Syftet med detta examensarbete var att utveckla ett hållbart ersättningsmaterial till akrylnitrilbutadienstyren plast (ABS), genom att applicera principerna för grön kemi och teknik. ABS är en icke-nedbrytbar plast som till exempel används i slagtåliga produkter för hyttinteriörer. Att utveckla ett nytt material baserat på en kravspecifikation med en specifik produkt i åtanke är av stor betydelse då en initial teoretiska utvärdering kan ge resultat som driver ytterligare innovation och säkerställer en god överensstämmelse med förväntningarna på produkten. Baserat på den genomförda litteraturutvärderingen och kravspecifikationen för produkten valdes polylaktid (PLA) som matrismaterial och blandades med nanofibrer av lignocellulosa (LCNF) och naturgummi (NR), där maleinsyraanhydrid (MA) användes som kompatibilisator. Denna modifieringsstrategi syftade till att förbättra PLAs styrka och minska dess sprödhet. Flera olika parametrar undersöktes, vilka inkluderar olika torkningsmetoder för LCNF:en och olika metoder för MA tillsats före bearbetningen av blandningen. Termisk analys av blandningarna visade att tillsatsen av LCHF och NR inte påverkar nedbrytningstemperaturen för PLA-matrisen i någon större utsträckning, men att kristalliniteten påverkades av dem och de olika behandlingsmetoderna. Styvheten hos de PLA-baserade materialen var likvärdig ABS, medan elasticitet var generellt likvärdig PLA och där tillsatsen av naturgummi förbättrade materialens deformationskapacitet. SEM bilder indikerade att de tre komponenterna var kompatibiliserade, då fibrösa strukturer och sammanflätade nätverk av LCNF och NR i PLA-matrisen kunde observeras. SEM bilderna visade också att NR agglomererade då stora agglomerat och porösa strukturer uppstod, vilket understryker vikten av att optimera framtida blandningsstrategier. En livscykelbedömning (LCA), enligt en vagga-till-graven metod, förväntas visa lägre koldioxidutsläpp för det föreslagna alternativet jämfört med ABS tack vare tillämpningen av principerna för grön kemi vid produktutformningen. Detta bekräftar den ursprungliga hypotesen om en ökad miljövänligheten hos PLA-baserade ersättningsmaterial jämfört med ABS. / This thesis aims to develop sustainable replacement for Acrylonitrile Butadiene Styrene (ABS) in high-impact applications within construction equipment’s Cab interior. Adhering to the principles of Green Chemistry and Engineering, the study focused on developing and accessing an environmentally friendly substitute for ABS, a commonly used non-biodegradable plastic. Investigating novel materials with a tailored requirements list is vital in materials science and engineering. Theoretical approaches can yield results which drive further innovation, ensuring comprehensive alignment with application expectations through a holistic approach to address critical factors. Following this guideline, the chosen alternative was Polylactide (PLA), fortified with a blend of lignocellulose nanofibers (LCNFs) and natural rubber (NR) at a 10 wt.% concentration, with the addition of Maleic Anhydride (MA) as a compatibilizer. This modification strategy aimed to enhance PLA's strength and reduce its brittleness. The investigation encompassed various parameters, including different LCNF drying methods and variations in additive treatment before melt-mixing with PLA. The outcomes from thermal analysis indicated that the inclusion of reinforcements does not significantly affect the degradation temperature of the PLA matrix. Crystallinity, on the other hand, was found to be influenced by the presence of lignocellulose reinforcements and natural rubber, with intriguing nuances emerging from the interplay of these components and different treatment methods. PLA-based alternatives performed similarly to low grade ABS and had similar stiffness levels. In terms of elasticity, most materials behaved similarly to neat PLA, but the addition of natural rubber enhanced their deformation capacity. Successful compatibilization between lignocellulose reinforcements, natural rubber, and PLA was assumed from the observed fibrous structures and interwoven networks within the PLA matrix. Additionally, the presence of aggregates and porous structures highlighted the challenges posed by rubber agglomeration. Finally, the observation of larger agglomerates beyond typical interphase sizes raised concerns about brittle behavior, emphasizing the need for optimizing blend toughening strategies. The input for a Life Cycle Assessment (LCA), following a cradle-to-gate approach, is anticipated to show lower carbon emissions for the proposed alternative in comparison to ABS due to the principles of Green Engineering applied in the product design, denoting the environmental viability of the PLA-based substitute.

Lignin als nachwachsendes, erneuerbares Biopolymer, welches als Nebenprodukt in der Zellstoffindustrie anfällt, besitzt das Potenzial Materialien auf der Basis von endlichen, fossilen Rohstoffen ganz oder teilweise zu ersetzen. Ziel der Arbeit war es Adsorptionsmaterialien auf der Basis von Lignin in Form von Hydrogelen herzustellen und ihre Adsorptionseigenschaften zu untersuchen. Hierfür wurden zunächst verschiedene technische Lignine (Kraftlignine, Ligninsulfonate und Sodalignine) eingehend charakterisiert, zu Hydrogelen vernetzt und die Adsorptionseigenschaften an den Metallionen Cu(II), Ni(II) und Zn(II) untersucht. Weiterhin wurde der Einfluss der Fraktionierung des Lignins auf die Adsorptionseigenschaften der resultierenden Ligninhydrogele untersucht. Hierfür wurde das Kraftlignin mittels Aceton : Wassermischungen über die unterschiedliche Löslichkeit der Fraktionen aufgetrennt. Die Fraktionierung des Ligninsulfonates erfolge über die Membranfiltration, bei der ein Reinigungsschritt mit kleinem Porendurchmesser vorausgesetzt wurde. Durch chemische Modifizierung des Ausgangslignins konnten die Adsorptionseigenschaften des Ligninhydrogels verändert werden. Hierfür wurden drei verschiedene Synthesewege durchgeführt: Die Einbringung von Dihydroxybenzol über eine sauerkatalysierte Substitutionsreaktion, das Anbinden von Iminodiessigsäure über die Mannich-Reaktion und mittels Epichlorhydrin, sowie die Einbringung von stickstofffunktionellen Gruppen mittels oxidativer Ammonolyse. Ferner wurden weitere Eigenschaften wie die Zyklenstabilität und Selektivität der Ligninhydrogele untersucht. Die während der Adsorption ablaufenden die Schrumpf- und Quelleigenschaften des Hydrogels konnten ausgenutzt werden, um ein Konzept für ein Sensorsystem zu entwickeln. Dazu wurde das Ligninhydrogel an kovalent an einen ITO-Träger angebunden und die Schrumpf- und Quellprozesse mittels QCM am Beispiel von verschieden konzentrieren Magnesium- und Natriumionenlösungen untersucht. An Aerogelen, welche durch Gefriertrocknung aus dem Kraftligninhydrogel hergestellt wurden, konnten weiterhin die Adsorption von Rohöl gezeigt werden. Außerdem wurde eine Maßstabsvergrößerung der Hydrogelsynthese von 5 g auf 1 kg durchgeführt.:Inhaltsverzeichnis Abkürzungsverzeichnis Formelzeichenverzeichnis Abbildungsverzeichnis Tabellenverzeichnis 1 Motivation und Zielstellung 2 Theorie 2.1 Lignin 2.1.1 Aufbau 2.1.2 Isolierungsmethoden 2.1.2.1 Kraftaufschluss 2.1.2.2 Sulfitaufschluss 2.1.2.3 Sodaaufschluss bzw. Alkaliaufschluss 2.1.3 Anwendungspotenzial des Lignins 2.1.4 Fraktionierung des Lignins 2.1.5 Modifizierung des Lignins 2.2 Hydrogele 2.2.1 Ligninhydrogele 2.2.2 Anwendung von Ligninhydrogelen 2.3 Adsorption 2.3.1 Adsorptionsparameter 2.3.2 Ionenaustauscher 2.3.3 Selektivität 2.4 Metallionen 2.4.1 Toxikologie und Abscheidung von Schwermetallen 2.4.2 Adsorption von Metallionen an Materialien auf Ligninbasis 3 Ergebnisse und Diskussion 3.1 Hydrogele aus Ligninen unterschiedlichen Ursprungs 3.1.1 Charakterisierung der Lignine 3.1.2 Synthese und Charakterisierung der Ligninhydrogele 3.1.3 Vergleich der Adsorptionskapazitäten der Ligninhydrogele 3.1.4 Fazit zur Hydrogelsynthese aus unterschiedlichen Ligninen 3.2 Adsorptionseigenschaften der Ligninhydrogele am Beispiel von Ca-HG und LS-HG 3.2.1 Bestimmung thermodynamische Kenngrößen 3.2.2 Bestimmung kinetische Kenngrößen 3.2.3 Äußere Einflussfaktoren 3.2.4 Fazit zur Untersuchung der Adsorptionseigenschaften 3.3 Fraktionierung ausgewählter Lignine 3.3.1 Fraktionierung des Kraftlignins KL mittels Lösungsmittelgradienten 3.3.1.1 Charakterisierung der fraktionierten Lignine 3.3.1.2 Synthese und Charakterisierung der fraktionierten Ligninhydrogele 3.3.1.3 Zwischenfazit Fraktionierung von KL 3.3.2 Fraktionierung des Ligninsulfonates LSE mittels Membranfiltration 3.3.2.1 Entfernung von Zuckern und schwefliger Säure aus der Dicklauge 3.3.2.2 Charakterisierung der fraktionierten Lignine 3.3.2.3 Charakterisierung und Vergleich der Adsorptionskapazitäten der fraktionierten Ligninhydrogele 3.3.2.4 Zwischenfazit zur Fraktionierung von LSE 3.3.3 Fazit zur Fraktionierung von Lignin 3.4 Chemische Modifizierung der Kraftlignine 3.4.1 Modifizierung mit Dihydroxybenzol 3.4.1.1 Charakterisierung der modifizierten Ligninhydrogele 3.4.1.2 Vergleich der Ligninhydrogele aus fraktioniertem Kraftlignin aus KL 3.4.1.3 Fazit der Modifizierung mit Dihydroxybenzenen 3.4.2 Modifizierung durch oxidative Ammonolyse 3.4.2.1 Charakterisierung der modifizierten Lignine 3.4.2.2 Charakterisierung und Vergleich der Adsorptionskapazitäten der modifizierten Ligninhydrogele 3.4.2.3 Fazit der Modifizierung mittels oxidativer Ammonolyse 3.4.3 Modifizierung mit Iminodiessigsäure 3.4.3.1 Charakterisierung der modifizierten Lignine 3.4.3.2 Charakterisierung und Vergleich der Adsorptionskapazitäten der modifizierten Ligninhydrogele 3.4.3.3 Fazit der Modifizierung mittels Iminodiessigsäure 3.5 Vergleich der Aufnahmekapazitäten der hergestellten Ligninhydrogele mit der Literatur 3.6 Anwendungsorientierte Untersuchungen 3.6.1 Ligninhydrogele als Adsorber für die Sorption von Metallionen aus wässrigen Medien 3.6.1.1 Zyklenstabilität des Säulenmaterials 3.6.1.2 Selektive Adsorption von Cu(II)-Ionen 3.6.1.3 Fazit aus der Verwendung von Ligninhydrogelen als Adsorber für Metallionen aus wässrigen Lösungen 3.6.2 Ligninhydrogele für Sensoranwendungen 3.6.2.1 Anbindung des Ligninhydrogels an einen Glasträger 3.6.2.2 Untersuchung des Ansprechverhalten des Ligninhydrogelsensors 3.6.2.3 Fazit der Verwendung von Ligninhydrogelen als Sensormaterial 3.6.3 Aerogele aus Kraftligninhydrogelen für die Sorption von Ölen 3.6.3.1 Synthese und Charakterisierung des Aerogels 3.6.3.2 Vergleich mit anderen Materialien aus nachwachsenden Rohstoffen 3.6.3.3 Fazit der Verwendung von Aerogelen aus Ligninhydrogelen für die Adsorption von Öl 3.6.4 Upscaling der Hydrogelsynthese 3.6.4.1 Planung und Aufbau der Syntheseanlage 3.6.4.2 Überprüfung der Anforderungen der Hydrogelsyntheseanlage 3.6.4.3 Fazit zum Upscaling der Hydrogelsynthese 4 Zusammenfassung und Ausblick 5 Experimentalteil 5.1 Chemikalien und Materialien 5.2 Lignine und Fraktionierung des Lignins 5.3 Modifizierung des Lignins 5.4 Synthese der Hydrogele, Aerogele und Xerogele 5.5 Anbindung des Ligninsulfonates an den Glasträger 5.6 Synthese von Referenzmaterialien 5.7 Vorversuche für die Herstellung der Hydrogelsyntheseanlage 5.8 Adsorptionsversuche 5.9 Analytische Methoden 6 Anhang 7 Literatur

In this paper, biochemicals with the potential to substitute fossil reference chemicals in Germany were identified using technological readiness and substitution potential criteria. Their greenhouse gas (GHG) emissions were quantified by using life cycle assessments (LCA) and their economic viabilities were determined by comparing their minimum selling prices with fossil references’ market prices. A bottom up mathematical optimization model, BioENergy OPTimization (BENOPT) was used to investigate the GHG abatement potential and the corresponding abatement costs for the biochemicals up to 2050. BENOPT determines the optimal biomass allocation pathways based on maximizing GHG abatement under resource, capacity, and demand constraints. The identified biochemicals were bioethylene, succinic acid, polylactic acid (PLA), and polyhydroxyalkanoates (PHA). Results show that only succinic acid is economically competitive. Bioethylene which is the least performing in terms of economics breaks even at a carbon price of 420 euros per ton carbon dioxide equivalent (€/tCO2eq). With full tax waivers, a carbon price of 134 €/tCO2eq is necessary. This would result in positive margins for PHA and PLA of 12% and 16%, respectively. From the available agricultural land, modeling results show high sensitivity to assumptions of carbon dioxide (CO2) sequestration in biochemicals and integrated biochemicals production. GHG abatement for scenarios where these assumptions were disregarded and where they were collectively taken into account increased by 370% resulting in a 75% reduction in the corresponding GHG abatement costs.

Dans un contexte de valorisation de molécules issues de la biomasse, de nouvelles architectures moléculaires et polyols ont été développé à partir du sorbitol et divers synthons biosourcés en se basant autant que possible sur les principes de la chimie verte. A partir de réactions d’estérifications contrôlées plusieurs polyols polyesters ont été synthétisés, en l’absence de solvant. Grace à l’utilisation de diols de différentes tailles (C2 à C12) comme monomères, la viscosité et la teneur en fonctions hydroxyles des polyols finaux ont pu être adaptée jusqu’à obtention de propriétés satisfaisantes à l’élaboration de mousses polyuréthanes. Ainsi, des mousses polyuréthanes semi-flexible et des mousses polyisocyanurate rigides ont pu être formulés avec des profils cinétiques de moussage rapide (inférieur à 3 min). Les mousses polyisocyanurates rigides présentent d’excellente propriétés mécaniques et thermiques pouvant pleinement satisfaire à la l’isolation thermique de bâtiment. D’autre part, une voie de transestérification entre le sorbitol et diméthyle carbonate a été étudié afin d’élaborer une nouvelle molécule plateforme bi-fonctionnelle : un bis-cyclocarbonate. A partir de cette molécule plateforme des réactions de polymérisation par ouverture de cycles et d’aminolyses ont été mise en place pour la synthèse de diols, polyéthers réticulés, et de polyuréthanes sans isocyanate (NIPU). Les synthèses de NIPU réalisées à partir de diamines courtes ou longues (issus de dimer d’acide gras) a permis d’étudier les relations existantes entre le choix des monomères et les températures de transitions vitreuses des matériaux polymères résultant. / In a context of renewable molecules valorization, new molecular architectures and polyols have been developed from sorbitol and various biobased building-blocks with respect to the green chemistry principles. Several polyesters polyol have been synthesized from controlled esterification reactions in bulk conditions. Thanks to the used of variable size diols (C2 to C12) monomers, polyols final viscosity and hydroxyls values were tuned until the obtaining of suitable properties for polyurethanes foams elaborations. Thus, semi-flexible polyurethane foams and rigid polyisocyanurate foams were formulated with fast foaming kinetic profiles (less than 3 min). Rigids polyisocyanurates foams exhibit excellent mechanical and thermal properties, in great agreement with building insulating application requirement. Otherwise, transesterifications reaction involving sorbitol and dimethyl carbonate were studied in order to develop a new bi-functional chemical platform, a bis-cyclocarbonate. Ring opening polymerization and aminolysis reactions were investigated from this chemical platform to the elaboration of cross-linked polyether and non-isocyanate polyurethanes (NIPU). NIPU syntheses were performed with short and long diamines in order to study the relationships between monomers choice and the resulting polymer material temperature of glass transition.

Les plastiques sont aujourd'hui des matériaux ubiquitaires utilisés dans tous les aspects de notre vie quotidienne, en particulier pour l'emballage alimentaire. Cependant, après usage, les plastiques sont une source de pollution de notre environnement naturel. Certains plastiques biodégradables et biosourcés sont déjà disponibles sur le marché, comme l’acide polylactique (PLA), mais ils présentent des performances inférieures. Ce travail de thèse vise à: 1) étudier la stabilité des films de PLA dans diverses conditions de température, d'humidité relative, de pH, d'exposition à des liquides ou à des vapeurs... 2) mieux comprendre l'impact de certains procédés industriels tels que les traitements corona ou pressage à chaud sur le PLA 3) combiner le PLA à des couches de gluten de blé afin de produire des complexes ayant des propriétés barrière plus élevées.Les films de PLA ont été produits par la société Taghleef Industries sur demande et avec des traitements de surface spécifiques, comme le traitement Corona. Des films et des enductions à basede gluten de blé ont été développés à l’échelle laboratoire ainsi que des complexes tricouches PLA- gluten-PLA. Les propriétés physiques et chimiques des films ont été étudiées par différentes techniques issues des sciences des matériaux et des aliments ont été utilisées, telles que l’analyse enthalpique différentielle (DSC), l'analyse thermogravimétrique (TGA), la chromatographie d'exclusion de taille (SEC), la microscopie de force atomique (AFM), la microscopie électronique (SEM), la spectroscopie infrarouge à transformée de Fourier (ATR-FTIR) et la spectroscopie de rayons X (XPS). Les propriétés fonctionnelles telles que la perméabilité à la vapeur d'eau, à l'oxygène (O2), au dioxyde de carbone (CO2) ou à l'hélium (He), la sorption de gaz et de vapeurs, les propriétés mécaniques et de surface ont également été étudiées.Exposés au CO2, les films de PLA présentent une isotherme de sorption linéaire avec l’augmentation de pression. Cependant les modifications physiques et chimiques induites à des pressions élevées n'affectent pas son utilisation dans le domaine d’application alimentaire. Au contraire, lorsque les films de PLA sont exposés à l'humidité à l'état liquide ou vapeur, leur dégradation survient après deux mois à 50 ° C (essai accéléré) suite à son hydrolyse. Cette détérioration chimique, mise en évidence par une diminution significative de la masse molaire, entraine une perte de transparence, mais également par une augmentation de la cristallinité. Par ailleurs, le pH n'affecte pas le taux d'hydrolyse, ce qui est d'un intérêt essentiel pour conditionner des aliments humides.Les films à base gluten de blé ont été choisis pour leurs propriétés de barrière élevées lorsque l’humidité relative reste faible. L'incorporation de lipides n'a pas apporté d'amélioration de leurs performances barrières. Cependant, l'utilisation d’un procédé d’homogénéisation à haute pression a permis une meilleure dispersion du gluten, ce qui a conduit à des films plus homogènes ayant ainsi de meilleures propriétés fonctionnelles. Ces conditions ont donc été retenues pour réaliser des complexes à 3 couches par assemblage d'une couche de gluten de blé entre deux couches de PLA en utilisant un pressage à chaud (10 MPa, 130 ° C, 10 min).La technologie de pressage à chaud montre une forte influence sur les films de PLA, de gluten et sur les tricouches. Elle induit une cristallisation accrue du PLA, ce qui augmente ses propriétés de barrière d'environ 40% et 60%, respectivement pour l'eau et l'oxygène. Cela masque par contre l’effet du traitement corona. D’autre part, le pressage à chaud induit une restructuration du réseau de gluten qui améliore les propriétés de barrière aux gaz des complexes, mais provoque aussi une évaporation de l'eau à l'interface gluten / PLA défavorable à l’adhésion des couches (...) / Poly(lactic acid) (PLA) is a biodegradable and renewable polyester, which is considered as the most promising eco-friendly substitute of conventional plastics. It is mainly used for food packaging applications, but some drawbacks still reduce its applications. On the one hand, its low barrier performance to gases (e.g. O2 and CO2) limits its use for applications requiring low gas transfer, such as modified atmosphere packaging (MAP) or for carbonate beverage packaging. On the other hand, its natural water sensitivity, which contributes to its biodegradation, limits its use for high moisture foods with long shelf life.Other biopolymers such as wheat gluten (WG) can be considered as interesting materials able to increase the PLA performances. WG is much more water sensitive, but it displays better gas barrier properties in dry surroundings. This complementarity in barrier performances drove us to study the development of multilayer complexes PLA-WG-PLA and to open unexplored application scenarios for these biopolymers.This project was thus intended to better understand how food components and use conditions could affect the performances of PLA films, and how these performances could be optimized by additional processing such as surface modifications (e.g. corona treatment and coatings).To that aim, three objectives were targeted:- To study the stability of industrially scale produced PLA films in contact with different molecules (CO2 and water) and in contact with vapour or liquid phases, with different pH, in order to mimic a wide range of food packaging applications.- To better understand the impact of some industrial processes such as corona or hot press treatments on PLA.- To combine PLA with WG layer to produce high barrier and biodegradable complexes.Different approaches coming from food engineering and material engineering were adopted. PLA films were produced at industrial scale by Taghleef Industries with specific surface treatments like corona. Wheat gluten films, coatings and layers were developed and optimized at lab scale as well as the 3-layers PLA-WG-PLA complexes. Different technologies able to mimic industrial processes were considered such as hot press, high pressure homogenization, ultrasounds, wet casting and spin coating. The physical and chemical properties of PLA films were then studied at the bulk and surface levels, from macroscopic to nanometer scale. The functional properties like permeability to gases (e.g. O2 and CO2) and water, gas and vapour sorption, mechanical and surface properties were also investigated.Exposed to CO2, PLA films exhibited a linear sorption behaviour with pressure, but the physical modifications induced by high pressure did not affect its use for food packaging. However, when exposed to moisture in both liquid and vapour state (i.e. environments from 50 to 100 % relative humidity (RH)), PLA was significantly degraded after two months at 50 °C (accelerated test) due to hydrolysis. This chemical deterioration was evidenced by a significant decrease of the molecular weight, which consequently induced a loss of transparency and an increase of the crystallinity. The hydrolysis was accelerated when the chemical potential of water was increased, and it was surprisingly higher for vapour compared to liquid state. In addition, pH did not affect the rate of hydrolysis.Knowing much better the limitation of PLA films, the challenge was to improve its functional properties by combining them with WG, as a high gas barrier bio-sourced and biodegradable polymer. The use of high pressure homogenization produced homogeneous WG coatings, with improved performances. This process was thus selected for making 3 layer complexes by assembly of a wheat gluten layer between two layers of PLA, together with corona treatment and hot press technologies.Corona treatment applied to PLA physically and chemically modified its surface at the nanometer scale (...) / I materiali plastici convenzionali trovano impiego in tutti campi della nostra vita, specialmente nel settore del packaging alimentare, ed in seguito all’utilizzo contaminano e danneggiano il nostro ecosistema. Materiali plastici derivanti da risorse naturali e biodegradabili, come acido polilattico (PLA), sono attualmente disponibili sul mercato anche se caratterizzati da performances inferiori.Questo progetto di dottorato è mirato 1) allo studio della stabilità di film di PLA a varie condizioni di stoccaggio come temperatura, umidità relativa, pH, o esposizione a vapori o gas; 2) a comprendere meglio le influenze di alcuni processi industriali come trattamento corona e hot press nelle proprietà dei film di PLA; 3) a sviluppare complessi multistrato tra film di PLA e di glutine che abbiano proprietà barriera più elevate rispetto ai singoli film.Gli imballaggi a base di PLA sono stati prodotti da Taghleef Industries, produttore leader nel settore e dotato di infrastrutture atte ai trattamenti di modificazione di superfice come il trattamento corona. I film a base di glutine e i coatings sono stati sviluppati e ottimizzati su scala di laboratorio, così come i complessi trilaminari PLA-glutine-PLA.Le proprietà fisiche e chimiche dei film di PLA sono state investigate a livello di superficie, così come a livello di bulk. Diverse tecniche analitiche, provenienti dal campo delle scienze dei materiali e delle scienze degli alimenti, sono state adottate in questo progetto di dottorato come calorimetria differenziale a scansione (DSC), termogravimetria (TGA), cromatografia di esclusione molecolare (SEC), microscopia a forza atomica (AFM), microscopia elettronica a scansione (SEM), spettrofotometria infrarossa a trasformata di Fourier in riflettanza totale attenuata (ATR-FTIR) e spettroscopia fotoelettronica a raggi X (XPS).Le proprietà funzionali come le permeabilità al vapore acqueo (H2O), all’ossigeno (O2), al diossido di carbonio (CO2) o all’elio (He) sono state investigate, cosi come l’assorbimento di gas e/o vapori, le proprietà meccaniche e le proprietà di superfice.Nonostante i film di PLA assorbano linearmente CO2 a pressioni crescenti, l’assorbimento di tale gas è ridotto a basse pressioni in modo da non modificare le sue proprietà fisiche – come contrariamente osservato quando il PLA è esposto a CO2 ad alte pressioni – e da non influenzare negativamente il suo utilizzo come imballaggio alimentare. Ad ogni modo, quando i film di PLA sono esposti ad ambienti umidi, o quando sono immersi in acqua liquida, sono significativamente degradati per idrolisi dopo due mesi di stoccaggio a 50 °C (test accelerato). Questo deterioramento chimico è stato evidenziato da una significativa riduzione del peso molecolare del PLA che, conseguentemente, induce una sua perdita di trasparenza e ne incrementa la sua cristallinità. Inoltre, è stato evidenziato che il pH non influenza la velocità di idrolisi. Quest’informazione ha importanza pratica per possibili utilizzi di PLA come imballaggio di alimenti ad alta umidità.Il glutine è stato scelto per le sue alte proprietà barriera, quando è protetto da ambienti ad alta umidità. Si è visto che l’incorporazione di lipidi non porta con sé grandi miglioramenti nelle performances dei film a base di glutine. Invece, l’utilizzo della tecnologia di omogeneizzazione ad alte pressioni permette una migliore dispersione del glutine, ottenendo film più omogenei e con migliori proprietà funzionali. Questa tecnologia è stata quindi scelta per produrre i complessi multistrato, intercalando i film di glutine tra due film di PLA, usando il trattamento hot press (10 MPa, 130 °C, 10 min). Si è osservato che il trattamento hot press modifica le proprietà dei film di PLA, di glutine e dei film multistrato Hot press induce cristallizzazione in PLA, e conseguentemente aumenta le sue proprietà barriera complessive, approssimativamente al 40 % all’acqua e al 60 % all’ossigeno (...) / Los materiales plásticos tradicionales son utilizados en todos los campos de nuestra vida y en particular modo como embajales de productos alimenticios; los cuales después de ser utilizados contaminan y dañan nuesto medio ambiente. Materiales plásticos derivados de recursos naturales y biodegradables, como el ácido poliláctico (PLA) se encuentran actualmente disponibles en el mercado a pesar de sus menores performances. Este proyecto de doctorado está orientado 1) al estudio de la estabilidad de películas de PLA bajo diferentes condiciones como temperatura, humedad relativa, pH o exposición a vapores o gases, 2) comprender los efectos en las propiedades de las películas de PLA de algunos procesos industriales como el tratamiento corona y hot press, 3) desarrollar complejos multicapas de PLA y gluten que tengan propiedades barrera mejores que las de las películas individuales.Los embalajes a base de PLA han sido producidos por Taghleef Industries, productor líder en el sector y dotado de las infraestructuras industriales adaptadas a los tratamientos superficiales como el tratamiento corona. Las películas de gluten y los coatings han sido desarrollados a escala de laboratorio, así como los complejos tricapa PLA-gluten-PLA.Las propiedades físicas y químicas de las películas de PLA han sido investigadas a nivel de superficie así como a nivel de bulk. Diferentes técnicas de análisis, frecuentemente utilizadas en los campos de las ciencias de los materiales y de las ciencias de los alimentos, han sido empleadas en este proyecto como calorimetría diferencial de barrido (DSC), análisis termogravimétrico (TGA), cromotagrafía de exclusión por tamaño (SEC), microscopía de fuerza atómica (AFM), microscopía electrónica de barrido (SEM), espectroscopía de infrarrojos por transformada de Fourier con reflectancia total atenuada (ATR-FTIR) y espectroscopía fotoelectrónica de rayos X (XPS).Las propiedades funcionales de los embalajes como las permeabilidades al vapor de agua, al oxígeno (O2), al dióxido de carbono (CO2) o al helio (He) han sido investigadas, asi como la absorción de gases/vapores, las propiedades mecánicas y las propiedades superficiales. A pesar de que las películas de PLA absorven linealmente CO2 a presiones mayores, la absorción del gas es reducida a bajas presiones y no modifica las propiedades físicas del PLA, como contrariamente sucede cuando el PLA es expuesto a altas presiones de CO2. Por lo tanto, su influencia en las propiedades funcionales del PLA es mínima en las normales aplicaciones alimentarias. De todos modos cuando los embalajes de PLA son expuestos a ambientes húmedos o cuando son sumergidos en agua, procesos de hidrólisis los degradan significativamente después de dos meses de conservación a 50 °C (test acelerado). Este deterioramiento químico ha sido evidenciado por una significativa reducción del peso molecular del PLA, que en consecuencia induce una pérdida de transparencia y un aumento de su cristalinidad. Además, se ha observado que el pH no influye en la velocidad de hidrólisis. Esta información tiene una importancia práctica para posibles usos del PLA como embalajes de alimentos a alta humedad. El gluten ha sido elegido por sus altas propiedades barrera cuando es protegido de ambientes a alta humedad. La incorporación de lípidos en las películas de gluten no han mejorado sus performances. Pero la tecnología de la homogenización a altas presiones ha permitido mejorar la dispersión del gluten, obteniendo películas más homogéneas y con mejores propiedades funcionales. Esta tecnología ha sido, por lo tanto, elegida para producir los complejos multicapa, intercalando las películas de gluten entre dos de PLA, utilizando el tratamiendo hot press (10 MPa, 130 °C, 10 min) (...)

SILVA, André Leandro. Nanobiocompósitos superparamagnéticos para aplicação como antenas ressoadoras dielétricas. 2014. 126 f. : Dissertação (mestrado) - Universidade Federal do Ceará, Departamento de Quimica Orgânica e Inorgânica, Programa de Pós-Graduação e Biotecnologia, Renorbio - Rede Nordeste de Biotecnologia, Fortaleza-CE, 2014. / Submitted by demia Maia (demiamlm@gmail.com) on 2016-05-20T13:09:52Z No. of bitstreams: 1 2014_tese_alsilva.pdf: 6480806 bytes, checksum: 946e32810e24c5137dfbba52bfd30bb8 (MD5) / Approved for entry into archive by demia Maia (demiamlm@gmail.com) on 2016-05-20T13:10:43Z (GMT) No. of bitstreams: 1 2014_tese_alsilva.pdf: 6480806 bytes, checksum: 946e32810e24c5137dfbba52bfd30bb8 (MD5) / Made available in DSpace on 2016-05-20T13:10:43Z (GMT). No. of bitstreams: 1 2014_tese_alsilva.pdf: 6480806 bytes, checksum: 946e32810e24c5137dfbba52bfd30bb8 (MD5) Previous issue date: 2014 / There is a growing global interest for the development of green technologies that allow the use of products with less damage to environment, as well as for maximum and sustainable use of natural resources. The main aim of this study was to develop superparamagnetic nanobiocomposites for application as dielectric resonator antennas. For this purpose, a biobased thermoset plastic was prepared by using cardanol as an alternative to petrochemical phenol. This thermoset plastic was used as a polymer matrix and biocomposites were prepared by using 15 wt% of untreated and modified sponge gourd fibers by chemical treatment (NaOH 5, 10, and 15 wt% and NaClO 1 wt%) as dispersed phase. For the nanobiocomposites preparation, besides the sponge gourd fibers insertion, the thermoset plastic were also impregnated with magnetite nanoparticles in different contents (1, 5, and 10 wt%). Techniques of Thermogravimetry (TG), Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA), Scanning Electron Microscopy (SEM), Optical Microscopy, Transmission Electron Microscopy (TEM), X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Mössbauer Spectroscopy, Tensile testing, Dielectric measurements, Vibrating Sample Magnetometry (VSM) and Biodegradation in simulated soil were performed for characterization. The results showed that alkaline treatment improved the thermal stability and the crystallinity index of the sponge gourd fiber. The crosslinking agent used (Diethylenetriamine) was efficient and enabled complete cure for all materials. The biocomposites reinforced by treated fiber showed better thermal stability, superior performance in Tensile testing and greater biodegradation rates, when compared to the biocomposite reinforced by raw fiber. The magnetite particles exhibited nanometric size, high purity and crystallinity, and superparamagnetic character. All nanobiocomposites showed superparamagnetic behavior, excellent thermal stability, good biodegradation rates, and better mechanical strength for the material with magnetite 10 wt%. All dielectric resonators antennas exhibited satisfactory return loss and suitability for commercial and technological applications, especially for performance in broadband. / É crescente o interesse mundial pelo desenvolvimento de tecnologias chamadas “verdes” que possibilitem o uso de produtos com menor impacto ao meio ambiente, assim como também se fortalecem as políticas de incentivo ao aproveitamento máximo e sustentável dos recursos naturais. O principal objetivo desse estudo foi desenvolver nanobiocompósitos superparamagnéticos para aplicação como antenas ressoadoras dielétricas. Para tal, um plástico termorrígido biobaseado foi preparado utilizando o cardanol em alternativa aos fenóis petroquímicos. Esse plástico termorrígido foi utilizado como matriz para o preparo de biocompósitos, utilizando 15% em massa de fibra de bucha bruta e também modificada por tratamento químico (NaOH 5, 10 e 15% e NaClO 1%) como fase dispersa. Para o preparo dos nanobiocompósitos, além da fibra de bucha, nanopartículas de magnetita, sintetizadas pelo método da coprecipitação, foram impregnadas no plástico termorrígido em diferentes teores de 1, 5 e 10% em massa. Técnicas de Termogravimetria (TG), Calorimetria exploratória diferencial (DSC), Análise dinâmico-mecânica (DMA), Microscopia eletrônica de varredura (MEV), Microscopia óptica, Microscopia eletrônica de transmissão (MET), Difração de raios X (DRX), Espectroscopia no infravermelho com transformada de Fourier (FTIR), Espectroscopia Mössbauer, Ensaios de resistência à tração, Medidas dielétricas, Magnetometria de amostra vibrante (VSM) e Biodegradação em solo simulado foram utilizadas para caracterização. Os resultados mostraram que o tratamento alcalino melhorou a estabilidade térmica e o índice de cristalinidade da fibra de bucha. O agente reticulador utilizado (DETA) mostrou-se eficiente, possibilitando a cura completa dos materiais. Os biocompósitos com fibra tratada apresentaram maior estabilidade térmica, resistência à tração superior e melhor índice de biodegradação em relação ao biocompósito com fibra natural. A magnetita sintetizada exibiu tamanho nanométrico, além de alta pureza, alta cristalinidade e caráter superparamagnético. Todos os nanobiocompósitos exibiram superparamagnetismo e mostraram excelente estabilidade térmica, boas taxas de biodegradação e melhor resistência mecânica para o material com 10% de magnetita. Todas as antenas ressoadoras dielétricas preparadas apresentaram perda de retorno satisfatória e, portanto, adequação para fins comerciais e tecnológicos, com maior potencial para atuação em banda larga.

Dans un contexte du développement durable, de nouvelles architectures macromoléculaires biosourcées ont été synthétisées à partir de synthons (diacides et diols) pouvant être obtenus par voies fermentaires à partir de sources carbonées issues de la biomasse. Dans un premier temps, différents copolyesters aliphatiques ont été synthétisés en masse, à l’aide d’un catalyseur organométallique à base de titane, à partir de diacides (acides succinique et adipique) et de diols (1,3-propanediol, 1,4-butanediol et 2,3-butanediol) courts. Dans un deuxième temps, des architectures macromoléculaires similaires ont été obtenues par catalyse enzymatique en solution à l’aide de la lipase B de Candida antarctica. L’influence de la longueur et de la structure des monomères sur leur réactivité en présence de la lipase a été particulièrement étudiée. Dans un troisième et dernier temps, des architectures macromoléculaires à base d’oligomères hydroxytéléchéliques d’un polyester bactérien : le poly((R)-3-hydroxybutyrate) (PHB)tels que des poly(ester-éther-uréthane)s et des copolyesters ont été obtenues soit par couplage de chaîne à l’aide d’un diisocyanate, ou par transestérification organométallique et enzymatique. Ces études ont permis d’analyser en détail l’effet de l’addition des synthons biosourcés dans les architectures macromoléculaires et notamment sur la structure cristalline, la stabilité thermique et les propriétés thermiques et optiques de ces polymères. De plus, le grand potentiel de la catalyse enzymatique pour la synthèse de polyesters et celui de l’utilisation d’oligomères de PHB pour l’élaboration de nouveaux matériaux performants ont pu être largement démontrés. / In the context of sustainable development, new biobased and aliphatic macromolecular architectures were synthesized from building blocks that can be obtained by fermentation routes using carbon sources from the biomass. First, several aliphatic copolyesters were synthesized in bulk from short dicarboxylic acids (such as succinic and adipic acids) and diols (such as 1,3-propanediol, 1,4-butanediol and 2,3-butanediol) by organometallic catalysis using an effective titanium-based catalyst. In a second time, similar macromolecular architectures were synthesized by an enzymatic process in solution using Candida antarctica lipase B as catalyst. The influence of the alkyl chain length and the structure of monomers on their reactivity toward the lipase were particularly discussed. In the third and last part, new macromolecular architectures based on hydroxytelechelic oligomers of a bacterial polyester: poly((R)-3-hydroxybutyrate) (PHB), such as poly(ester-ether-urethane)s and copolyesters, were obtained by either chain-coupling using a diisocyanate, or organometallic and enzymatic transesterification, respectively.These studies permitted to determine a close relationship between the effect of the building blocks structure integrated in the final macromolecular architectures and the intrinsic properties, such as the crystalline structure, the thermal stability and the thermal and optical properties, of these polymers. In addition, the great potential of the lipase-catalyzed synthesis of polyesters and the use of PHB oligomers for developing new high performance materials has been clearly established.

[pt] Resinas epóxi do éter diglicidílico de bisfenol A (DGEBA) são amplamente usadas como matriz de materiais compósitos. No entanto, o principal monômero utilizado para a sua produção, o Bisfenol A (BPA), apresenta significativos efeitos negativos na saúde humana. Implicações ambientais que limitam o uso BPA fazem necessária a substituição dos monômeros base para a preparação de resinas epóxi por outros mais seguros e ambientalmente sustentáveis. Por outro lado, resinas epóxi preparadas a partir de fontes renováveis constituem uma alternativa ao uso de resinas derivadas do petróleo na produção de materiais compósitos. Assim, óleos naturais derivados de fontes vegetais são considerados uma matéria-prima alternativa para a obtenção de resinas epóxi de base biológica por causa da sua disponibilidade e uma ampla variedade de possibilidades para transformações químicas. Além disso, materiais compósitos fabricados a partir de resinas termo-endurecíveis de origem vegetal e fibras lignocelulósicas como material de reforço, poderiam contribuir com a produção sustentável de materiais de baixo custo e menor densidade que possuam propriedades estruturais funcionais. Neste trabalho propõe-se a preparação de laminados utilizando como matriz resinas epóxi biobaseadas obtidas a partir de óleo de soja epoxidado e cardanol epoxidado (proveniente da casca de castanha de caju) e fibras lignocelulósicas de bucha (Luffa cylindrica) como reforço. Os efeitos estruturais, morfológicos e térmicos de tratamentos superficiais de hornificação, mercerização e acetilação nas fibras foram estudados usando espectroscopia no infravermelho por transformada de Fourier (FTIR), difração de raios X (DRX), microscopia eletrônica de varredura (MEV), microscopia de força atômica (AFM) e análise termogravimétrica (TGA). Compósitos DGEBA/Bucha e Resina natural/Bucha foram fabricados pelo método lay-up manual e suas propriedades mecânicas foram avaliadas por meio de ensaios de flexão em três pontos e da técnica não destrutiva de excitação por impulso (TEI). Esta técnica também foi utilizada para a determinação experimental dos módulos dinâmicos e das propriedades de amortecimento dos compósitos durante o envelhecimento por UV e por absorção de água. O comportamento dinâmico-mecânico dos compósitos foi avaliado por meio da análise dinâmico-mecânica (DMA). Resinas preparadas com 50 por cento de cardanol epoxidado e 50 por cento de resorcinol curadas com diamina de isoforona apresentaram melhores propriedades térmicas e mecânicas, comparados com sistemas com óleo de soja epoxidado, com uma temperatura de transição vítrea média de 74 graus Celsius e módulo de armazenamento de 880,5 MPa, constituindo uma alternativa mais sustentável para a fabricação de materiais compósitos pela substituição do sistema bisfenol A clássico analisado também neste trabalho, com valores Tg igual a 77,5 graus Celsius e E linha igual a 849 MPa. A adição de fibras de bucha em forma de manta permitiu a obtenção de compósitos com modos de fratura controlada. Além disso, foi observada uma melhora na aderência na interfase fibra-resina em compósitos com 30 por cento de fibras de bucha mercerizada. / [en] Diglycidyl ether of bisphenol A (DGEBA) currently represents the most widely used type of epoxy resin in the world in several applications. However, the main monomer used for its production, Bisphenol A (BPA) is considered an endocrine disruptor with estrogenic activity that has significant negative effects on human health. Environmental implications and laws limiting the use of BPA in several countries make it necessary to replace the base monomers for the preparation of epoxy resins with safer and more environmentally sustainable ones. Epoxy resins prepared from renewable sources are an alternative to the use of petroleum resins in the production of composite materials. Thus, natural oils derived from vegetable sources are considered as an alternative raw material for obtaining biologically based epoxy resins because of their availability, their relatively low price and a wide variety of possibilities for chemical transformations. On the other hand, composite materials made from thermosetting resins of vegetable origin and lignocellulosic fibers as reinforcement material could contribute to the sustainable production of low cost and lower density materials that have functional structural properties. This work proposes the preparation of composite materials, using biobased epoxy resins obtained from epoxidized soybean oil and epoxidized cardanol from cashew nuts as well as lignocellulosic (Luffa cylindrica) fibers modified by surface treatments of hornification, mercerization and acetylation. The structural, morphological and thermal effects of surface treatments on the fibers were studied using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). DGEBA/Luffa and Biobased resin/Luffa fiber composites were fabricated by the manual lay-up method and their mechanical properties were evaluated by three-point bending tests and the non-destructive impulse excitation technique (TEI). This technique was also used for the experimental determination of the dynamic modules and the damping properties of the laminates obtained during UV aging and water absorption. The effect of the introduction of the binder fibers and the different treatments performed on the fibers on the dynamic-mechanical behavior of the composites was performed by dynamic-mechanical analysis (DMA). Resins prepared with 50 percent epoxidized cardanol and 50 percent resorcinol cured with isophorone diamine presented better thermal and mechanical properties, compared to systems with epoxidized soybean oil, with an average glass transition temperature of 74 degrees Celsius and a storage modulus of 880, 5 MPa, constituting a sustainable alternative for the manufacture of composite materials by replacing the classic bisphenol A system also analyzed in this work, with values Tg equal to 77.5 degrees Celsius and E line equal to 849 MPa. The addition of luffa fibers allowed the production of composites with controlled fracture modes. In addition, an improvement in the fiber-resin interface adhesion was observed in composites with 30 percent mercerized fibers.

Due to the rapid development of technology, electrical products are being shipped all over the world. The electronic components have gotten greater in capacity but are smaller in size, making them sensitive to electrostatic discharge (ESD). ESD packaging protects sensitive components from electrostatic discharge and electrical fields. There are different types of packaging solutions depending on the sensitivity of the product. Rigid packaging of insulating paperboard, impregnated with a thin, conductive carbon layer was used in this study. The conductive material is supposed to lead the static electricity away from the product, to the packaging which is insulated, where it safely can discharge. The inside of the packaging, normally dressed in a foam to protect the device inside, is supposed to be replaced with paperboard. The purpose of this master thesis is to investigate whether or not an ESD-packaging can be created by coating a paperboard with a dispersion containing nanographite and nanocellulose. Solid Bleached Board is a paperboard made by the mill Iggesund Paperboard, used for graphical products and packaging of high quality. Paperboard is made from cellulose, an environmentally sustainable raw material from the forest. Classifications of materials used in ESD packaging-solutions are divided into how quickly electricity moves through the material. Carbon is normally within the range of 10^2 to 10^6 Ω for sheet- and volume resistance. Maximal charge and maximal electrical discharge of the packaging are by standard not supposed to exceed 100 V and 50 nJ. Two different nanographite dispersions with different binders (polyvinyl alcohol and cellulose nanofibres) have been made. These have been coated onto the paperboard using a bench-coater. Measurements of ESD- and paperboard-properties have been performed onto the paperboard. The measured values were within the range of what was considered acceptable to be able to create an ESD packaging. The prototype was designed materially with solid bleached board, coated with a dispersion made of 220g nanographite, 22g cellulose nanofibres and 3791g water with a solid content of 8,2%. The design has been developed with the company's existing packaging in mind together with information about the already existing ESD packages. The results from the measurements show that it is fully possible to create and produce ESD-packaging, but needs further testing after this thesis. Societal, ethical and environmental aspects have been considered during the entire study. / På grund av den snabba tekniska utvecklingen transporteras elektriska produkter över hela världen. Elektroniska komponenter har fått större kapacitet men är mindre i storleken vilket gör dem känsliga för elektrostatisk urladdning (ESD). ESD-förpackningar skyddar känsliga komponenter från elektrostatisk urladdning och elektriska fält. Det finns olika typer av förpackningslösningar beroende på produktens känslighet. Styva förpackningar av isolerande kartong, impregnerade med ett tunt, elektriskt ledande kolskikt användes i denna studie. Det ledande materialet leder den statiska elektriciteten bort från produkten, till förpackningen som är isolerad, där den säkert kan urladdas. Förpackningens insida, som normalt är klädd med ett skum för att skydda produkten inuti, är tänkt att ersättas med kartong. Syftet med examensarbetet är att undersöka om en ESD-förpackning kan skapas genom att bestryka ett kartongark med en dispersion innehållande nanografit och nanocellulosa. Homogen helblekt kartong (Solid Bleached Board, SBB) är en kartong tillverkad av pappersbruket Iggesund Paperboard, som används för grafiska produkter och förpackningar av hög kvalitet. Kartong är tillverkad av cellulosa, ett miljövänligt och hållbart material från skogen. Klassificeringar av material som används i ESD-förpackningar är indelade i hur snabbt elektricitet rör sig genom materialet. Kol ligger normalt inom intervallet 10^2 till 10^6 Ω för yt- och volymresistans. Maximal uppladdning och maximal elektrisk urladdning av förpackningen ska inte överstiga 100 V och 50 nJ. Två olika dispersioner med olika bindemedel (polyvinylalkohol och cellulosa nanofibrer) har tillverkats. Dessa har bestrukits på kartongen med en bänkbestrykare. Mätningar av ESD- och kartong-egenskaper har utförts på kartongen. Mätdata låg inom det intervall som ansågs vara acceptabelt för att kunna skapa en ESD-kartong. Prototypen, sample B, är designad materiellt med homogen helblekt kartong, bestruken med en dispersion gjord av 220g nanografit, 22g cellulosa nanofibrer och 3791g vatten med en torrhalt på 8,2%. Designen har utvecklats med företagets befintliga förpackningar i åtanke tillsammans med information om de redan existerande ESD-förpackningarna. Resultaten från mätningarna visar att det är fullt möjligt att skapa och producera ESD-kartong, men det kräver ytterligare tester efter denna studie. Samhälleliga-, etiska- och miljöaspekter kommer att beaktas under hela studien.

Cette thèse présente l’élaboration de thermodurcissables et de composites biosourcés synthétisés à partir d’huiles végétales époxydées (lin et soja) et d’alcool furfurylique (FA). La première partie de ce travail concerne l’étude de la polymérisation du FA en polyalcool furfurylique (PFA) (i) en solvants protiques polaires, (ii) en combinaison avec le bois et (iii) suivant l’ajout de nouveaux amorceurs. En solvant, les changements de structures observés ont été reliés aux propriétés thermomécaniques. Une autre modification de structure du PFA a été obtenue grâce au 2,5 diméthylfurane. Ce travail a permis d’obtenir une meilleure compréhension de la réactivité du FA au sein du bois et montre que les composites bois/PFA ont une densité et une résistance plus élevées que leurs homologues non modifiés. Enfin, l’amorçage des réactions du FA par l’acide lévulinique ou par le p-toluène sulfonylhydrazine permet de proposer deux nouveaux amorceurs, respectivement biosourcé et « latent ». La seconde partie de ce travail concerne l’élaboration d’une résine époxyde totalement biosourcée et synthétisée à partir d’huiles végétales époxydées. L’huile de lin et de soja ont été chacune copolymérisées avec un acide dicarboxylique. Un premier travail fondamental a consisté à corréler la réactivité de copolymérisation avec les structures des polymères obtenus puis à établir le lien avec les propriétés thermomécaniques. Ensuite, des nanocomposites ont été synthétisés à partir de ces résines époxydes et de sépiolite. Les différentes voies de dispersion et de modification de la sépiolite mises en œuvre conduisent à des niveaux de dispersion différents de la nanocharge au sein de la matrice. / The work presents the elaboration of biobased thermosets and composites synthesized from epoxidized vegetable oils (linseed and soybean) and furfuryl alcohol (FA). A first area of research focused on the study of the polymerisation of FA into polyfurfuryl alcohol (PFA) (i) in protic polar solvents, (ii) in combination with wood and (iii) in the presence of new reaction initiators. In presence of solvents, the observed structural changes have been linked to the thermomechanical properties. Another PFA structure modification was obtained with 2,5 dimethylfuran. This work allowed a better understanding of the reactivity of FA within the wood and shows that the obtained wood/PFA composites have higher density and resistance than their non-modified equivalents. Finally, the initiation of FA polymerization by levulinic acid and p-toluene sulfonylhydrazine, respectively biobased and « latent » initiators has been studied. The second topic of thesis concerns a new type of fully bio-based epoxy resin synthesized from epoxidized vegetable oils. Linseed and soybean oils have both been copolymerized with a dicarboxylic acid as curing agent. A first fundamental work was to correlate the reactivity of copolymerization with the polymer structure and to link them with thermomechanical properties. The obtained thermosets have been used to prepare nanocomposites with sepiolite. Different methods of dispersion and/or modification of sepiolite conduct to diverse morphologies of nanofiller dispersions into the matrix.