Hydroxyapatite (HA) is a biologically active ceramic used in surgery to replace bone. While HA promotes bone growth, it suffers from weak mechanical properties and does not possess any antibacterial property. Multi walled carbon nanotubes (MWCNTs), as one of the strongest and stiffest materials, have the potential to strengthen and toughen HA, thus expanding the range of clinical uses for the material. Furthermore, Silver nanoparticles (Ag NPs) can be decorated to sidewalls of the MWCNTs which could be released over a period of time to prevent infection following surgery. This work sought to develop and characterise Ag NPs- MWCNTs – HA composites in four main areas: 1) production and characterisation of the composite, 2) evaluation of mechanical properties, 3) investigation of antimicrobial property and 4) assessment of biological response to in vitro cell culture. Pristine (p-MWCNTs) and acid treated MWCNTs (f-MWCNTs) were decorated with Ag NPs. In the presence of 0.5 wt % Ag NPs-MWCNTs, HA was precipitated by the wet precipitation method in the presence of either poly vinyl alcohol (PVA) or Hexadecyl trimethyl ammonium bromide (HTAB) as the surfactant. Composites were characterised using various techniques and the diameteral tensile strength and compressive strength of the composites were measured. The antibacterial effect of these composites was investigated against clinically relevant microbe, Staphylococcus aureus. To determine the ability of the HOB cells to differentiate and mineralize in the presence of the composite, HOB cells were cultured on the composites for 21 days. Gene expression studies was performed along with the biochemical assays and scanning electron microscopy was used for qualitative analysis. Pure HA was used as control in all the studies. The study revealed that both the MWCNTs and surfactants play a crucial role in the nucleation and growth of the HA. XRD and FTIR characterisation revealed that HA was the primary phase in all the synthesised powders. Composites made with f-MWCNTs were found to have better dispersion and better interaction with the HA compared to composites with p-MWCNTs. Although mechanical strength was improved in all the composites, p-MWCNTs composites exhibiting maximum strength. Antibacterial studies showed 80% bacterial reduction in the treatment composites compared to pure HA. The biocompatibility study showed reduced activity of the HOB cells, however, no significant difference was observed between the control and the treatments. This systematic study of the synthesis and properties of the Ag NPs- MWCNTs-HA composites has resulted in improved understanding of the production and processing of these materials and the effect of MWCNTs and silver nanoparticles on primary human osteoblast cells. Additionally, it has yielded interesting biocompatibility result favouring the use of MWCNTs in the development of implants. There is potential to translate Ag NPs-MWCNTs-HA composites into clinically approved product.

Flax fiber-reinforced plastic composites have attracted increasing interest because of the advantages of flax fibers, such as low density, relatively high toughness, high strength and stiffness, and biodegradability. Thus, oilseed flax fiber derived from flax straw, a renewable resource available in Western Canada, is recognized as a potential replacement for glass fiber in composites. Among plastics, polyethylene is a suitable material for use as a matrix in composites. However, there are not many studies in this area. Therefore, the main goal of this research was to develop flax fiber-polyethylene (PE) biocomposites via injection molding and investigate the effect of material properties and processing parameters on their properties. <p>Alkali, silane, potassium permanganate, sodium chlorite, and acrylic acid treatments were employed to flax fiber to decrease the hydrophilic of fiber and improve the adhesion between the fiber and the matrix. All chemically treated fiber-HDPE biocomposites had higher tensile strength and lower water absorption compared with non-chemically treated ones. Acrylic acid treatment of the fiber resulted in slight increase in its degradation temperature; using this treated fiber resulted in biocomposites with the best performance. Therefore, the morphological, chemical, and thermal properties of acrylic acid treated fiber were also studied. <p>Linear Low Density Polyethylene (LLDPE) and High Density Polyethylene (HDPE) were the main matrices investigated in this research. Showing a high tensile strength and similar water absorption, HDPE was used as the matrix in further research. Flax fiber with 98-99% purity was chosen as reinforcement since the flax shive mixed with the fiber decreased the tensile and flexural properties but increased the water absorption of the biocomposite. <p>Acrylic acid-treated fiber-HDPE biocomposites had been developed through injection molding under different processing conditions. Increasing the fiber content of biocomposite increased its tensile and flexural strengths, especially flexural modulus, but its water absorption capacity also increased. It was possible to improve the mechanical properties of biocomposites and decrease the water absorption by adjusting injection temperature and pressure. Injection temperature had more influence on the quality of the biocomposite than injection pressure. Injection temperature lower than 195°C was recommended to achieve good composite quality. <p>Melts of HDPE and flax fiber-HDPE biocomposites were categorized as power-law fluids. Apparent viscosity, consistency coefficient, and flow behavior index of biocomposites were determined to study their flow behavior. The statistical relationship of these parameters with temperature and fiber content were modeled using the SAS and SPSS softwares. The injection filling time was related to the material rheological properties: biocomposites required longer filling time than pure HDPE. Low injection temperature also resulted in long filling time.<p>The thermal conductivity, thermal diffusivity, and specific heat of biocomposites containing 10, 20, and 30% fiber by mass were determined in the processing temperature range of 170 to 200°C. Fiber content showed a significant influence on the thermal properties of the biocomposites. The predicted minimum cooling time increased with the thickness of the molded material, mold temperature, and injection temperature, but it decreased with the ejection temperature.

Flax fiber-reinforced plastic composites have attracted increasing interest because of the advantages of flax fibers, such as low density, relatively high toughness, high strength and stiffness, and biodegradability. Thus, oilseed flax fiber derived from flax straw, a renewable resource available in Western Canada, is recognized as a potential replacement for glass fiber in composites. Among plastics, polyethylene is a suitable material for use as a matrix in composites. However, there are not many studies in this area. Therefore, the main goal of this research was to develop flax fiber-polyethylene (PE) biocomposites via injection molding and investigate the effect of material properties and processing parameters on their properties. <p>Alkali, silane, potassium permanganate, sodium chlorite, and acrylic acid treatments were employed to flax fiber to decrease the hydrophilic of fiber and improve the adhesion between the fiber and the matrix. All chemically treated fiber-HDPE biocomposites had higher tensile strength and lower water absorption compared with non-chemically treated ones. Acrylic acid treatment of the fiber resulted in slight increase in its degradation temperature; using this treated fiber resulted in biocomposites with the best performance. Therefore, the morphological, chemical, and thermal properties of acrylic acid treated fiber were also studied. <p>Linear Low Density Polyethylene (LLDPE) and High Density Polyethylene (HDPE) were the main matrices investigated in this research. Showing a high tensile strength and similar water absorption, HDPE was used as the matrix in further research. Flax fiber with 98-99% purity was chosen as reinforcement since the flax shive mixed with the fiber decreased the tensile and flexural properties but increased the water absorption of the biocomposite. <p>Acrylic acid-treated fiber-HDPE biocomposites had been developed through injection molding under different processing conditions. Increasing the fiber content of biocomposite increased its tensile and flexural strengths, especially flexural modulus, but its water absorption capacity also increased. It was possible to improve the mechanical properties of biocomposites and decrease the water absorption by adjusting injection temperature and pressure. Injection temperature had more influence on the quality of the biocomposite than injection pressure. Injection temperature lower than 195°C was recommended to achieve good composite quality. <p>Melts of HDPE and flax fiber-HDPE biocomposites were categorized as power-law fluids. Apparent viscosity, consistency coefficient, and flow behavior index of biocomposites were determined to study their flow behavior. The statistical relationship of these parameters with temperature and fiber content were modeled using the SAS and SPSS softwares. The injection filling time was related to the material rheological properties: biocomposites required longer filling time than pure HDPE. Low injection temperature also resulted in long filling time.<p>The thermal conductivity, thermal diffusivity, and specific heat of biocomposites containing 10, 20, and 30% fiber by mass were determined in the processing temperature range of 170 to 200°C. Fiber content showed a significant influence on the thermal properties of the biocomposites. The predicted minimum cooling time increased with the thickness of the molded material, mold temperature, and injection temperature, but it decreased with the ejection temperature.

Dans cette étude, les matériaux composites poly 3-hydroxybutyrate-co-4-hydroxybutyrate (P34HB) / fibres de bambou et polybutylène succinate (PBS) / fibres de bambou ont été préparés en utilisant le mélangeur interne et le moulage par compression. Les propriétés thermo-mécaniques de P34HB et de PBS ont été caractérisées. Les fibres de bambou ont été modifiées par des traitements chimiques. Les propriétés mécaniques telles que la résistance à la traction, la résistance à la flexion, le module d’élasticité et les propriétés thermiques ont été étudiées. Pour les deux types de composites (P34HB et PBS), le module est significativement amélioré, cependant, la résistance du composite est légèrement diminuée. L'allongement à la rupture est plus faible que celui des polymères purs, ce qui indiquerait une bonne adhérence entre la matrice et les fibres. L'étude révèle que l'adhésion est améliorée avec les fibres modifiées avec le silane et l'acide acétique, ce qui entraîne une augmentation des propriétés mécaniques du matériau, par rapport à celles des composites renforcés avec des fibres non traitées. En outre, le taux de 20% de fibres est considéré comme la bonne composition de fibres pour garantir de bonnes propriétés thermo-mécaniques et une absorption d'eau faible.En étudiant ces matériaux composites, nous visons à produire des matériaux respectueux de l'environnement. De plus, l’abondance des fibres de bambou permettra de réduire le coût de la matière première. Ce travail porte principalement sur la modification des fibres de bambou afin d'améliorer les propriétés globales des composites et sur la comparaison de ces propriétés par rapport à celles des fibres non traitées. Pour atteindre une meilleure adhérence matrice-fibre, un agent de couplage et/ou compatibilisant peuvent être étudiés et utilisés dans une future étude. / In this study, poly 3,4 hydroxy butyrate (P34HB)/bamboo fibers and polybutylene succinate (PBS)/bamboo fibers composites were prepared by internal mixer and compression molding. P34HB and PBS were characterized with mechanical and thermal methods while bamboo fibers were modified with chemical treatments. Mechanical properties such as tensile strength, flexural strength, modulus and thermal properties were investigated. For both 2 kinds of composites (from P34HB and PBS), it was found that the modulus was significantly improved, however, the strength of the composite was slightly decreased and the elongation at break was a lower than the neat polymer suggesting that the adhesion between matrix and reinforcement should be improved more. The study reveals that modifying the fibers with both silane and acetic acid would improve the adhesion, resulting to the better mechanical properties of the material, compared with composites reinforced with untreated fiber or fiber treated with other methods. Also, 20 % of fiber content is regarded as the good composition of fiber to guarantee the good mechanical, water absorption and thermal properties.By taking advantage of P34HB, PBS and bamboo fibers, we aim to produce the material which is environmental friendly. Moreover, the abundant bamboo fibers can be used and these bamboo fibers will reduce the cost of the material. Within this work, we focus on the modification of bamboo fibers to reach our goal of improving the overall properties of the composites, compared with composites reinforced with untreated fibers. To achieve the better adhesion between fibers and matrix, coupling agent and compatibilizer may be used and studied in our future study.

La plupart des outils d’aide à la conception industrielle disponibles aujourd’hui sont basés sur l’utilisation des modèles analytiques et statistiques. Ces modèles permettent de caractériser les relations entre les facteurs de conception et les critères de qualité afin de prédire la qualité d’un nouveau produit sans effectuer de nouveaux essais expérimentaux. Néanmoins, en raison de la complexité du comportement du produit et/ou du procédé, de l’incertitude dans le processus de conception et du faible nombre de données expérimentales, ces modèles classiques sont souvent moins efficaces pour traiter des applications complexes. Dans le cadre de ma thèse doctorale, nous travaillons essentiellement sur la conception des matériaux composites multifonctionnels à base de fibres. Dans ce contexte, nous avons amélioré les outils d’aide à la conception industrielle afin de développer, de façon systématique, des nouveaux matériaux. Pour cela, nous proposons une démarche utilisant non seulement les techniques classiques d’analyse de données, mais aussi les techniques de calcul avancé. En nous appuyant sur ces techniques, nous avons réalisé un système intégral en langage UML et programmation informatique, permettant d’identifier les paramètres pertinents du procédé et de la structure du matériau composite étudié selon les propriétés fonctionnelles souhaitées. Ce système a été appliqué à la maîtrise d’un procédé textile de renfort par aiguilletage et au développement de matériaux biocomposites pour lesquels les performances mécaniques et acoustiques sont pris en compte simultanément. / Most of the industrial design assistant tools that are available nowadays are based on the use of analytical and statistical models. Those methods enable to characterize the relations between the design factors and the quality criterions in order to predict the quality of a new product without doing new experimental tests. Nevertheless, because of the behavioural complexity of the product or the method, the uncertainty in the design process and the weak number of experimental data, those classical models are often less efficient to treat complex applications. As part of my doctoral thesis, we have essentially worked (si tu veux mettre au present we work) on the design of multifunctional composite materials made of fibres. In this context, we have improved the industrial design assistant tools in order to develop in a systematic way, new materials. For this, we propose an approach that not only uses the classical technics of data analysis but also the advanced calculation technics. By using those technics, we realized an integral system in UML language and an oriented object computer programming, that allow to identify the pertinent parameters of the method and of the structure of the composite material studied according to the desired functional properties. This system was applied to the control of a textile reinforcement process by needling and development of biocomposites materials which the mechanical and acoustical performances are simultaneously considered.

An improved method to evaluate Young's modulus of bacterial cellulose (BC) nanofibrils is presented. This estimation takes into account polarisation configurations, nanofibril orientation and tensile deformation axis direction. A range of 79 - 88 GPa has been obtained showing their great potential to be used as reinforcement in composite materials. BC bio-composites, constituted of a BC layer embedded in-between two matrix layers, have been prepared by compression moulding. The stress-transfer from the matrix to the reinforcement has been quantified using Raman spectroscopy. This has been carried out by following the shift of the Raman band initially located at a wavenumber position of ~1095 cm-1. Polylactide (PLA) was chosen as matrix material due to its biodegradability and bio-sourced origin. Transparent polylactide films were obtained in specific processing conditions to suppress crystallisation. This allowed the laser to penetrate the matrix and interact with the upper layer of BC networks. Several factors that could affect the interface in these composites have been studied. The influence of the culturing time of BC networks on the composite interfaces has been investigated. Higher Raman band shift rates with respect to strain and stress have been measured for composites manufactured using BC networks having a low culturing time. This led to enhanced coupling between PLA and the upper layer of BC networks. Scanning electron microscopy imaging of the tensile fracture surface of these composites revealed that delamination between the BC layers was occurring rather than failure at the BC/PLA interface. Cross-linking of BC networks using glyoxal was performed to consolidate their layered structure. Raman spectroscopy was used to probe the stress-transfer of unmodified and cross-linked BC networks. These data revealed that cross-linked materials exhibit an enhanced stress-transfer both in the dry and wet states compared to unmodified BC networks. Cross-linked BC networks were used to design composites but no significant stress-transfer improvement was observed. As a result, maleated polylactide (MAPLA) was produced and used as a matrix material in order to consolidate the interface between PLA and both the upper and lower layer of cross-linked BC networks. Composites designed using cross-linked BC networks and MAPLA showed a significant stress-transfer improvement over composites designed using unmodified BC networks and PLA. Also the determination of the bulk tensile mechanical properties of the composites revealed a significant increase of relative Young's modulus. This increase is thought to be due to reduced molecular mobility at both the cross-linked BC/MAPLA interface and between cross-linked BC layers. This is further supported by scanning electron imaging of the tensile fracture surfaces.

Face à la nécessité de trouver des alternatives aux ressources d’origine fossile et de limiter les impacts environnementaux de l’activité humaine, un important effort de recherche est actuellement en cours pour favoriser et accroître l’utilisation de produits issus de ressources renouvelables, comme les fibres végétales, dans la conception de pièces industrielles. Toutefois, de nombreux verrous scientifiques et technologiques restent encore à lever avant de pouvoir valoriser de façon fiable et durable ces fibres dans un contexte technique exigeant tel que celui du secteur l’automobile. Ainsi, l’amélioration de la qualité de l’interface fibres végétales / matrice polymère est un enjeu de taille car elle constitue une condition permettant de satisfaire les performances mécaniques requises telles que la rigidité, la résistance ou la tenue au choc. Dans ce contexte, l’objectif de la thèse a été le développement de fibres courtes de chanvre à propriétés de surface maitrisées et ciblées. Des solutions de fonctionnalisation de surface applicables par des procédés industrialisables ont été développées dans le but d’incorporer ces fibres dans une matrice polypropylène (PP). Les fibres de chanvre ont ainsi été traitées selon différentes stratégies de fonctionnalisation incluant l’utilisant du polypropylène greffé anhydride maléique (PP-g-MA), d’organosilanes, d’un acide aminé, d’isocyanates et d’un polyuréthane. Deux procédés de traitement à faible impact environnemental ont été comparés : le sprayage direct des fibres par les molécules de fonctionnalisation et l’incorporation de ces molécules par extrusion réactive. Les traitements en extrusion réactive se sont montrés plus efficaces que ceux réalisés par sprayage dans le cas du PP-g-MA. Trois voies de fonctionnalisation se sont avérées pertinentes au regard des propriétés mécaniques visées  : i) l’utilisation de PP-g-MA seul en extrusion réactive ; ii) la fonctionnalisation par sprayage d’un aminosilane ou d’un acide aminé couplée à l’incorporation du PP-g-MA en extrusion réactive. S’appuyant sur le développement de moyens expérimentaux et d’analyses spécifiques, l’étude du comportement au choc des biocomposites a montré que les composites renforcés fibres de chanvre permettent d’absorber d’avantage d’énergie que les composites PP / verre (à taux volumique de renfort identique) pour une longueur de fissuration similaire. Une modélisation par éléments finis du comportement au choc des composites étudiés est également proposée. / Due to the necessity to find alternatives to fossil resources and to reduce the environmental impacts of human activity, a major research effort is currently ongoing in order to develop and increase the use of biobased products from renewable resources, such as natural fibers, in the design of industrial parts. However, many scientific and technological hurdles have yet to be removed so as to promote these products before we can reliably and durably use these fibers in a demanding technical context as in automotive sector. Thus, improving the quality of the interface between natural fibers and polymer matrix is a major challenge, since it constitutes a condition for satisfying the required mechanical performances, such as stiffness, tensile or impact strengths. In this context, the thesis objective was to develop short hemp fibers with controlled and targeted surface properties. Surface-functionalization solutions have been developed, to be used by industrial processes, with the aim of incorporating these fibers in a polypropylene (PP) matrix. Therefore, hemp fibers have been treated according to various functionalization strategies including the use of grafted polypropylene maleic anhydride (PP-g-MA), organosilanes, an amino acid, isocyanates and a polyurethane. Two treatments processes, with low environmental impact, were compared: the direct spraying of functionalization molecules on fibers and reactive extrusion incorporation of these molecules. Reactive extrusion treatments were more efficient than those performed by spraying in the case of PP-g-MA. Three functionalization lanes have been found to be relevant regarding the mechanical properties targeted: i) using PP-g-MA alone in reactive extrusion; ii) spraying-functionalization of an aminosilane or of an amino acid coupled with the incorporation of PP-g-MA into the reactive extrusion. Based on the development of experimental means and specific analyzes, the study of the impact behavior of biocomposites has shown that hemp fiber reinforced composites allow to absorb more energy than PP / glass composites (at identical reinforcing volume rate) for a similar crack length. Also, a finite element modeling of the impact behavior of the studied composites is propounded.

Les matériaux biocomposites, en particulier les composites matrice thermoplastique biosourcée ou non renforcée de charges ou de fibres végétales, connaissent actuellement un essor significatif et présentent pour l'avenir un gisement grandissant de matières en fin de vie. En conséquence, l'étude du comportement de ces matériaux au regard de différents scénarios de fin de vie que sont le recyclage mécanique, le compostage et l'incinération constitue un enjeu scientifique et technologique important. Le premier objectif de cette thèse est d'étudier la fin de vie par retransformation (cycles successifs d'injection et de broyage) de biocomposites à matrice polypropylène (PP) chargé de farine de bois. L'impact de la taille des particules de bois et d'un agent de couplage a été évalué. Une très bonne stabilité mécanique jusqu'à 7 cycles de retransformation a été observée malgré des dégradations des différents composants du matériau. Le comportement face à la retransformation après vieillissement artificiel accéléré ou après une exposition naturelle en extérieur a été étudié. La tendance majeure dégagée est un phénomène de « régénération » des propriétés mécaniques par retransformation, et cela malgré des dégradations importantes après vieillissement. Il a été également été observé que l'ajout de bois a tendance à limiter la photodégradation du PP. Le second objectif est d'étudier la fin de vie de biocomposites à matrice acide polylactique (PLA) renforcé de fibres de lin. L'impact de différents paramètres de formulation, de la technique de mise en œuvre et d'un vieillissement hygrothermique sur la retransformation de ces matériaux a été évalué. Les mêmes phénomènes de « régénération » sont observés, ce qui montre l'effet bénéfique de la retransformation. La fin de vie par compostage et par biodégradation est traitée. Des mesures d'énergies de combustion ont enfin permis d'estimer le potentiel de valorisation par incinération qui serait en lien avec le niveau de dégradation du PLA. / Nowadays, biocomposite materials are booming and will be a growing end-of-life issue for the future. They are based on a thermoplastic matrix (oil-based or bio-based) reinforced with vegetable fillers or fibers. Consequently, the study of their end of life through recycling, composting and incineration is a scientific and technologic challenge.The first goal of this thesis is to study the reprocessing end of life (successive injection and grinding cycles) of polypropylene (PP) based biocomposites filled with wood flour. The impact of the wood particle size and a coupling agent was assessed. Thus, a very good mechanical stability was observed up to 7 reprocessing cycles despite some degradation from the material components. Then, the reprocessing after artificial or natural UV weathering was carried out. The major trend is a “regeneration” phenomenon of mechanical properties after reprocessing in spite of strong degradations after UV weathering. Moreover, the addition of wood filler tends to restrain the PP photochemical degradation.The second goal is to study the end of life of polylactic acid (PLA) based biocomposites reinforced with flax fibers. The impact of the composition, the processing technic and humidity weathering on the reprocessing was assessed. Similar “regeneration” phenomena were observed leading to conclude to the beneficial effect of reprocessing. Then composting and biodegradation aspects were investigated. Heat release rate measurements enabled to estimate the incineration potential which could be linked to the PLA degradation rate.

L'objectif de ce travail de thèse, réalisé dans le cadre de la Chaire Industrielle Bioplastiques financée par Mines ParisTech et Arkema, l'Oreal, Nestle, PSA et Schneider Electric, est de fournir une étude systématique sur les relations entre les conditions opératoires du procédé de compoundage et la structure de biocomposites polypropylène/fibres lin et Tencel®. En particulier, le comportement et la rupture des fibres ont été étudiés de manière détaillée pendant la mise en œuvre à l'état fondu en mélangeur interne et par extrusion bivis.Les fibres ont été observées in-situ en écoulement dans la matrice grâce à un système rhéo-optique. Ainsi, il a été montré que la décohésion des faisceaux de lin est facilitée par un rapport de forme initial plus grand. La fragmentation des fibres résulte d'un phénomène de fatigue et est provoquée par l'accumulation des déformations et de l'énergie mécanique. Au niveau de leur point de rupture, les fibres de lin et de Tencel® se déchirent et fibrillent, alors que les fibres élémentaires de lin cassent près de leurs « genoux ». Des analyses de distributions de tailles des fibres après compoundage avec la matrice ont corroboré les observations rhéo-optiques. Lorsque les conditions de mélange sont sévères, chaque « genou » devient un point de rupture et la longueur finale des fibres de lin se retrouve être égale à la longueur moyenne entre les « genoux ». Les faisceaux de lin initialement plus courts ne se dissocient et ne se fragmentent que très peu. La rupture des fibres de lin est différente en fonction de leur taille initiale et ces fibres ne conduisent pas au même comportement rhéologique pour les composites. En revanche, pour les fibres unitaires Tencel®, la taille initiale n'a que très peu d'influence sur leurs dimensions finales, à condition que les fibres ne soient pas trop longues et trop difficiles à disperser. Le temps de mélange est apparu déterminant pour préserver le rapport de forme des fibres. La déformation cumulée s'est révélée être un meilleur paramètre que l'énergie mécanique spécifique pour décrire à la fois la rupture des fibres de lin et de Tencel®. Les propriétés mécaniques en traction uniaxiale ont enfin été caractérisées et mises en relation avec les conditions de mélange et les dimensions finales des fibres. / The objective of this work, performed in the frame of the Industrial Chair in Bioplastics, financed by Mines ParisTech and Arkema, l'Oreal, Nestle, PSA and Schneider Electric, is to provide a systematic study of the relationships between the compounding conditions and the structure of biocomposites based on polypropylene/ flax and Tencel® fibres. In particular, the behaviour and the rupture of fibres were studied in detail during melt processing in an internal mixer and a twin screw extruder.The fibres were observed in situ during shear flow in a matrix by rheo-optics. The decohesion of flax bundles was shown to be made easier for fibres with higher initial aspect ratio. The fibres fragmentation occured by fatigue and is caused by an accumulation of strain and mechanical energy. At the breaking point, flax and Tencel® fibres are tearing and fibrillating, whereas elementary flax fibres break at “kink bands”. The analysis of fibres size distributions after compounding has corroborated rheo-optical observations. When processing conditions are severe, each “kink band” becomes a breaking point, and the final fibres length is equal to the mean length between two “kind bands”. The short flax bundles dissociate and break up less after compounding as compared to long bundles. As a result, the rheological properties of composites are different. The initial size of Tencel® fibres has almost no effect on fibre final dimensions, provided that they are not too long and thus do not make agglomerates. The mixing time seems to be decisive to preserve fibres aspect ratio. The cumulative strain was shown to be a better parameter than specific mechanical energy to describe fibres rupture for both Tencel® and flax fibres. Uniaxial tensile properties were characterized and correlated to the processing conditions and to final dimensions of fibres.

Neste trabalho, foram utilizadas fibras de curauá visando ação como reforço de matriz termoplástica de biopolietileno de alta densidade. O polietileno utilizado neste trabalho foi obtido pela polimerização de eteno, gerado a partir do etanol de cana de açúcar. Este polímero é também chamado de biopolietileno (BPEAD), por ser preparado a partir de material oriundo de fonte natural. Desta forma, pretendeu-se contribuir para com o desenvolvimento de materiais que, dentre outras propriedades, na sua produção, utilização e substituição, ocorra menor emissão de CO2 para a atmosfera, comparativamente a outros materiais. A superfície das fibras de curauá foi modificada via tratamento com ar ionizado, visando uma melhor impregnação da fibra pela matriz, o que possivelmente levaria a uma otimização da interface entre a matriz e a fibra. As propriedades dos compósitos reforçados com esta fibra (distribuição aleatória, comprimento de 1cm, diferentes proporções; materiais obtidos em misturador interno e por termoprensagem), foram comparadas com aquelas do reforçado com fibras não modificadas. Adicionalmente, polibutadieno líquido hidroxilado (PBHL) foi acrescentado à formulação do compósito, visando um aumento na resistência à propagação da trinca durante impacto. Os compósitos e as fibras foram caracterizados por várias técnicas, tais como, microscopia eletrônica de varredura (MEV), Calorimetria Exploratória Diferencial (DSC), Termogravimetria (TG), além, da caracterização dos compósitos quanto à Análise Térmica Dinâmico-Mecânica (DMTA), propriedades mecânicas (impacto e flexão) e absorção de água. A presença das fibras de curauá diminuiu algumas propriedades do BPEAD, como resistência ao impacto. A análise de DMTA mostrou que a presença de fibras leva a um material mais rígido. Pode-se considerar que a introdução de PBHL na formulação do material foi eficiente, levando a uma maior resistência ao impacto do compósito BPEAD/PBHL/fibra, quando comparado ao compósito BPEAD/fibra. A partir de 15% de PBHL adicionado ao compósito não houve mistura eficiente deste com os outros componentes, conforme evidenciado pelos resultados de resistência à flexão. As propriedades mecânicas dos materiais, no geral, não sofreram grande influência de as fibras terem sido tratadas com ar ionizado. Os resultados apontam no sentido que parâmetros de processo podem ser explorados, visando minimizar a degradação do polímero, além de trazerem outros inidicadores importantes, como que provavelmente uma borracha de maior massa molar média que a usada no presente trabalho possa apresentar uma ação mais significativa como modificadora de impacto; que fibras mais longas que aquelas consideradas, na mesma proporção em massa, podem ser testadas, já que fibras curtas implicam em grande número de pontas, as quais podem agir como concentradoras de tensão e prejudicar as propriedades mecânicas do compósito. / In this work, curaua fibers were used in the reinforcement of a high-density (HDPE) thermoplastic matrix. The polyethylene used in this study was obtained by polymerization of ethene produced from sugarcane ethanol. This polymer, also called high-density biopolyethylene (HDBPE), was prepared from a natural source material. The aim of the present study was to contribute to the development of materials that, among other properties, release less CO2 into the atmosphere as compared to other materials. The curaua fiber surface was modified by treatment with ionized air, seeking improved fiber impregnation by the matrix, which would possibly enhance the fiber/matrix interface adhesion. The properties of the composites reinforced with this fiber (randomly distributed, 1-cm long, different amounts, thermopressed materials) were compared with those reinforced with non-modified fibers. Additionally, liquid hydroxylated polybutadiene (LHPB) was added to the composite formulation, aiming at improving resistance to crack spreading during impact. The fibers and their composites were characterized by several techniques, such as scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermal gravimetry (TG). The composites were also characterized by dynamic mechanical thermal analysis (DMTA), mechanical properties (flexural and impact strength), and water absorption. The presence of curaua fibers reduced some of the properties of the HDBPE, such as flexural and impact strength. DMTA showed that the presence of the fibers results in a more rigid material. The addition of LHPB to the formulation was efficient, leading to greater impact strength for the HDBPE/LHPB/fiber composite, as compared to the HDBPE/fiber composite. The addition of over 15% LHPB to the composite resulted in a poor mixture of the component, as evidenced by the flexural strength. The mechanical properties of the materials were not greatly influenced by their reinforcement with fibers treated with ionized air as a whole, showing that the process parameters can be further investigated to minimize the degradation of the materials. The use of a rubber with a higher average molar mass that the one currently used may have a greater effect on the impact strength. Longer fibers in equal mass proportions to those used in the present study can be tested, since shorter fibers mean a larger number of ends, which may act as stress concentrators and worsen some mechanical properties of the composite.