Le hêtre est une essence très répandue sur le territoire français et plus particulièrement dans la région Grand-Est. Toutefois, son bois est peu exploité, notamment pour des utilisations en conditions extérieures en raison de sa faible durabilité et son instabilité dimensionnelle. Pour favoriser et développer son utilisation, il est nécessaire de le traiter afin de limiter sa reprise en humidité et de le protéger contre les champignons de pourriture. Par ailleurs, la réglementation actuelle sur les produits de traitement du bois impose la mise au point de solutions alternatives respectueuses de l’environnement et de la santé. Dans ce cadre, les travaux développés durant cette thèse visent la valorisation du hêtre en tant que matériau via sa protection par un traitement « non-biocide », la furfurylation. Cette méthode consiste à polymériser in situ de l’alcool furfurylique dans le bois de hêtre. La mise au point du procédé a permis d’aboutir à du hêtre composite dont la durabilité et la stabilité dimensionnelle sont nettement améliorées. D’autre part, le hêtre est une essence feuillue pour laquelle la fraction hémicellulosique est riche en pentoses et plus précisément en xylose, précurseur de furfural. Des travaux ont donc été menés pour produire du furfural par hydrodistillation acide à partir de connexes issus de l’industrie de la première transformation du hêtre. Le furfural a ensuite été réduit en alcool furfurylique par transfert d’hydrogène. Les résultats prometteurs obtenus montrent qu’il est possible de mettre en place une filière locale alliant le hêtre comme source de molécules furaniques et le bois de hêtre comme matériau / Beech is a wood species present in the French territory, particularly in the Grand-Est region. However, beech is a under used wood, especially for outdoor uses, because it is non durability and it is dimensional unstability. To promote and develop its use, it is necessary to limit its recovery in moisture and treat to protect it against fungi decay. Futhermore, current regulation on wood treatment products imposes the development of alternative wood treatments more respectful of the environment and health. In this context, the work developed during this thesis is focused on valorisation of beech as a material through its protection by a “non-biocide” treatment, furfurylation. This method consists in an polymerisation in situ by heating a furfuryl alcohol solution into beech solid wood. The development of process led to a bio-based beech composite with significantly improved durability and dimensional stability.On the other hand, beech is a hardwood species in which the hemicellulosic fraction is rich in pentoses, and more precisely in xylose, precursor of furfural. Work has been done to produce furfural by acidic steam distillation, from beech primary wood processing by products. This molecule is then chemically reduced to furfuryl alcohol by hydrogen transfer.These promising results to show that it is possible to set up a local production combining beech as a local source of furanic molecules and beech wood as a solid material

Biobased materials made from renewable resources, such as wood, play an important role in the sustainable development of society. One main challenge of biobased building materials is their inherent moisture sensitivity, a major cause for fungal decay, mold growth and dimensional instability, resulting in decreased service life as well as costly maintenance. A new building material known as wood-plastic composites (WPCs) has emerged. WPCs are a combination of a thermoplastic matrix and a wood component, the former is usually recycled polyethylene or polypropylene, and the latter a wood processing residual, e.g. sawdust and wood shavings. The objective of this thesis was to gain more insight about characteristics of WPCs containing a modified wood component. The hypothesis was that a modified wood component in WPCs would increase the moisture resistance and durability in outdoor applications. The study comprises both injection molded and extruded WPC samples made with an unmodified, acetylated, thermally modified or furfurylated wood component in a polypropylene (PP), high density polyethylene (HDPE), cellulose ester (CAP, a cellulose ester containing both acetate and propionate substituents) or polylactate (PLA) matrix. The WPCs were prepared with 50-70 weight-% wood. The emphasis was on studying the moisture sorption, fungal resistance and micromorphological features of these new types of composites. Water sorption in both liquid and vapor phases was studied, and the biological performance was studied both in laboratory and in long term outdoor field tests. Micromorphological features were assessed by analyzing of the wood component prior to and after processing, and by studying the composite microstructure by means of a new sample preparation technique based on UV excimer laser ablation combined with scanning electron microscopy (SEM). Results showed that the WPCs with a modified wood component had a distinctly lower hygroscopicity than the WPCs with unmodified wood, which resulted in less wood-plastic interfacial cracks when subjected to a moisture soaking-drying cycle. Durability assessments in field and marine tests showed that WPCs with PP or CAP as a matrix and 70 weight-% unmodified wood degraded severely within a few years, whereas the corresponding WPCs with a modified wood component were sound after 7 years in field tests and 6 years in marine tests. Accelerated durability tests of WPCs with PLA as a matrix showed only low mass losses due to decay. However, strength losses due to moisture sorption suggest that the compatibility between the PLA and the different wood components must be improved. The micromorphological studies showed that WPC processing distinctly reduces the size and changes the shape of the wood component. The change was most pronounced in the thermally modified wood component which became significantly reduced in size. The disintegration of the modified wood components during processing also creates a more homogeneous micromorphology of the WPCs, which may be beneficial from a mechanical performance perspective. Future studies are suggested to include analyses of the surface composition, the surface energy and the surface energy heterogeneity of both wood and polymer components in order to tailor new compatible wood-polymer combinations in WPCs and biocomposites. / <p>QC 20121119</p>

<p>Wood plastic composite (WPC) materials have seen a continuous market growth worldwide in the last decade. So-called extruded WPC profiles are today mainly used in outdoor applications, e.g. decking, railing and fencing. In outdoor conditions, moisture sorption in the wood component combined with temperature induced movements of the polymer matrix causes deformations of such composites. On the macroscopic scale this may lead to unacceptable warp, cup and bow of the WPC products, but on a microscopic scale, the movements will cause interfacial cracks between the particles and the matrix, resulting in little or no ability to transfer and re-distribute loads throughout the material. Moisture within the composite will also allow fungi and micro organisms to attack the wood particles.</p><p>The conceptual idea of this work is to use a chemically modified wood component in WPCs to enhance their long term performance. These chemically modified wood particles exhibit reduced susceptibility to moisture, resulting in better dimensional stability and a higher resistance to biological degradation as compared to that of unmodified wood. The objective of this thesis is to study the effects of using modified wood in WPCs on their moisture sorption behaviour, micromorphology and microbiological durability. The modification methods used were acetylation, heat treatment and furfurylation.</p><p>Equilibrium moisture content (EMC) and sorption behaviour of WPCs were determined by water vapour sorption experiments. The use of thin sections of the composites enabled EMC to be reached within a comparably short time span. The micromorphology was studied by LV-SEM (low vacuum-scanning electron microscope) using a specially designed sample preparation technique based on UV laser. The biological durability was evaluated by laboratory fungal test methods.</p><p>The moisture sorption experiments showed lower moisture levels for all the composites when modified wood particles were used. This was also reflected in the micromorphological studies where pronounced wood-plastic interfacial cracks were formed due to moisture movement in the composites with unmodified wood particles. The sample preparation technique by UV laser proved to be a powerful tool for preparing surfaces for micromorphological studies without adding mechanical defects caused by the sample preparation technique itself. Results from the durability test showed that WPCs with modified wood particles are highly resistant to decay by fungi.</p>

Despite many excellent properties of wood which make it suitable for many applications, it suffers from a number of disadvantages limiting its use. For instance, modification is needed to reduce water sorption and to improve decay resistance, dimensional stability and weathering performance. In addition, wood/liquid interaction such as water wettability on wood plays an important role in design and characteristics of many processes and phenomena such as adhesion, coating, waterproofing, wood chemical modification, and weathering. This thesis focuses on enhancing the understanding of wetting of wood, with emphasis on modified wood. The influence of surface chemical composition of wood and its microstructural characteristics on wetting and swelling properties has also been studied. A multicycle Wilhelmy plate technique has been developed to evaluate wetting properties of porous materials, such as wood, in which the samples were subjected to repeated immersions and withdrawals in a swelling liquid (water) and in a non-swelling liquid (octane). This method was utilized to dynamically investigate contact angle, sorption and swelling properties, as well as dimensional stability of unmodified, chemically and surface modified wood samples. Scots pine sapwood and heartwood samples were utilized to establish the principles of the technique. Acetylated and furfurylated wood samples with different level of modification were thereafter examined utilizing the developed technique for wetting measurements. A perimeter model based on a linear combination of the measured force and final change in sample perimeter was suggested to evaluate the dynamic dimensional stability of wood veneers. The feasibility of this method for studying dynamic wettability was investigated by measuring the changes of advancing and receding contact angles over repeated cycles on surface modified wood samples, created by combining liquid flame spray and plasma polymerisation methods. X-ray photoelectron spectroscopy (XPS) and X-ray computed tomography (XCT) were employed to study the surface chemical composition and microstructural properties of the samples, respectively. Three different kinetic regimes were observed in the wetting measurements: i) fast wetting and spreading of the liquid on the wood surface, ii) void filling and wicking and iii) swelling, which was the slowest of the three. The multicycle Wilhelmy plate method was found to be suitable for studying liquid penetration, sorption, and dimensional stability of swelling materials. The results demonstrate that the wetting properties of wood are highly affected by surface chemistry and microstructure. It was shown that using both swelling and non-swelling liquids in wetting measurements allow to distinguish between capillary liquid uptake and swelling. Based on this, for chemically modified samples, it was demonstrated that acetylation mostly reduces swelling, while furfurylation reduces both swelling and capillary uptake. This is in line with the microstructural study with X-ray computed tomography where a significant change in the porosity was found as a result of furfurylation, conversely acetylation left the total porosity values unchanged. Wetting results for hydrophobised wood samples demonstrate that the multi-scale roughness obtained by combination of nanoparticle coating and plasma polymerization increased both the hydrophobicity and the forced wetting durability compared to the micro-scale roughness found on wood modified with plasma polymerisation alone. / <p>QC 20151029</p> / Sustainable wood modification

Wood plastic composite (WPC) materials have seen a continuous market growth worldwide in the last decade. So-called extruded WPC profiles are today mainly used in outdoor applications, e.g. decking, railing and fencing. In outdoor conditions, moisture sorption in the wood component combined with temperature induced movements of the polymer matrix causes deformations of such composites. On the macroscopic scale this may lead to unacceptable warp, cup and bow of the WPC products, but on a microscopic scale, the movements will cause interfacial cracks between the particles and the matrix, resulting in little or no ability to transfer and re-distribute loads throughout the material. Moisture within the composite will also allow fungi and micro organisms to attack the wood particles. The conceptual idea of this work is to use a chemically modified wood component in WPCs to enhance their long term performance. These chemically modified wood particles exhibit reduced susceptibility to moisture, resulting in better dimensional stability and a higher resistance to biological degradation as compared to that of unmodified wood. The objective of this thesis is to study the effects of using modified wood in WPCs on their moisture sorption behaviour, micromorphology and microbiological durability. The modification methods used were acetylation, heat treatment and furfurylation. Equilibrium moisture content (EMC) and sorption behaviour of WPCs were determined by water vapour sorption experiments. The use of thin sections of the composites enabled EMC to be reached within a comparably short time span. The micromorphology was studied by LV-SEM (low vacuum-scanning electron microscope) using a specially designed sample preparation technique based on UV laser. The biological durability was evaluated by laboratory fungal test methods. The moisture sorption experiments showed lower moisture levels for all the composites when modified wood particles were used. This was also reflected in the micromorphological studies where pronounced wood-plastic interfacial cracks were formed due to moisture movement in the composites with unmodified wood particles. The sample preparation technique by UV laser proved to be a powerful tool for preparing surfaces for micromorphological studies without adding mechanical defects caused by the sample preparation technique itself. Results from the durability test showed that WPCs with modified wood particles are highly resistant to decay by fungi. / QC 20101116