Composites and foams based on polylactic acid (PLA)

Cette étude est destinée à la production et à la caractérisation des composites d’acide polylactique (PLA) et des fibres naturelles (lin, poudre de bois). Le moussage du PLA et ses composites ont également été étudiés afin d’évaluer les effets des conditions de moulage par injection et du renfort sur les propriétés finales de ces matériaux. Dans la première partie, les composites constitués de PLA et des fibres de lin ont été produits par extrusion suivit par un moulage en injection. L’effet de la variation du taux de charge (15, 25 et 40% en poids) sur les caractéristiques morphologique, mécanique, thermique et rhéologique des composites a été évalué. Dans la deuxième étape, la poudre de bois (WF) a été choisie pour renforcer le PLA. La préparation des composites de PLA et WF a été effectuée comme dans la première partie et une série complète de caractérisations morphologique, mécanique, thermique et l’analyse mécanique dynamique ont été effectués afin d’obtenir une évaluation complète de l’effet du taux de charge (15, 25 et 40% en poids) sur les propriétés du PLA. Finalement, la troisième partie de cette étude porte sur les composites de PLA et de renfort naturel afin de produire des composites moussés. Ces mousses ont été réalisées à l’aide d’un agent moussant exothermique (azodicarbonamide) via le moulage par injection, suite à un mélange du PLA et de fibres naturelles. Dans ce cas, la charge d’injection (quantité de matière injectée dans le moule: 31, 33, 36, 38 et 43% de la capacité de la presse à injection) et la concentration en poudre de bois (15, 25 et 40% en poids) ont été variées. La caractérisation des propriétés mécanique et thermique a été effectuée et les résultats ont démontré que les renforts naturels étudiés (lin et poudre de bois) permettaient d’améliorer les propriétés mécaniques des composites, notamment le module de flexion et la résistance au choc du polymère (PLA). En outre, la formation de la mousse était également efficace pour le PLA vierge et ses composites car les masses volumiques ont été significativement réduites.

Applications for nanomaterials in critical technologies

This thesis is devoted to the development, synthesis, properties, and applications of nano materials for critical technologies, including three areas: (1) Microbial contamination of drinking water is a serious problem of global significance. About 51% of the waterborne disease outbreaks in the United States can be attributed to contaminated ground water. Development of metal oxide nanoparticles, as viricidal materials is of technological and fundamental scientific importance. Nanoparticles with high surface areas and ultra small particle sizes have dramatically enhanced efficiency and capacity of virus inactivation, which cannot be achieved by their bulk counterparts. A series of metal oxide nanoparticles, such as iron oxide nanoparticles, zinc oxide nanoparticles and iron oxide-silver nanoparticles, coated on fiber substrates was developed in this research for evaluation of their viricidal activity. We also carried out XRD, TEM, SEM, XPS, surface area measurements, and zeta potential of these nanoparticles. MS2 virus inactivation experiments showed that these metal oxide nanoparticle coated fibers were extremely powerful viricidal materials. Results from this research suggest that zinc oxide nanoparticles with diameter of 3.5 nm, showing an isoelectric point (IEP) at 9.0, were well dispersed on fiberglass. These fibers offer an increase in capacity by orders of magnitude over all other materials. Compared to iron oxide nanoparticles, zinc oxide nanoparticles didn’t show an improvement in inactivation kinetics but inactivation capacities did increase by two orders of magnitude to 99.99%. Furthermore, zinc oxide nanoparticles have higher affinity to viruses than the iron oxide nanoparticles in presence of competing ions. The advantages of zinc oxide depend on high surface charge density, small nanoparticle sizes and capabilities of generating reactive oxygen species. The research at its present stage of development appears to offer the best avenue to remove viruses from water. Without additional chemicals and energy input, this system can be implemented by both points of use (POU) and large-scale use water treatment technology, which will have a significant impact on the water purification industry. (2) A new family of aliphatic polyester lubricants has been developed for use in micro-electromechanical systems (MEMS), specifically for hard disk drives that operate at high spindle speeds (>15000rpm). Our program was initiated to address current problems with spin-off of the perfluoroether (PFPE) lubricants. The new polyester lubricant appears to alleviate spin-off problems and at the same time improves the chemical and thermal stability. This new system provides a low cost alternative to PFPE along with improved adhesion to the substrates. In addition, it displays a much lower viscosity, which may be of importance to stiction related problems. The synthetic route is readily scalable in case additional interest emerges in other areas including small motors. (3) The demand for increased signal transmission speed and device density for the next generation of multilevel integrated circuits has placed stringent demands on materials performance. Currently, integration of the ultra low-k materials in dual Damascene processing requires chemical mechanical polishing (CMP) to planarize the copper. Unfortunately, none of the commercially proposed dielectric candidates display the desired mechanical and thermal properties for successful CMP. A new polydiacetylene thermosetting polymer (DEB-TEB), which displays a low dielectric constant (low-k) of 2.7, was recently developed. This novel material appears to offer the only avenue for designing an ultra low k dielectric (1.85k), which can still display the desired modulus (7.7Gpa) and hardness (2.0Gpa) sufficient to withstand the process of CMP. We focused on further characterization of the thermal properties of spin-on poly (DEB-TEB) ultra-thin film. These include the coefficient of thermal expansion (CTE), biaxial thermal stress, and thermal conductivity. Thus the CTE is 2.0*10-5K-1 in the perpendicular direction and 8.0*10-6 K-1 in the planar direction. The low CTE provides a better match to the Si substrate which minimizes interfacial stress and greatly enhances the reliability of the microprocessors. Initial experiments with oxygen plasma etching suggest a high probability of success for achieving vertical profiles.

Structure dependencies for multiscale polymer composites using extrusion processes

Multiscale reinforcement, using carbon microfibers and multi-walled carbon nanotubes, of polymer matrix composites manufactured by twin-screw extrusion is investigated for enhanced mechanical and thermal properties with an emphasis on the use of a diverging flow in the die for fluid mechanical fiber manipulation. Using fillers at different length scales (microscale and nanoscale), synergistic combinations have been identified to produce distinct mechanical and thermal behavior. Fiber manipulation has been demonstrated experimentally and computationally, and has been shown to enhance thermal conductivity significantly. Finally, a new physics driven predictive model for thermal conductivity has been developed based on fiber orientation during flow, which is shown to successfully capture composite thermal conductivity.

Síntese, extração e caracterização de biopolímeros de origem microalgal para desenvolvimento de nanofibras

Pesquisas com microalgas estão crescendo devido aos possíveis bioprodutos oriundos de sua biomassa, bem como as suas diferentes aplicabilidades. Microalgas podem ser cultivadas para a produção de biopolímeros com características de biocompatibilidade e biodegradabilidade. Nanofibras produzidas por electrospinning a partir de poli-β-hidroxibutirato (PHB) geram produtos com aplicabilidade na área de alimentos e médica. O objetivo deste trabalho foi selecionar microalgas com maior potencial para síntese de biopolímeros, em diferentes meios de cultivo, bem como purificar poli-β-hidroxibutirato e desenvolver nanofibras. Este trabalho foi dividido em cinco artigos: (1) Seleção de microalgas produtoras de biopolímeros; (2) Produção de biopolímeros pela microalga Spirulina sp. LEB 18 em cultivo com diferentes fontes de carbono e redução de nitrogênio; (3) Síntese de biopolímeros pela microalga Spirulina sp. LEB 18 em cultivos autotróficos e mixotróficos; (4) Purificação de poli-β- hidroxibutirato extraído da microalga Spirulina sp. LEB 18; e (5) Produção de nanofibras a partir de poli-β-hidroxibutirato de origem microalgal. Foram estudadas as microalgas Cyanobium sp., Nostoc ellipsosporum, Spirulina sp. LEB 18 e Synechococcus nidulans. Os biopolímeros foram extraídos nos tempos de 5, 10, 15, 20 e 25 d de cultivo a partir de digestão diferencial. Para os experimentos com diferentes nutrientes, foi utilizado como fonte de carbono, bicarbonato de sódio, acetato de sódio, glicose e glicerina modificando-se as concentrações de nitrogênio e fósforo. Os cultivos foram realizados em fotobiorreatores fechados de 2 L. A concentração inicial de inóculo foi 0,15 g.L-1 e os ensaios foram mantidos em estufa termostatizada a 30 ºC com iluminância de 41,6 µmolfótons.m -2 .s -1 e fotoperíodo 12 h claro/escuro. Para a purificação de PHB, foi utilizada a biomassa da cianobactéria Spirulina sp. LEB 18, cultivada em meio Zarrouk. Após a extração do biopolímero bruto, a amostra foi desengordurada com hexano e purificada com 1,2-carbonato de propileno. Foram determinadas as purezas e as propriedades térmicas no PHB purificado. O biopolímero utilizado para produzir as nanofibras apresentava 70 % de pureza. A técnica para produção de nanofibras foi o electrospinning. As microalgas que apresentaram máxima produtividade foram Nostoc ellipsosporum e Spirulina sp. LEB 18 com rendimento de biopolímero 19,27 e 20,62 % em 10 e 15 d, respectivamente, na fase de máximo crescimento celular. O maior rendimento de biopolímeros (54,48 %) foi obtido quando se utilizou 8,4 g.L-1 de NaHCO3, 0,05 g.L-1 de NaNO3 e 0,1 g.L-1 de K2HPO4. A condição que proporcionou maior pureza do PHB foi a 130 ºC e 5 min de contato entre o solvente (1,2-carbonato de propileno) e o PHB. As análises térmicas para todas as amostras foram semelhantes em relação ao PHB padrão (Sigma-Aldrich). A purificação com 1,2-carbonato de propileno foi eficiente para o PHB extraído de microalga, alcançando pureza acima de 90 %. A condição que apresentou menores diâmetros de nanofibras foi ao utilizar solução contendo 20 % de biopolímero solubilizado em clorofórmio. As condições do electrospinning que apresentou nanofibras com diâmetros de 470 e 537 nm foram, vazão 150 µL.h-1 , diâmetro do capilar 0,45 mm e voltagens entre 24,1 e 29,6 kV, respectivamente. A microalga Spirulina sp. LEB 18 produz PHB ao utilizar menores concentrações de nutrientes no meio de cultivo, que pode ser purificado com 1,2-carbonato de propileno. Este biopolímero possui aplicabilidade para produção de nanofibras.

Numerical analysis of wooden slabs with perforations under fire conditions

Wood is considered an ideal solution for floors and roofs building construction, due the mechanical and thermal properties, associated with acoustic conditions. These constructions have good sound absorption, heat insulation and relevant architectonic characteristics. They are used in many civil applications: concert and conference halls, auditoriums, ceilings, walls… However, the high vulnerability of wooden elements submitted to fire conditions requires the evaluation of its structural behaviour with accuracy. The main objective of this work is to present a numerical model to assess the fire resistance of wooden cellular slabs with different perforations. Also the thermal behaviour of the wooden slabs will be compared considering different material insulation, with different sizes, inside the cavities. A transient thermal analysis with nonlinear material behaviour will be solved using ANSYS© program. This study allows to verify the fire resistance, the temperature evolution and the char-layer, throughout a wooden cellular slab with perforations and considering the insulation effect inside the cavities.

Análise de propriedades térmicas e mecânicas de compósitos de argamassa e resíduo de borracha

Although already to exist alternative technique and economically viable for destination of used tires, quantitative data on properties of constructive elements that use the rubber waste as aggregate still are restricted. In the present work, the waste proceeding from industry of retreading as material for manufacture of composite destined to the production of constructive elements was considered. Mechanical and thermal properties of mortar had been analyzed Portland cement with addition of waste without treatment, in the ratios of 10%, 20% and 30% in mass in relation to the mass of the cement, substituting the aggregate in the trace in mortar 1:5 mass cement and sand. The size of the used residue varied between 0,30mm and 4,8mm (passing in the bolter 4,8mm and being restrained in the one of 0,30mm), being it in the formats fibers and granular. The influences of the size and the percentage of residue added to the mortar (in substitution to the aggregate) in the thermal and mechanical properties had been considered. Assays of body-of-test in thestates had been become fullfilled cool (consistency index) and hardened (absorption of water for capillarity, strength the compression, traction and strength flexural). The work is centralized in the problem of the relation thermal performance /strength mechanics of used constructive systems in regions of low latitudes (Been of the Piauí), characterized for raised indices of solar radiation.

Synthesis of innovative polyelectrolytes using monomers coming from renewable sources

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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.

Efficient P(3HB) extraction from Burkholderia sacchari cells using non-chlorinated solvents

© 2015. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/

Modeling, Simulation, and Characterization of Space Debris in low-Earth Orbit

Every space launch increases the overall amount of space debris. Satellites have limited awareness of nearby objects that might pose a collision hazard. Astrometric, radiometric, and thermal models for the study of space debris in low-Earth orbit have been developed. This modeled approach proposes analysis methods that provide increased Local Area Awareness for satellites in low-Earth and geostationary orbit. Local Area Awareness is defined as the ability to detect, characterize, and extract useful information regarding resident space objects as they move through the space environment surrounding a spacecraft. The study of space debris is of critical importance to all space-faring nations. Characterization efforts are proposed using long-wave infrared sensors for space-based observations of debris objects in low-Earth orbit. Long-wave infrared sensors are commercially available and do not require solar illumination to be observed, as their received signal is temperature dependent. The characterization of debris objects through means of passive imaging techniques allows for further studies into the origination, specifications, and future trajectory of debris objects. Conclusions are made regarding the aforementioned thermal analysis as a function of debris orbit, geometry, orientation with respect to time, and material properties. Development of a thermal model permits the characterization of debris objects based upon their received long-wave infrared signals. Information regarding the material type, size, and tumble-rate of the observed debris objects are extracted. This investigation proposes the utilization of long-wave infrared radiometric models of typical debris to develop techniques for the detection and characterization of debris objects via signal analysis of unresolved imagery. Knowledge regarding the orbital type and semi-major axis of the observed debris object are extracted via astrometric analysis. This knowledge may aid in the constraint of the admissible region for the initial orbit determination process. The resultant orbital information is then fused with the radiometric characterization analysis enabling further characterization efforts of the observed debris object. This fused analysis, yielding orbital, material, and thermal properties, significantly increases a satellite’s Local Area Awareness via an intimate understanding of the debris environment surrounding the spacecraft.

Some comments about the use of GHP in Alentejo (Portugal)

In this work we advocate the use of geothermal pumps to cool the isolated houses that can be observed in the plain of Alentejo. Passive cooling of the houses, made for centuries, becomes insufficient when it aims to promote tourism in the region. The climatic characteristics of the region and the relatively high values of the thermal conductivity of the ground favour this type of use. The available land around the houses provide places where you can drill or make trenches to put the pipes under the surface . Some values of pipe lengths were obtained using values appropriate for the region. The need to try to preserve the shape of the typical houses of the region discourages the use of solar panels placed on the roofs. The length and time of use of the equipment is another factor to take into account in the analysis of the costs.

Homogenization of nonlinear composites for multiscale analysis

A composite is a material made out of two or more constituents (phases) combined together in order to achieve desirable mechanical or thermal properties. Such innovative materials have been widely used in a large variety of engineering fields in the past decades. The design of a composite structure requires the resolution of a multiscale problem that involves a macroscale (i.e. the structural scale) and a microscale. The latter plays a crucial role in the determination of the material behavior at the macroscale, especially when dealing with constituents characterized by nonlinearities. For this reason, numerical tools are required in order to design composite structures by taking into account of their microstructure. These tools need to provide an accurate yet efficient solution in terms of time and memory requirements, due to the large number of internal variables of the problem. This issue is addressed by different methods that overcome this problem by reducing the number of internal variables. Within this framework, this thesis focuses on the development of a new homogenization technique named Mixed TFA (MxTFA) in order to solve the homogenization problem for nonlinear composites. This technique is based on a mixed-stress variational approach involving self-equilibrated stresses and plastic multiplier as independent variables on the Reference Volume Element (RVE). The MxTFA is developed for the case of elastoplasticity and viscoplasticity, and it is implemented into a multiscale analysis for nonlinear composites. Numerical results show the efficiency of the presented techniques, both at microscale and at macroscale level.

Advanced electrospun nanofibrous mats for hindering delamination, improving damping and for sensing of composite laminates

Carbon Fiber Reinforced Polymers (CFRPs) display high specific mechanical properties, allowing the creation of lightweight components and products by metals replacement. To reach outstanding mechanical performances, the use of stiff thermoset matrices, like epoxy, is preferred. Laminated composites are commonly used for their ease of manipulation during object manufacturing. However, the natural anisotropic structure of laminates makes them vulnerable toward delamination. Moreover, epoxy-based CFRPs are very stiff materials, thus showing low damping capacity, which results in unwanted vibrations and structure-borne noise that may contribute to delamination triggering. Hence, searching for systems able to limit these drawbacks is of primary importance for safety reasons, as well as for economic ones. In this experimental thesis, the production and integration of innovative rubbery nanofibrous mats into CFRP laminates are presented. A smart approach, based on single-needle electrospinning of rubber-containing blends, is proposed for producing dimensionally stable rubbery nanofibers without the need for rubber crosslinking. Nano-modified laminates aim at obtaining structural composites with improved delamination resistance and enhanced damping capacity, without significantly lowering other relevant mechanical properties. The possibility of producing nanofibers nano-reinforced with graphene to be applied for reinforcing composite laminates is also investigated. Moreover, the use of piezoelectric nanofibrous mats in hybrid composite laminates for achieving self-sensing capability is presented too as a different approach to prevent the catastrophic consequences of possible structural laminate failure. Finally, an accurate, systematic, and critical study concerning tensile testing of nonwovens, using electrospun Nylon 66 random nanofibrous mats as a case study, is proposed. Nanofibers diameter and specimen geometry were investigated to thoroughly describe the nanomat tensile behaviour, also considering the polymer thermal properties, and the number of nanofibers crossings as a function of the nanofibers diameter. Stress-strain data were also analysed using a phenomenological data fitting model to interpret the tensile behaviour better.

Development of a numerical platform for the modeling and optimal control of liquid metal flows

The main purpose of this work is to develop a numerical platform for the turbulence modeling and optimal control of liquid metal flows. Thanks to their interesting thermal properties, liquid metals are widely studied as coolants for heat transfer applications in the nuclear context. However, due to their low Prandtl numbers, the standard turbulence models commonly used for coolants as air or water are inadequate. Advanced turbulence models able to capture the anisotropy in the flow and heat transfer are then necessary. In this thesis, a new anisotropic four-parameter turbulence model is presented and validated. The proposed model is based on explicit algebraic models and solves four additional transport equations for dynamical and thermal turbulent variables. For the validation of the model, several flow configurations are considered for different Reynolds and Prandtl numbers, namely fully developed flows in a plane channel and cylindrical pipe, and forced and mixed convection in a backward-facing step geometry. Since buoyancy effects cannot be neglected in liquid metals-cooled fast reactors, the second aim of this work is to provide mathematical and numerical tools for the simulation and optimization of liquid metals in mixed and natural convection. Optimal control problems for turbulent buoyant flows are studied and analyzed with the Lagrange multipliers method. Numerical algorithms for optimal control problems are integrated into the numerical platform and several simulations are performed to show the robustness, consistency, and feasibility of the method.