Desenvolvimento e caracterização de compósitos poli(tereftalato de etileno) reciclado (PET reciclado) com flocos de vidro.

The growing concern with the solid residues management, observed in the last decade, due to its huge amount and impact, has motivated the search for recycling processes, where these residues can be reprocessed to generate new products, enlarging the cycle of materials and energy which are present. Among the polymeric residues, there is poly (ethylene terephthalate) (PET). PET is used in food packaging, preferably in the bottling of carbonated beverages. The reintegration of post-consumer PET in half can be considered a productive action mitigation of environmental impacts caused by these wastes and it is done through the preparation of several different products at the origin, i.e. food packaging, with recycling rates increasing to each year. This work focused on the development and characterization mechanical, thermal, thermo-mechanical, dynamic mechanical thermal and morphology of the pure recycled PET and recycled PET composites with glass flakes in the weight fraction of 5%, 10% and 20% processed in a single screw extruder, using the following analytical techniques: thermogravimetry (TG), differential scanning calorimetry (DSC), tensile, Izod impact, Rockwell hardness, Vicat softening temperature, melt flow rate, burn rate, dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM). The results of thermal analysis and mechanical properties leading to a positive evaluation, because in the thermograms the addition of glass flakes showed increasing behavior in the initial temperatures of thermal decomposition and melting crystalline, Furthermore was observed growing behavior in the mechanical performance of polymer composites, whose morphological structure was observed by SEM, verifying a good distribution of glass flakes, showing difference orientation in the center and in the surface layer of test body of composites with 10 and 20% of glass flakes. The results of DMTA Tg values of the composites obtained from the peak of tan ä showed little reductions due to poor interfacial adhesion between PET and recycled glass flakes.

Evaluation of recycled carbon fibers as PLA reinforcement for additive manufacturing applications

The increased exploitation of carbon fiber reinforced polymers (CFRP) is inevitably bringing about an increase in production scraps and end-of-life components, resulting in a sharp increase in CFRP waste. Therefore, it is of paramount importance to find efficient ways to reintroduce waste into the manufacturing cycle. At present, several recycling methods for treating CFRPs are available, even if all of them still have to be optimized. The step after CFRP recycling, and also the key to build a solid and sustainable CFRP recycling market, is represented by the utilization of Re-CFs. The smartest way to utilize recovered carbon fibers is through the manufacturing of recycled CFRPs, that can be done by re-impregnating the recovered fibers with a new polymeric matrix. Fused Filament Fabrication (FFF) is one of the most widely used additive manufacturing (3D printing) techniques that fabricates parts with a polymeric filament deposition process that allows to produce parts adding material layer-by-layer, only where it is needed, saving energy, raw material cost, and waste. The filament can also contain fillers or reinforcements such as recycled short carbon fibers and this makes it perfectly compliant with the re-application of the shortened recycled CF. Therefore, in this thesis work recycled and virgin carbon fiber reinforced PLA filaments have been initially produced using 5% and 10% of CFs load. Properties and characteristics of the filaments have been determined conducting different analysis (TGA, DMA, DSC). Subsequently the 5%wt. Re-CFs filament has been used to 3D print specimens for mechanical characterization (DMA, tensile test and CTE), in order to evaluate properties of printed PLA composites containing Re-CFs and evaluate the feasibility of Re-CFs in 3D printing application.

Synthesis of Na-PSS geopolymers and analysis of the H2O/Na2O molar ratio influence over their mechanical properties

Geopolymers are solid aluminosilicate material made by mixing an activating solution and a solid precursor. This work studied the mechanisms of synthesis of metakaolin-based geopolymers and the influence of water content, described by the molar ratio H2O/Na2O, on the final product. The samples were tested using a Uniaxial Compressive Test (UCT) to define their compressive resistance. Two geopolymers series were synthetized and let them rest for 7- days and 28-days, each of them composed by six different sets. 7-day rest series showed that water addition had no relevant effect over its resistance while the 28-day rest series almost doubled the compressive resistance, although those with the highest H2O/Na2O molar ratio showed instead a drastic reduction. Two other series were synthesized by adding silt aggregate, a waste material obtained in the production of aggregate for concrete, corresponding to 10wt% and 20wt%of the metakaolin used. After 28 days of aging, these samples were tested via UCT to measure the variation of the compressive resistance after the silt addition. The aggregate has disruptive effects over the compressive resistance, but the 20wt% samples achieved a higher compressive resistance. Samples with highest and lowest compressive resistance have been chosen to carry out an XRD analysis. In all the samples it has been recognized the presence of Anatase (TiO2), a titanium oxide found in the metakaolin and Thermonatrite, a hydrated sodium carbonate [Na2CO3 • (H2O)]. Scanning Electron Microscopy was carried out on the samples with the highest compressive resistance and showed that the samples with lower water content developed a homogeneous geopolymeric texture, while those with higher water content showed instead a spongy-like texture and a higher air or pore solution bubbles presence. Silt/geopolymer composites showed a fracture system developing across the interstitial transition zone between the geopolymer matrix and the aggregate particle.

Influence of Granulometry and Organic Treatment of a Brazilian Montmorillonite on the Properties of Poly(styrene-co-n-butyl acrylate)/Layered Silicate Nanocomposites Prepared by Miniemulsion Polymerization

The influence of granulometry and organic treatment of a Brazilian montmorillonite (MMT) clay on the synthesis and properties of poly(styrene-co-n-butyl acrylate)/layered silicate nanocomposites was studied. Hybrid latexes of poly(styrene-co-butyl acrylate)/MMT were synthesized via miniemulsion polymerization using either sodium or organically modified MMT. Five clay granulometries ranging from clay particles smaller than 75 mu m to colloidal size were selected. The size of the clay particles was evaluated by Specific surface area measurements (BET). Cetyl trimethyl ammonium chloride was used as an organic modifier to enhance the clay compatibility with the monomer phase before polymerization and to improve the clav distribution and dispersion within the polymeric matrix after polymerization. The sodium and organically modified natural clays as well as the composites were characterized by X-ray diffraction analysis. The latexes were characterized by dynamic light scattering. The mechanical, thermal, and rheological properties of the composites obtained were characterized by dynamical-mechanical analysis, thermogravimetry, and small amplitude oscillatory, shear tests, respectively. The results showed that smaller the size of the organically modified MMT, the higher the degree of exfoliation of nanoplatelets. Hybrid latexes in presence of Na-MMT resulted in materials with intercalated structures. (C) 2009 Wiley, Periodicals, Inc. J Appl Polym Sci 112: 1949-1958, 2009

Thermoplastic starch modified during melt processing with organic acids: The effect of molar mass on thermal and mechanical properties

Thermoplastic starch (TPS) was modified with ascorbic acid and citric acid by melt processing of native starch with glycerol as plasticizer in an intensive batch mixer at 160 degrees C. It was found that the molar mass decreases with acid content and processing time causing the reduction in melting temperature (T(m)). As observed by the results of X-ray diffraction and DSC measurements, crystallinity was not changed by the reaction with organic acids. T(m) depression with falling molar mass was interpreted on the basis of the effect of concentration of end-chain units, which act as diluents. FTIR did not show any appreciable change in starch chemical compositions, leading to the conclusion that the main changes observed were produced by the variation in molar mass of the material. We demonstrated that it is possible to decrease melt viscosity without the need for more plasticizer thus avoiding side-effects such as an increase in water affinity or relevant changes in the dynamic mechanical properties. (C) 2010 Elsevier B.V. All rights reserved.

Finite element analysis of concrete cracking at early age

The study of the early age concrete properties is becoming more important, as the thermal effects and the shrinkage, even in the first hours, could generate cracks, increasing the permeability of the structure and being able to induce problems of durability and functionality in the same ones. The detailed study of the stresses development during the construction process can be decisive to keep low the cracking levels. In this work a computational model, based on the finite element method, was implemented to simulate the early age concrete behavior and, specially, the evaluation of the cracking risk. The finite element analysis encloses the computational modeling of the following phenomena: chemical, thermal, moisture diffusion and mechanical which occur at the first days after the concrete cast. The developed software results were compared with experimental values found in the literature, demonstrating an excellent approach for all the implemented analysis.

Quantum phase-space analysis of the pendular cavity

We perform a quantum-mechanical analysis of the pendular cavity, using the positive-P representation, showing that the quantum state of the moving mirror, a macroscopic object, has noticeable effects on the dynamics. This system has previously been proposed as a candidate for the quantum-limited measurement of small displacements of the mirror due to radiation pressure, for the production of states with entanglement between the mirror and the field, and even for superposition states of the mirror. However, when we treat the oscillating mirror quantum mechanically, we find that it always oscillates, has no stationary steady state, and exhibits uncertainties in position and momentum which are typically larger than the mean values. This means that previous linearized fluctuation analyses which have been used to predict these highly quantum states are of limited use. We find that the achievable accuracy in measurement is fat, worse than the standard quantum limit due to thermal noise, which, for typical experimental parameters, is overwhelming even at 2 mK

Dynamic stability of laminated FGM plates based on higher-order shear deformation theory

This paper conducts a dynamic stability analysis of symmetrically laminated FGM rectangular plates with general out-of-plane supporting conditions, subjected to a uniaxial periodic in-plane load and undergoing uniform temperature change. Theoretical formulations are based on Reddy's third-order shear deformation plate theory, and account for the temperature dependence of material properties. A semi-analytical Galerkin-differential quadrature approach is employed to convert the governing equations into a linear system of Mathieu-Hill equations from which the boundary points on the unstable regions are determined by Bolotin's method. Free vibration and bifurcation buckling are also discussed as subset problems. Numerical results are presented in both dimensionless tabular and graphical forms for laminated plates with FGM layers made of silicon nitride and stainless steel. The influences of various parameters such as material composition, layer thickness ratio, temperature change, static load level, boundary constraints on the dynamic stability, buckling and vibration frequencies are examined in detail through parametric studies.

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.

Análise do comportamento dinâmico de uma plataforma sísmica e de um pórtico em betão armado e a sua evolução com o dano acumulado

Trabalho de Dissertação de Natureza Científica para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização em Estruturas

Desenvolvimento de programa em linguagem Matlab® para cálculo pelo método de elementos finitos

Para o projeto de qualquer estrutura existente (edifícios, pontes, veículos, máquinas, etc.) é necessário conhecer as condições de carga, geometria e comportamento de todas as suas partes, assim como respeitar as normativas em vigor nos países nos quais a estrutura será aplicada. A primeira parte de qualquer projeto nesta área passa pela fase da análise estrutural, onde são calculadas todas as interações e efeitos de cargas sobre as estruturas físicas e os seus componentes de maneira a verificar a aptidão da estrutura para o seu uso. Inicialmente parte-se de uma estrutura de geometria simplificada, pondo de parte os elementos físicos irrelevantes (elementos de fixação, revestimentos, etc.) de maneira a simplificar o cálculo de estruturas complexas e, em função dos resultados obtidos da análise estrutural, melhorar a estrutura se necessário. A análise por elementos finitos é a ferramenta principal durante esta primeira fase do projeto. E atualmente, devido às exigências do mercado, é imprescindível o suporte computorizado de maneira a agilizar esta fase do projeto. Existe para esta finalidade uma vasta gama de programas que permitem realizar tarefas que passam pelo desenho de estruturas, análise estática de cargas, análise dinâmica e vibrações, visualização do comportamento físico (deformações) em tempo real, que permitem a otimização da estrutura em análise. Porém, estes programas demostram uma certa complexidade durante a introdução dos parâmetros, levando muitas vezes a resultados errados. Assim sendo, é essencial para o projetista ter uma ferramenta fiável e simples de usar que possa ser usada para fins de projeto de estruturas e otimização. Sobre esta base nasce este projeto tese onde se elaborou um programa com interface gráfica no ambiente Matlab® para a análise de estruturas por elementos finitos, com elementos do tipo Barra e Viga, quer em 2D ou 3D. Este programa permite definir a estrutura por meio de coordenadas, introdução de forma rápida e clara, propriedades mecânicas dos elementos, condições fronteira e cargas a aplicar. Como resultados devolve ao utilizador as reações, deformações e distribuição de tensões nos elementos quer em forma tabular quer em representação gráfica sobre a estrutura em análise. Existe ainda a possibilidade de importação de dados e exportação dos resultados em ficheiros XLS e XLSX, de maneira a facilitar a gestão de informação. Foram realizados diferentes testes e análises de estruturas de forma a validar os resultados do programa e a sua integridade. Os resultados foram todos satisfatórios e convergem para os resultados de outros programas, publicados em livros, e para cálculo a mão feitos pelo autor.

Preparation and properties of starch-based biopolymers modified with difunctional isocyanates

The present work reports on the preparation of thermoplastic starch (TPS) modified in situ with a diisocyanate derivative. Evidence of the condensation reaction between the hydroxyl groups of starch and glycerol with the isocyanate function (NCO) was confirmed by FTIR analysis. The evolution of the properties of the ensuing TPS, in term of mechanical properties, microstructure, and water sensitivity, was investigated using tensile mechanical, dynamic mechanical thermal analysis (DMTA), X-ray diffraction (XRD), and water uptake. The results showed that the addition of isocyanate did not affect the crystallinity of the TPS and slightly reduced the water uptake of the material. The evolution of the mechanical properties with ageing became less pronounced by the addition of the isocyanate as their amount exceeded 4 to 6wt%.

Poliuretanos obtenidos a partir de aceite de higuerilla modificado y poli-isocianatos de lisina: síntesis, propiedades mecánicas y térmicas y degradación in vitro

Biodegradable polyurethanes (PUR) were prepared from polyols derived from castor oil by transesterification of pentaerythritol-modified castor oil and lysine polyisocyanates (LDI and LTI). The polyurethanes obtained were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA), and dynamic mechanical thermal analysis (DMTA). The mechanical behavior of the polyurethanes was measured by Shore A hardness and tensile testing (stress-strain curves). The biodegradable nature of the material was determined by contact angle, water absorption tests, and in vitro degradation in PBS solution. This study aims to examine the effect of the structure and functionality of diisocyanate on the mechanical properties and in vitro degradation of the material. The results were compared with homologous materials obtained from isophorone diisocyanate (IPDI) used in previous works. The objective was to evaluate candidate materials that can be potentially used in tissue engineering.

Modification of commercial poly-lactide for extrusion coated food packaging applications

Poly-L-lactide (PLLA) is a widely used sustainable and biodegradable alternative to replace synthetic non-degradable plastic materials in the packaging industry. Conversely, its processing properties are not always optimal, e.g. insufficient melt strength at higher temperatures (necessary in extrusion coating processes). This thesis reports on research to improve properties of commercial PLLA grade (3051D from NatureWorks), to satisfy and extend end-use applications, such as food packaging by blending with modified PLLA. Adjustment of the processability by chain branching of commercial poly-L-lactide initiated by peroxide was evaluated. Several well-defined branched structures with four arms (sPLLA) were synthesized using pentaerythritol as a tetra-functional initiator. Finally, several block copolymers consisting of polyethylene glycol and PLLA (i.e. PEGLA) were produced to obtain a well extruded material with improved heat sealing properties. Reactive extrusion of poly-L-lactide was carried out in the presence of 0.1, 0.3 and 0.5 wt% of various peroxides [tert-butyl-peroxybenzoate (TBPB), 2,5-dimethyl-2,5-(tert-butylperoxy)-hexane (Lupersol 101; LOL1) and benzoyl peroxide (BPO)] at 190C. The peroxide-treated PLLAs showed increased complex viscosity and storage modulus at lower frequencies, indicating the formation of branched/cross linked architectures. The material property changes were dependent on the peroxide, and the used peroxide concentration. Gel fraction analysis showed that the peroxides, afforded different gel contents, and especially 0.5 wt% peroxide, produced both an extremely high molar mass, and a cross linked structure, not perhaps well suited for e.g. further use in a blending step. The thermal behavior was somewhat unexpected as the materials prepared with 0.5 wt% peroxide showed the highest ability for crystallization and cold crystallization, despite substantial cross linking. The peroxide-modified PLLA, i.e. PLLA melt extruded with 0.3 wt% of TBPB and LOL1 and 0.5 wt% BPO was added to linear PLLA in ratios of 5, 15 and 30 wt%. All blends showed increased zero shear viscosity, elastic nature (storage modulus) and shear sensitivity. All blends remained amorphous, though the ability of annealing was improved slightly. Extrusion coating on paperboard was conducted with PLLA, and peroxide-modified PLLA blends (90:10). All blends were processable, but only PLLA with 0.3 wt% of LOL1 afforded a smooth high quality surface with improved line speed. Adhesion levels between fiber and plastic, as well as heat seal performance were marginally reduced compared with pure 3051D. The water vapor transmission measurements (WVTR) of the blends containing LOL1 showed acceptable levels, only slightly lower than for comparable PLLA 3051D. A series of four-arm star-shaped poly-L-lactide (sPLLA) with different branch length was synthesized by ring opening polymerization (ROP) of L-lactide using pentaerythritol as initiator and stannous octoate as catalyst. The star-shaped polymers were further blended with its linear resin and studied for their melt flow and thermal properties. Blends containing 30 wt% of sPLLA with low molecular weight (30 wt%; Mwtotal: 2500 g mol-1 and 15000 g mol-1) showed lower zero shear viscosity and significantly increased shear thinning, while at the same time slightly increased crystallization of the blend. However, the amount of crystallization increased significantly with the higher molecular weight sPLLA, therefore the star-shaped structure may play a role as nucleating agent. PLLA-polyethylene glycol–PLLA triblock copolymers (PEGLA) with different PLLA block length were synthesized and their applicability as blends with linear PLLA (3051D NatureWorks) was investigated with the intention of improving heat-seal and adhesion properties of extrusion-coated paperboard. PLLA-PEG-PLLA was obtained by ring opening polymerization (ROP) of L-lactide using PEG (molecular weight 6000 g mol-1) as an initiator, and stannous octoate as catalyst. The structures of the PEGLAs were characterized by proton nuclear magnetic resonance spectroscopy (1H-NMR). The melt flow and thermal properties of all PEGLAs and their blends were evaluated using dynamic rheology, and differential scanning calorimeter (DSC). All blends containing 30 wt% of PEGLAs showed slightly higher zero shear viscosity, higher shear thinning and increased melt elasticity (based on tan delta). Nevertheless, no significant changes in thermal properties were distinguished. High molecular weight PEGLAs were used in extrusion coating line with 3051D without problems.

Carbon Nanotubes-Reinforced PET Nanocomposite by Melt-Compounding

Poly(ethylene terephthalate) (PET) nanocomposites with single-walled carbon nanotubes (SWNTs) have been prepared by a simple melt compounding method. With increasing concentration (0-3 wt %) of SWNTs, the mechanical and dynamic mechanical properties improved, corresponding to effective reinforcement. Melt rheological characterization indicated the effective entanglements provided by SWNTs in the melt state as well. Thermogravimetric analysis suggested no influence of SWNTs on the thermal stability of PET. Electrical conductivity measurements on the composite films pointed out that the melt compounded SWNTs can result in electrical percolation albeit at concentrations exceeding 2 wt %.