 x 10(-11) m(2) s(-1) for poly(HEMA-co-VP) with a composition of 1:1. However, NMR-imaging studies showed that, while the profiles of the water diffusion fronts for cylinders with high HEMA contents were Fickian, that for the 1:1 copolymer was not and indicated that the mechanism was Case III. The polymers which were rich in VP were characterized by a water-sorption process which follows Case-III behaviour. (C) 2003 Society of Chemical Industry.

Polyethylene-layered silicate nanocomposites for rotational moulding

A series of polyethylene-layered silicate nanocomposites has been studied as possible new candidates for rotational moulding. Two organically treated layered silicates were melt-compounded into a maleated linear low-density polyethylene host polymer at loadings of 6 and 9%, by weight. The morphology and properties of the nanocomposites were assessed by using dynamic mechanical thermal analysis, parallel-plate rheometry, wide-angle X-ray diffraction and transmission electron microscopy. The sintering behaviour of the nanocomposites was qualitatively assessed via hot-stage microscopy, indicating that the choice of nanofiller will play an important role in terms of producing nanocomposite materials with acceptable processability for rotational moulding. (C) 2003 Society of Chemical Industry.

A technique to assess small-scale heterogeneity of chemical properties in soil aggregates

A new method is presented which allows the separation of the soil aggregate exterior from the aggregate core. The method employs a combination of aggregate freezing with rapid separation of aggregate exteriors using ultrasonic energy. The factors influencing the thickness of the removed aggregate surface layer include water content of the aggregate prior to freezing, temperature difference between that of the frozen aggregate and that of the liquid it is submerged in during sonification, sonification time and energy, and the type of the immersion liquid. The success of the method and the thickness of the removed aggregate surface were examined using barium ( Ba2+) as a tracer. Barium ( as BaCl2) is rapidly absorbed by soil and is present at only very low levels in natural soils. Surface layers of 0.2 - 0.4 cm thickness were successfully removed from aggregates of 1 - 4 cm diameter. Two examples are given from soils in northern NSW to demonstrate the occurrence of small- scale heterogeneity in soil chemical properties. Compared with the surface fraction, a 4 - 7% higher calcium concentration was found in the core fraction of a clay loam soil ( Dermosol). Conversely, on a cracking clay soil ( Vertosol), atrazine concentration was around 15 times greater in the aggregate surface fractions compared with core fractions. Compared with the traditional estimation of soil chemical properties on homogenised bulk soil samples, it is suggested that separate analysis of aggregate surface and core fractions could provide useful additional information on the relationships between soil properties and environmental responses.

Variation of the crystalline structure of coal char during gasification

The variation of the crystallite structure of several coal chars during gasification in air and carbon dioxide was studied by high-resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) techniques. The XRD analysis of the partially gasified coal chars, based on two approaches, Scherrer's equation and Alexander and Sommer's method, shows a contradictory trend of the variation of the crystallite height with carbon conversion, despite giving a similar trend for the crystallite width change. The HRTEM fringe images of the partially gasified coal chars indicate that large and highly ordered crystallites exist at conversion levels as high as 86%. It is also demonstrated that the crystalline structure of chars can be very different although their pore structures are similar, suggesting a combination of crystalline structure analysis with pore structure analysis in studies of carbon gasification.

An investigation of the thermal and tensile properties of PFA following γ-radiolysis

For some applications for fluoropolymers they must be subjected to high-energy radiation, e.g., when they are grafted with styrene using an irradiation method to produce fuel cell membranes or matrix supports for combinatorial chemistry. In some of these applications they may be subjected to mechanical stress or elevated temperature, so it is important to elucidate the effects of the radiolysis on these properties. In the present work the effect of gamma-radiolysis on the glass transition, melting behavior, and thermal stability of PFA has been studied as well as the effect of the radiolysis on the tensile properties of the polymer.

Variation of the pore structure of coal chars during gasification

The variation of the pore structure of several coal chars during gasification in air and carbon dioxide was studied by argon adsorption at 87 K and CO2 adsorption at 273 K. It is found that the surface area and volume of the small pores (10 Å for air gasification is constant over a wide range of conversion (>20%), while for CO2 gasification similar results are obtained using the total surface area. However, in the early stages of gasification (

Variação radial da retratibilidade e densidade básica da madeira de Eucalyptus saligna Sm.

A ultra-estrutura e a composição química da madeira, bem como suas propriedades físicas e mecânicas, variam significativamente entre espécies, entre árvores de uma mesma espécie e, mesmo, entre diferentes partes de uma mesma árvore. Com este trabalho objetivou-se o estudo dos parâmetros de retratibilidade e de densidade básica da madeira Eucalyptus saligna, com idade de 16 anos, proveniente de talhões experimentais da EMBRAPA Florestas, de Colombo, Paraná. As amostras foram retiradas à altura do DAP de quatro posições eqüidistantes a partir da medula em direção à periferia, correspondendo a 0, 33, 66 e 100%, com dimensões nominais de 1,0 x 2,0 x 3,0 cm, sendo a última dimensão no sentido longitudinal. Elas foram mantidas em câmara fechada com ventilação, próximo de soluções salinas supersaturadas, com o objetivo de proporcionar diferentes condições de umidade relativa. Uma vez atingidas as distintas condições de umidade de equilíbrio, as amostras foram secas em estufa a 105 ºC e obtidos os dados de retratibilidade e densidade básica da madeira nas posições mencionadas. Constataram-se valores de contração volumétrica mais baixos na região medular, apresentando um acréscimo para as demais posições. Comportamento semelhante foi observado para os coeficientes das contrações lineares nas direções tangencial e radial. O fator anisotrópico foi consideravelmente mais elevado na região medular, decrescendo substancialmente em direção ao alburno. A densidade básica não mostrou sinais efetivos de estabilidade, apesar de mostrar tendência de aumento em direção à periferia do tronco.

Uma avaliação das metodologias de desagregação da exergia física para a modelagem termoeconômica de sistemas

Talvez não seja nenhum exagero afirmar que há quase um consenso entre os praticantes da Termoeconomia de que a exergia, ao invés de só entalpia, seja a magnitude Termodinâmica mais adequada para ser combinada com o conceito de custo na modelagem termoeconômica, pois esta leva em conta aspectos da Segunda Lei da Termodinâmica e permite identificar as irreversibilidades. Porém, muitas vezes durante a modelagem termoeconômica se usa a exergia desagregada em suas parcelas (química, térmica e mecânica), ou ainda, se inclui a neguentropia que é um fluxo fictício, permitindo assim a desagregação do sistema em seus componentes (ou subsistemas) visando melhorar e detalhar a modelagem para a otimização local, diagnóstico e alocação dos resíduos e equipamentos dissipativos. Alguns autores também afirmam que a desagregação da exergia física em suas parcelas (térmica e mecânica) permite aumentar a precisão dos resultados na alocação de custos, apesar de fazer aumentar a complexidade do modelo termoeconômico e consequentemente os custos computacionais envolvidos. Recentemente alguns autores apontaram restrições e possíveis inconsistências do uso da neguentropia e deste tipo de desagregação da exergia física, propondo assim alternativas para o tratamento de resíduos e equipamentos dissipativos que permitem a desagregação dos sistemas em seus componentes. Estas alternativas consistem, basicamente, de novas propostas de desagregação da exergia física na modelagem termoeconômica. Sendo assim, este trabalho tem como objetivo avaliar as diferentes metodologias de desagregação da exergia física para a modelagem termoeconômica, tendo em conta alguns aspectos como vantagens, restrições, inconsistências, melhoria na precisão dos resultados, aumento da complexidade e do esforço computacional e o tratamento dos resíduos e equipamentos dissipativos para a total desagregação do sistema térmico. Para isso, as diferentes metodologias e níveis de desagregação da exergia física são aplicados na alocação de custos para os produtos finais (potência líquida e calor útil) em diferentes plantas de cogeração considerando como fluido de trabalho tanto o gás ideal bem como o fluido real. Plantas essas com equipamentos dissipativos (condensador ou válvula) ou resíduos (gases de exaustão da caldeira de recuperação). Porém, foi necessário que uma das plantas de cogeração não incorporasse equipamentos dissipativos e nem caldeira de recuperação com o intuito de avaliar isoladamente o efeito da desagregação da exergia física na melhoria da precisão dos resultados da alocação de custos para os produtos finais.

Mechanical, electrical and electro-mechanical properties of thermoplastic elastomer styrene–butadiene–styrene/multiwal carbon nanotubes composites

Composites of styrene–butadiene–styrene (SBS) block copolymer with multiwall carbon nanotubes were processed by solution casting to investigate the influence of filler content, the different ratios of styrene/butadiene in the copolymer and the architecture of the SBS matrix on the electrical, mechanical and electro-mechanical properties of the composites. It was found that filler content and elastomer matrix architecture influence the percolation threshold and consequently the overall composite electrical conductivity. Themechanical properties aremainly affected by the styrene and filler content. Hopping between nearest fillers is proposed as the main mechanism for the composite conduction. The variation of the electrical resistivity is linear with the deformation. This fact, together with the gauge factor values in the range of 2–18, results in appropriate composites to be used as (large) deformation sensors.

Mechanical, electrical and electro-mechanical properties of thermoplastic elastomer styrene–butadiene–styrene/multiwall carbon nanotubes composites

Composites of styrene–butadiene–styrene (SBS) block copolymer with multiwall carbon nanotubes were processed by solution casting to investigate the influence of filler content, the different ratios of styrene/butadiene in the copolymer and the architecture of the SBS matrix on the electrical, mechanical and electro-mechanical properties of the composites. It was found that filler content and elastomer matrix architecture influence the percolation threshold and consequently the overall composite electrical conductivity. The mechanical properties are mainly affected by the styrene and filler content. Hopping between nearest fillers is proposed as the main mechanism for the composite conduction. The variation of the electrical resistivity is linear with the deformation. This fact, together with the gauge factor values in the range of 2–18, results in appropriate composites to be used as (large) deformation sensors.

Thermomechanical environment characterisation in injection moulding and its relation to the mechanical properties of talc-filled polypropylene

This study is focused on the establishment of relationships between the injection moulding processing conditions, the applied thermomechanical environment (TME) and the tensile properties of talc-filled polypropylene,adopting a new extended concept of thermomechanical indices (TMI). In this approach, TMI are calculated from computational simulations of the moulding process that characterise the TME during processing, which are then related to the mechanical properties of the mouldings. In this study, this concept is extended to both the filling and the packing phases, with new TMI defined related to the morphology developed during these phases. A design of experiments approach based on Taguchi orthogonal arrays was adopted to vary the injection moulding parameters (injection flow rate, injection temperature, mould wall temperature and holding pressure), and thus, the TME. Results from analysis of variance for injection-moulded tensile specimens have shown that among the considered processing conditions, the flow rate is the most significant parameter for the Young’s modulus; the flow rate and melt temperature are the most significant for the strain at break; and the holding pressure and flow rate are the most significant for the stress at yield. The yield stress and Young’s modulus were found to be governed mostly by the thermostress index (TSI, related to the orientation of the skin layer), whilst the strain at break depends on both the TSI and the cooling index (CI, associated to the crystallinity degree of the core region). The proposed TMI approach provides predictive capabilities of the mechanical response of injection-moulded components, which is a valuable input during their design stage.

Effect of the Impact Conditions on the Mechanical Properties of Injection-Molded Parts

This work focused on the study of the impact event on molded parts in the framework of automotive components. The influence of the impact conditions and processing parameters on the mechanical behavior of talc-filled polypropylene specimens was analyzed. The specimens were lateral-gate discs produced by injection molding, and the mechanical characterization was performed through instrumented falling weight impact tests concomitantly assisted with high-speed videography. Results analyzed using the analysis of variance (ANOVA) method have shown that from the considered parameters, only the dart diameter and test temperature have significant influence on the falling weight impact properties. Higher dart diameter leads to higher peak force and peak energy results. Conversely, higher levels of test temperatures lead to lower values of peak force and peak energy. By means of high-speed videography, a more brittle fracture was observed for experiments with higher levels of test velocity and dart diameter and lower levels of test temperature. The injection-molding process conditions assessed in this study have an influence on the impact response of moldings, mainly on the deformation capabilities of the moldings.

Multi-scale modeling of the mechanical behavior of polymer-based materials

Polymers have become the reference material for high reliability and performance applications. In this work, a multi-scale approach is proposed to investigate the mechanical properties of polymeric based material under strain. To achieve a better understanding of phenomena occurring at the smaller scales, a coupling of a Finite Element Method (FEM) and Molecular Dynamics (MD) modeling in an iterative procedure was employed, enabling the prediction of the macroscopic constitutive response. As the mechanical response can be related to the local microstructure, which in turn depends on the nano-scale structure, the previous described multi-scale method computes the stress-strain relationship at every analysis point of the macro-structure by detailed modeling of the underlying micro- and meso-scale deformation phenomena. The proposed multi-scale approach can enable prediction of properties at the macroscale while taking into consideration phenomena that occur at the mesoscale, thus offering an increased potential accuracy compared to traditional methods.