The use of natural fibres (e.g. flax, hemp etc.) instead of synthetic fibres (carbon and glass etc.) as composite reinforcements not only benefits the environment, but also provides economical lightweight products for transports. Although there are a few studies reported in literature on use of flax fibres, there is no comprehensive guide on use of flax fibres with bio-resins to re-engineer bio- composite systems that can be used in vehicle structures. The state-of-art of the current research towards using natural fibre reinforced composites is reviewed by the thesis. The review covers the performances of flax composites, concentrating on the effect of matrix types and existing development methods. The review also identifies the rational of selecting tannin resins and bio-epoxy resins to combine with flax fibre reinforcements. In the experimental work, mimosa tannin resin (natural phenolic resin) and pine- oil derived supersap epoxy resin are selected to manufacture the fully renewable flax composites. By tailoring the fibre configurations and chemical surface treatments, the resultant composites were investigated to provide information for engineers to understand the composite behaviours and properties. Mechanical properties (tension, flexural, shear, impact etc.) and physical properties (moisture, ageing etc.) were assessed through adequate tests and analysing methods. In addition, bio-sandwich structures based on the novel studied composites and commercial bio-foams were evaluated to study the energy absorption which could be very important in vehicle design. Based on the results, flax/supersap epoxy and flax/tannin composites are suitable for possible exterior structural and interior non-structural applications, respectively. The developed flax fibre composites with innovative bio-matrices have a potential to prevail in modern vehicle applications, due to the competitive performances, economic viability and environmental acceptability.

The content of this thesis was to draw up the literary owerview around Japanese quail breeding and fattening and to execute the practice experiment whitch aim was to analyse the efect of the inclusion of extruded flax seed to the diet for quails.

Les fibres naturelles telles que le coton et le lin sont utilisées depuis longtemps dans l'industrie textile. De plus, elles prennent de plus en plus d'importance dans l'industrie des composites comme substituants des fibres de verre, de carbone ou d'aramide. Cependant, les fibres naturelles doivent être modifiées pour surmonter certains inconvénients tels que l'inflammabilité, l'hydrophilie et l'oléophilie. Dans ce travail, les retardateurs de flamme (RF) phosphorés et fluoro-phosphorés sont greffés par bombardement électronique et par modification chimique sur des tissus de lin afin d’améliorer leur comportement au feu, l’hydrophobicité et l’oléophobie. L'effet de la composition chimique sur le greffage a été également évalué en utilisant des fibres de miscanthus comparativement aux tissus de lin. La réactivité de la double liaison C = C des monomères phosphorés est étudiée pour contrôler l’efficacité de greffage de différents RF. Les étapes du radiogreffage sont étudiées et contrôlées. L'efficacité de greffage a été évaluée par fluorescence X et analyse par rayons X à dispersion d'énergie (EDS) / microscopie électronique à balayage (SEM). La résonance magnétique nucléaire du proton est utilisée pour analyser l'effet de l'irradiation sur les différents monomères. Le comportement au feu des tissus modifiés est étudié en utilisant l’analyse thermogravimétrique, la microcalorimétrie de combustion, cône calorimètre et un test au feu préliminaire. Des tissus ignifuges et oléophobes ont été développés avec succès. / Many natural fibers have been used for a long time in textile industry as cotton and flax. Moreover, natural fibers are getting more importance in composites industry as a substitute for glass, carbon, or aramid fibers. However, they must be modified to overcome some disadvantages such as flammability, hydrophilicity and oleophilicity. In this work, phosphorus and fluoro-phosphorus flame retardants were grafted by e-beam radiation and chemical modification on flax fabrics to improve their flame retardancy, hydrophobicity and oleophobicity. The effect of chemical composition on grafting were also evaluated using miscanthus fibers in comparison to flax fabrics. The reactivity of the double bond C=C of the P-monomers was studied to control the grafting yield of various FRs. Radiation grafting steps were studied and controlled carefully. Grafting efficiency was assessed by X-ray fluorescence and Energy Dispersive X-Ray Analysis (EDX) / Scanning Electron Microscopy (SEM). Proton nuclear magnetic resonance was used to analyze the effect of irradiation on different monomers. Fire behavior of the modified fabrics was studied using thermogravimetric analysis, pyrolysis combustion flow calorimetry, cone calorimetry and a preliminary fire test. Flame retardant and oleophobic fabrics were successfully developed.

Avec les préoccupations environnementales actuelles, la recherche se tourne vers des solutions alternatives à l’utilisation de fibres synthétiques. Les fibres végétales apparaissent comme de bonnes candidates, avec de bonnes propriétés spécifiques. Cependant, leur faible durabilité constitue une problématique majeure, notamment lorsque les composites sont soumis à des sollicitations hygro(hygro)thermiques.L’objectif de cette thèse est donc d’analyser et de comprendre les mécanismes de dégradation au cours de sollicitations hydro-thermo-mécaniques, afin de réaliser un modèle prédictif de la durabilité de ces composites.Pour cela, le procédé de fabrication a été étudié et optimisé afin d’obtenir des composites robustes et répétables. Deux matériaux ont ainsi été fabriqués, différenciés par leurs taux volumiques de fibres, de 37.7 % et 51.1 %.Des campagnes expérimentales avaient pour but la caractérisation du comportement mécanique des matériaux sous différentes sollicitations. Un vieillissement hydrothermique a été étudié via des essais sous chargement monotone et des essais sous chargement cyclique (fatigue) en immersion in situ. Aussi, un vieillissement hygrothermique cyclique a été étudié afin de se rapprocher des conditions de service visées.Ces différentes campagnes expérimentales ont mis en évidence le fait que les composites étudiés présentent une forte chute de propriétés mécaniques en fonction du vieillissement, avec une influence finalement peu significative du taux volumique de fibres sur les propriétés après vieillissement, ce qui permet de questionner l’utilité industrielle d’atteindre ces taux volumiques de fibres.Les propriétés mécaniques élastiques sous chargement monotone après des cycles de sollicitations hygrothermiques sont stables après le premier cycle, ce qui peut être rassurant pour une utilisation de ces matériaux. En revanche, des endommagements semblent s’accumuler jusqu’à environ 4 cycles avant de se stabiliser.Les résultats en fatigue montrent également que la saturation peut améliorer la résistance en fatigue en dessous d’une certaine contrainte maximale appliquée, ce qui est particulièrement intéressant pour l’utilisation industrielle visée.Un modèle a pu être implémenté, intégrant l’évolution des propriétés mécaniques au cours de la diffusion, étudiée sur une surface. Ce modèle a permis non seulement de montrer que le matériau est globalement en compression, ce qui est cohérent avec le gonflement contraint des fibres dans la résine, notamment, mais également de mettre en évidence des développements qui seraient nécessaires afin d’aboutir à un modèle prédictif robuste, dont notamment des couplages forts en intégrant une modification de la diffusion en fonction de l’état de contraintes et de déformations des constituants.De nombreuses perspectives ont été discutées, notamment sur des campagnes expérimentales lors de sollicitations mécaniques multiaxiales ou avec des modes de rupture différents (choc, fluage). De plus, le modèle prédictif n’est pas encore atteint et des développements nécessaires ont été identifiés. / With the current environmental concerns, research turns to alternative solutions to synthetic fibres. Vegetal fibers appears as good candidates, with good mechanical properties. However, their low durability is a major issue, especially when the composites are exposed to hydro(hygro)thermal loadings.The purpore of this thesis is to analyse and understand the degradation mechanisms when hydro-thermo-mechanical loadings are applied, in order to implement a predictive modelisation of the composite durability.The manufacturing process wasstudied and optimised to produce reproducible and strong composites. Two materials were produced. Their only difference is their volumetric fiber contents (37.7 % and 51.1 %).Experimental campaigns were led to characterize the composite mechanical behavior under different loadings. A hydrothermal ageing was studied through monotonic mechanical testing and cyclic mechanical testing (fatigue) with in situ immersion. A hydrothermal ageing was also studied in order to be closer to the aimed service conditions.These differents test campaigns showed an important loss of mechanical properties with the ageing processes. The volumetric fiber contents also showed almost no difference after the hydrothermal ageing. The industrial use of a high fiber content can then be questionned.After the first hygrothermal cycle, the composite mechanical elastic properties were found constant, which is reassuring for an industrial use. However, damages accumulated throughout the first 4 cycles before stabilizing.Fatigue results showed that the saturation can enhance the fatigue resistance below a certain maximal loading, which is very interesting for the aimed industrial use.A surfacic numeric modelisation was implemented with the evolution of the mechanical properties thoughout the diffusion process. This modelisation showed that the composite is mostly in compression, which is expected from the constrained swelling of the fibers within the resin, but also showed some developpement ideas which would be necessary to achieve an accurate predictive modelisation. Among these ideas, strong coupling between the diffusion process and the internal strains/stresses of the components.Numerous perspectives were discussed. Multiaxial loadings or breakage mode with impact or creep tests were mentionned. Moreover, the predictive modelisation that was aimed was not achieved yet, but amelioration axes were identified.

Dans ce travail de thèse on a examiné expérimentalement l’efficacité épuratoire d’un dispositif de filtration, constitué de sable concassé et de nappes de géotextile en fibre de lin, à l’échelle de laboratoire afin d’installer en conditions locales (Agglomération Havraise) un site expérimental en vraie grandeur. Deux types d’essais ont été utilisés : (1) Des essais batch pour quantifier le potentiel de sorption des ions plomb, cuivre et zinc par les étoupes de fibres de lin à partir d'une solution aqueuse. (2) Des essais de filtration de longue durée dans des colonnes en laboratoire remplie de sable concassé avec et sans strates de géotextile en fibres de lin pour étudier l'influence de la présence de géotextiles sur le transfert et la rétention (i) des particules en suspension non polluées (particules de kaolinite) (ii) des métaux lourds solubles dans l'eau (iii) des métaux lourds sous forme particulaire (ions métalliques adsorbés sur les particules de kaolinite en suspension) et métaux lourds et solubles dans l'eau. Les essais de sorption ont montré que l'adsorption des ions métalliques par les fibres de lin est favorable avec une capacité d'adsorption maximale de 9,9 ; 10,7 et 8,4 mg g-1 respectivement pour le cuivre, le plomb et le zinc. Les essais de filtration ont montré que la présence des géotextiles dans le sable influence le transfert des métaux lourds, sous les deux formes soluble et particulaire. La rétention des métaux dans le sable est favorisée et les profils de rétention sont modifiés. De plus, et contrairement aux géotextiles synthétiques, les géotextiles en fibres de lin contribuent eux-mêmes à la rétention d’une fraction non négligeable de polluants métalliques sous forme soluble et particulaire dans leur propre structure. L’efficacité globale de rétention des métaux par le dispositif de filtration est améliorée. Ces résultats sont de bons indicateurs pour envisager l'utilisation de matériaux à base de fibre de lin dans la conception de systèmes de traitement local des eaux de ruissellement et l'élimination de polluants métalliques. / In this thesis work, the purification efficiency of a filtration device, consisting of crushed sand and flax fiber geotextile layers, was investigated experimentally at the laboratory scale in order to install in local conditions (Havre agglomeration) an experimental site in full size. Two types of tests were used: (1) Batch tests to quantify the sorption potential of lead, copper and zinc ions by flax fiber tows from an aqueous solution , (2) Long-term filtration tests in laboratory columns filled with crushed sand with and without flax fiber geotextile layers to study the influence of the presence of geotextiles on the transfer and retention of (i) particles in unpolluted suspension (kaolinite particles) (ii) water-soluble heavy metals (iii) heavy metals in particulate form (metal ions adsorbed on suspended kaolinite particles) and heavy and water-soluble metals. Sorption tests have shown that the adsorption of metal ions by flax fibers is favorable with a maximum adsorption capacity of 9.9; 10.7 and 8.4 mg g-1 respectively for copper, lead and zinc. Filtration tests have shown that the presence of geotextiles in sand influences the transfer of heavy metals, in both soluble and particulate forms. The retention of metals in the sand is favored and the retention profiles are modified. In addition, and unlike synthetic geotextiles, flax fiber geotextiles themselves contribute to the retention of a significant fraction of metal pollutants in soluble and particulate form in their own structure. The overall metal retention efficiency of the filtration device is improved. These results are good indicators for considering the use of flax fiber materials in the design of local stormwater treatment systems and the removal of metal pollutants.

Le lin (Linum usitatissimum L.) est une plante aux intérêts multiples. Sa tige est source de fibres, depuis longtemps utilisées dans le domaine du textile. Ce potentiel économique justifie la sélection variétale du lin en vue de développer des variétés plus riches en fibres et offrant une meilleure résistance aux maladies et la verse. Plus récemment, les fibres de lin ont vu leur utilisation s’étendre au renfort de matériaux composites grâce à leurs étonnantes propriétés mécaniques et morphologiques. Ces propriétés singulières s’expliquent grâce à leur développement et à leurs fonctions dans la tige. Ainsi, ce travail de thèse propose une caractérisation multi-échelle du lin, de la tige jusqu’à la paroi cellulaire de la fibre, afin de comprendre le lien entre les paramètres de croissance de la plante, le développement des fibres et leurs propriétés. L’architecture générale d’une tige de lin est explorée, ainsi que les conséquences de la sélection variétale sur cette structure et sur les propriétés des fibres. De plus, l’évolution des propriétés mécaniques des parois de fibres au cours de la croissance de la plante et de la phase de rouissage est caractérisée. En complément, la contribution des fibres à la rigidité en flexion d’une tige est mise en évidence, de même que leur rôle dans la résistance des tiges au flambage. Enfin, l’influence des conditions de culture sur les architectures des tiges et propriétés des fibres est étudiée par le biais de cultures en serre ou encore en simulant un phénomène de verse. Cette approche originale met en valeur les caractéristiques remarquables du lin qui en font un modèle de bioinspiration pour les matériaux composites de demain / Flax (Linum usitatissimum L.) is a plant with multiple interests. Its stem provides fibers, which have long been used in the textile industry. The economic potential of flax explains its varietal selection, aiming at developing varieties exhibiting higher fiber yields as well as greater resistance toward diseases and lodging. More recently, flax fibers have been dedicated to the reinforcement of composite materials due to their outstanding mechanical and morphological properties. These singular characteristics are related to fiber development and functions within the stem. Thus, the present work offers a multi-scale characterization of flax, from the stem to the fiber cell wall, in order to understand the link between plant growth parameters, the development of its fibers and their properties. The general architecture of a flax stem is investigated, as well as the impact of the varietal selection on this structure and on fiber performances. Moreover, changes in mechanical properties of fiber cell walls over plant growth and retting process are characterized. In addition, the fiber contribution to the stem stiffness is highlighted, as well as the fiber role in the resistance of the stem to buckling. The influence of culture conditions on stem architecture and fiber features is also studied through cultivations in greenhouse and by simulating a lodging event. This original approach emphasizes the uncommon characteristics of flax, which make this plant an instructive model toward future bioinspired composite materials.

<p>Pectinases are a group of enzymes produced by bacteria, fungi, higher plants and animals. Pectinases can modify and degrade pectins, a class of heterogeneous and multifunctional polysaccharides present in middle lamellae and primary cell walls of plants. Pectins have been showed to play diverse roles in cell physiology, growth, adhesion and separation. Pectinases are used technically in the processing of fiber production and fruit juice or wine making. We have studied the mechanisms and applications of pectinases, especially in retting, a microbiological process where bast fibers in flax and other bast fiber cultivars are released from each other and from the woody core.</p><p>A strong correlation was found between the ability to perform retting and the degradation of sparsely esterified pectin, a substrate of polygalacturonase. This led to the conclusion that polygalacturonase plays a key role in the enzymatic retting of flax. We purified and characterized an extracellular polygalacturonase produced by Rhizopus oryzae, a very potent retting organism. The purified enzyme which appeared to be the single active component in retting, has non-methylated polygalacturonan as its preferred substrate. Peptide sequences indicate that the enzyme, like another polygalacturonase (EC. 3.2.1.15), belongs to glycosyl hydrolase family 28. It contains, however, an N-terminal sequence absent from other fungal pectinases, but present in an enzyme from the phytopathogenic bacterium, Ralstonia solanacearum.</p><p>Our finding that removal of calcium ions from the plant material by pre-incubation in dilute acid in enzymatic retting could reduce enzyme consumption by several orders of magnitude, improves the economical feasibility of the enzymatic retting process. Comparisons with different acids showed that the action was mainly pH dependent.</p><p>Pectinases were employed as analytical tools in a study of stored wood discoloration and, together with cellulases, in a mechanical process for making pulp from flax and hemp in paper production. </p>

Pectinases are a group of enzymes produced by bacteria, fungi, higher plants and animals. Pectinases can modify and degrade pectins, a class of heterogeneous and multifunctional polysaccharides present in middle lamellae and primary cell walls of plants. Pectins have been showed to play diverse roles in cell physiology, growth, adhesion and separation. Pectinases are used technically in the processing of fiber production and fruit juice or wine making. We have studied the mechanisms and applications of pectinases, especially in retting, a microbiological process where bast fibers in flax and other bast fiber cultivars are released from each other and from the woody core. A strong correlation was found between the ability to perform retting and the degradation of sparsely esterified pectin, a substrate of polygalacturonase. This led to the conclusion that polygalacturonase plays a key role in the enzymatic retting of flax. We purified and characterized an extracellular polygalacturonase produced by Rhizopus oryzae, a very potent retting organism. The purified enzyme which appeared to be the single active component in retting, has non-methylated polygalacturonan as its preferred substrate. Peptide sequences indicate that the enzyme, like another polygalacturonase (EC. 3.2.1.15), belongs to glycosyl hydrolase family 28. It contains, however, an N-terminal sequence absent from other fungal pectinases, but present in an enzyme from the phytopathogenic bacterium, Ralstonia solanacearum. Our finding that removal of calcium ions from the plant material by pre-incubation in dilute acid in enzymatic retting could reduce enzyme consumption by several orders of magnitude, improves the economical feasibility of the enzymatic retting process. Comparisons with different acids showed that the action was mainly pH dependent. Pectinases were employed as analytical tools in a study of stored wood discoloration and, together with cellulases, in a mechanical process for making pulp from flax and hemp in paper production.

Thermoplastic composites using natural fibres are studied intensively and widely used in applications including automotive, packaging, consumer goods and construction. Good balance of mechanical properties, processability and low cost are great advantages of these materials on top of the environmental benefits. Recently, there have been various efforts to amplify the positive effects on the environment by replacing the conventional polymers by bio-derived renewable polymers in the composites. Recent studies conducted from our research group showed competitiveness of plant fibre-thermoplastic composites. Implementing the promising results and experience, a new composite design using renewable polyethylene as the matrix material was studied. This polyethylene is a renewable thermoplastic that was derived from sugar cane ethanol. The objectives of this study were to employ renewable high density polyethylene (HDPE) into composites using wheat straw and flax fibre to extend the range of properties of the HDPE while keeping the amount of renewable content to nearly 100%. The chemical resistance of these materials has not been reported before and it was investigated here by measuring and comparing the properties before and after accelerated chemical ageing. Both wheat straw and flax fibre had two different grades in size. Each of them was compounded with HDPE and additives (antioxidant and coupling agent) in a co-rotating twin screw extruder. The concentrations of fibres were varied from 0 to 30 wt-%. Then, injection molded samples were prepared for measurement of properties: tensile, flexural, impact tests. The effects of reinforcing fibre size were studied first. Both length and aspect ratio were considered. For both types of fibre composites, a general trend was observed. There was no clear evidence of improvements in flexural (strength and modulus) and tensile (strength, percentage elongation at break) properties with respect to the change in fibre size. However, impact (IZOD impact strength, Gardner impact failure energy) properties showed some improvements. This result was due to no substantial difference in size and aspect ratios in post-processed fibres that were actually residing in the matrix. There were remarkable improvements in flexural strength and modulus when the fibre content increased. However, minor decreases in tensile properties were observed. Furthermore, the impact properties were very sensitive to the concentration of fibres. As the fibre concentration went up, there were significant decreases in both IZOD impact strength and Gardner impact failure energy. Chemical resistance of these composites was studied by exposing them in six different chemical solutions (hydrochloric acid, acetic acid, sodium hydroxide, ethyl alcohol, industrial detergent, water) for up to thirty days. The increase in weight and leaching behaviour was observed. As the fibre content increased within the composites, the weight gain was more rapid during chemical ageing. Because there were more fibres exposed on the surface after chemical ageing, it is likely that they contributed to the higher flux of liquids (used for chemical ageing) inside the sample. Among the physical properties, tensile properties were most susceptible to the chemical ageing. One possible reason could be due to the exposed surface area to volume ratio, which was the highest in tensile bars and therefore faster mass transfer taking place into the matrix per volume. Finally, morphological study using scanned electron spectroscopy (SEM) revealed the damage on the surface when exposed to the chemicals. The fibres on the surface had been leached out in the sodium hydroxide solution leaving empty spaces. The fractured surface was also monitored via SEM. Though there was not enough evidence of strong interfacial interactions between the fibre and the polymer, good dispersions were observed.

Extrusion compounding addresses such problems as the non-homogeneity of the mixture and separation of fiber from the polymer during rotational molding, which consequently affect the mechanical and physical properties of the resulting composites. <p>Using triethoxyvinylsilane as chemical pre-treatment on flax fibers and linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) as polymer matrices, this study focused on the effects of flax fiber content (0%, 12.5% or 25%) and extrusion parameters such as barrel zone temperatures (75-110-120-130-140°C or 75-120-130-140-150°C) and screw speed (110 or 150 rpm) on the extrudate and composite properties (extrudate color, extrudate density, extrudate melt flow index, extrudate morphology, composite color, composite density, composite morphology, composite tensile strength and composite water absorption). <p>A mixture of chemically pre-treated flax fibers and powdered polyethylene matrices underwent extrusion compounding using a twin-screw extruder. The extrudates were then pelletized, ground, rotationally molded and cut into test specimens (composites). The mechanical and physical properties of both the extrudates and the composites from different treatments were then measured and compared. <p>Using multiple linear regression, models were generated to show quantitatively the significant effects of the process variables on the response variables. Finally, using response surface methodology and superposition surface methodology on the preceding data, the following optimum values for fiber content and extrusion parameters were determined: for LLDPE composites, fiber content = 6.25%, temperatures = 75-117.3-127.3-137.3-147.3°C, screw speed = 117.5 rpm; for HDPE composites, fiber content = 5.02%, temperatures = 75-118.1-128.1-138.1-148.1°C, screw speed = 125.56 rpm.