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

Polymeric composites reinforced with bio-materials have advantages over composites with synthetic reinforcements. Bio-based composites use low-cost and renewable reinforcements, have nonabrasive properties for machining, have improved damping characteristics, and have potential for energy recycling. However, the limited use of bio-based composites is because their mechanical properties are typically much lower than those of synthetic composites. The objective of this study was to combine state-of-the-art imaging tools with emerging numerical modeling methods for an integrated, multi-level characterization of bio-based reinforcements and their composites. Digital photography (2D) will allow collection of full-field digital images of the surface of sample composites, which will be used for characterization of the morphological structure of fillers (copper wire or wood particle) and of model composites. Mechanical experiments (tension load) on isolated fillers and on model composites will allow imaging of the deformed material. By correlating relative positions of thousands of surface features between consecutive images, digital image correlation (DIC) algorithms can be used to map surface deformation fields and calculate surface strain fields. Digital imaging methods can only record deformations and strains. The interpretation of those strains in terms of material properties, such as position-dependent modulus of a heterogeneous composite material, requires simultaneous modeling. The modeling must use morphology-based methods that can handle anisotropy, heterogeneity, and the complex structure of bio-based composites such as wood plastic composites. This research used the material point method (MPM) as a modeling tool. MPM is a particle-based, meshless method for solving problems in computational mechanics. The crucial advantage of MPM over other methods is the relative ease of translating pixels from digital images into material points in the analysis. Thus digital images (2D) used in our experiments were used as direct input to the MPM software, so that the actual morphologies, rather than idealized geometries, were modeled. This procedure removes typical uncertainties connected with idealization of the internal features of modeled materials. It also removes variability of specimen to specimen due to morphology variations. Full-field imaging techniques and computer modeling methods for analysis of complex materials have developed independently. This research Coupled imaging and modeling and used inverse problem methodology for studying bio-particulate composites. The potential of coupling experiments with morphology-based modeling is a relatively new area. This work studied the morphology and mechanical properties of copper wire (for validation experiments) and wood particles used for reinforcement in polymer composites. The goal was to determine the in situ mechanical and interfacial properties of copper wire and then wood particles. By comparison of DIC results to MPM, the conclusion is MPM simulation works well by simulating 3D composite structure and using Matlab software to do qualitative and quantitative comparisons. Copper validation tests showed that copper wire is too stiff compared to polymer such that the inclusion modulus had low effect on the surface strains (DIC experimental results). Wood particle worked better because modulus of wood is much lower than copper. By qualitative comparison of the wood particle specimens, we could deduce that the in situ properties of wood particles are lower than bulk wood. Quantitative analysis concentrated on small area and got more exact results. In a 90 degree particle quantitative study, MPM simulations were shown to be capable of tracking the structure of wood particle plastic, which involved failure. The entire approach, however, is not very robust. We can get some results for mechanical properties, but it does not seem possible to extract all anisotropic properties from a few DIC tests, as some researcher have suggested. / Graduation date: 2012

The current sensitiveness about environment, sustainable development and petroleum depletion restrictions, are promoting new research in the field of high environmental efficiency materials and technologies. In the last decades, important advances in the field of renewable and/or biodegradable polymers have been reached; nevertheless, these polymers still find some restrictions at industrial scale. On the other hand, with the aim of protecting forests areas, legislation is promoting the development of polymer materials and composites that could potentially substitute wood. These materials, called Wood Plastic Composites (WPC), combine a polymeric matrix, mainly from petroleum-based polymers, with a reinforcement that comes from the wastes generated by the wood industry. Currently, the concept of WPCs has been widened including any polymer (independently from its origin and/or biodegradability) and any lignocellulosic component coming from industry. The present work has been focused on the development, formulation, analysis and optimization of WPCs from a renewable polymer matrix, polylactic acid (PLA) and lignocellulosic reinforcements from hazelnut shell flour wastes (HSF). Due to the intrinsic fragility of PLA and its low impact resistance, new formulations containing epoxidized linseed oil (ELO) have been developed. The obtained results show that the hazelnut shell flour allows obtaining stiffer materials, as much as stiffer as the hazelnut shell flour content increases. On the other hand, the impact strength decreases with increasing hazelnut shell flour with regard to neat PLA. The results also suggest that epoxidized linseed oil (ELO) provides a dual effect: on one hand its plasticization effect is evident as the glass transition temperature (Tg) is reduced due to increased polymer chain mobility. On the other hand, the obtained results also suggest a compatibilizing effect, due to the interactions between the oxirane groups in ELO and the hydroxil groups in both lignocellulosic filler and terminal groups in PLA chains. Addition of ELO improves in a remarkable way the overall properties of these biocomposites. This research also assesses the effect of the water uptake and the biodegradation or disintegration in compost conditions, to offer a range of formulations with high potential technology transfer to industry. / La actual sensibilidad por el medio ambiente, el desarrollo sostenible y las limitaciones de los recursos fósiles, están propiciando que la tecnología de materiales dirija sus investigaciones al desarrollo de materiales de alto rendimiento ambiental. En las últimas décadas se han conseguido grandes avances en polímeros de origen renovable y/o biodegradables, aunque todavía encuentran ciertas limitaciones a nivel industrial. Por otro lado, la protección de las áreas forestales, desde el plano legislativo, está impulsando el desarrollo de materiales plásticos y compuestos que imitan el acabado de la madera. Estos materiales, conocidos como Wood Plastic Composites (WPC), combinan una matriz polimérica, fundamentalmente de origen petroquímico, con un refuerzo procedente de residuos de la industria maderera. Actualmente, el concepto de WPCs se ha ampliado y contempla cualquier tipo de matriz polimérica (independientemente de su origen y/o biodegradabilidad) y cualquier componente de tipo lignocelulósico procedente de diversas industrias. El presente trabajo se ha centrado en el desarrollo, formulación, análisis y optimización de WPCs basados en matrices poliméricas de origen renovable, ácido poliláctico (PLA) y refuerzos lignocelulósicos procedentes de la cáscara de avellana en forma de harina. Dada la fragilidad intrínseca del PLA y su baja resistencia al impacto se han desarrollado formulaciones con plastificantes de alto rendimiento medioambiental derivados de aceite de linaza epoxidado (ELO). Los resultados obtenidos indican que la harina de cáscara de avellana permite obtener materiales más rígidos cuanto mayor es su contenido. A medida que se incrementa el contenido de harina de cáscara de avellana, la energía de impacto del compuesto disminuye con respecto a la del PLA virgen. Los resultados demuestran que el plastificante de aceite de linaza epoxidado (ELO) ofrece un efecto dual: por un lado, actúa como plastificante, con la consiguiente reducción de la temperatura de transición vítrea (Tg) e incremento de movilidad de cadenas poliméricas. Por otro lado, los resultados sugieren un efecto compatibilizante, resultado de la interacción de los grupos oxirano del ELO con los grupos hidroxilo del refuerzo lignocelulósico y con grupos terminales de la cadena de PLA. La incorporación de aceite de linaza epoxidado mejora sustancialmente las propiedades globales de los biocompuestos. Esta investigación también revisa el efecto de la humedad en los procesos de absorción de agua, así como la biodegradación o desintegración en condiciones de compostaje, ofreciendo un grupo de formulaciones con alto potencial de transferencia a escala industrial. / L'actual sensibilitat pel medi ambient, el desenvolupament sostenible i les restriccions lligades als recursos fòssils, estan propiciant que la tecnologia de materials dirigisca les seues recerques cap al desenvolupament de materials d'alt rendiment ambiental. En les últimes dècades s'han aconseguit importants avanços en polímers d'origen renovable i/o biodegradables, malgrat que encara troben certes limitacions a nivell industrial. D'altra banda, amb l'objectiu de protegir les àrees forestals, la legislació està, també, propiciant el desenvolupament de materials plàstics i compòsits que imiten l'aparença de la fusta. Aquests materials, coneguts com Wood Plastic Composites (WPC), combinen una matriu polimèrica, fonamentalment d'origen petroquímic, amb un reforç procedent de residus de la indústria de la fusta. Actualment, el concepte de WPCs s'ha ampliat i contempla qualsevol tipus de matriu polimèrica (independentment del seu origen i/o biodegradabilidad) i qualsevol component de tipus lignocel·lulòsic procedent de diverses indústries. El present treball s'ha centrat en el desenvolupament, formulació, anàlisi i optimització de WPCs basats en matrius polimèriques d'origen renovable, àcid polilàctic (PLA) i reforços lignocel·lulòsics procedents de la corfa d'avellana en forma de farina. Donada la fragilitat intrínseca del PLA i la seua baixa resistència a l'impacte, s'han desenvolupat formulacions amb plastificants d'alt rendiment mediambiental derivats de l'oli llinós epoxidat (ELO). Els resultats obtinguts indiquen que la corfa d'avellana, en forma de farina, permet obtindré materials més rígids, tant més quan major és la quantitat de farina de corfa d'avellana. A mesura que s'incrementa el contingut en farina de corfa d'avellana, l'energia d'impacte disminueix en comparació amb el PLA verge. Els resultats obtinguts demostren que el plastificant d'oli llinós epoxidat (ELO) ofereix un efecte dual: per una banda, actua com a plastificant, amb la associada disminució de la temperatura de transició vítria (Tg) i l'increment de la mobilitat de les cadenes. Per altra banda, els resultats suggereixen un efecte compatibilitzant, resultat de les interaccions entre els grups oxirà de l'ELO amb els grups hidroxil del reforç lignocel·lulòsic i els grups terminals en les cadenes polimèriques de PLA. La incorporació d'oli llinós epoxidat millora substancialment les propietats globals dels biocompòsits. Aquest recerca també revisa l'efecte de la humitat en els processos d'absorció d'aigua així com la biodegradació o desintegració en condicions de compostatge, oferint un grup de formulacions amb alt potencial de transferència a escala industrial. / Balart Gimeno, JF. (2017). Desarrollo y caracterización de WPCs basados en ácido poliláctico (PLA) y refuerzos derivados de la cáscara de avellana [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/85982 / TESIS