Lignin is an undervalued product that does not yet provide economic returns. Finding value-added applications of lignin is needed to achieve economic sustainability. Carbon nanoparticles have great technological and industrial importance because of their enhanced physicochemical, electrical, thermal and mechanical properties. In this work a novel method has been explored to produce carbon nanoparticles from lignin. The objective of this work is to synthesize carbon nanoparticles with high surface area from lignin through the carbonization process. Lignin was dissolved in alkaline solutions with different weight ratios of lignin and potassium hydroxide. An intermediate sublimation process was adopted to reduce agglomeration of particles. The lignin was thermo-stabilized after the sublimation process in oxidizing atmosphere followed by the carbonization process in an inert atmosphere at 700oC using tubular furnace. The increase in glass transition tem-perature during thermo-stabilization process was confirmed by DSC analysis. The con-densation reactions during thermo-stabilization process were confirmed by FTIR analysis. The formation of carbon nanoparticles was confirmed by transmission electron microscopy (TEM) analysis. Carbon nanoparticles with high specific surface area of 42 m2/g were produced. From the DLS particle size distribution it was found that 5 wt% KOH is the optimum concentration for synthesizing carbon nanoparticles from lignin. / Ontario Ministry of Agriculture, Food and Rural Affairs (OMAFRA) New Directions Research Program for funding the project (number SR 225).

Sustainability has been a driving factor in the recent development of protective coating systems, from reducing volatile organic compounds (VOC’s), integrating biomass for the replacement of petrochemicals, to reducing the number of synthetic or processing steps within a coating system. Incorporating changes to established technologies requires research initiatives focused on matching or exceeding performance properties while maintaining or lowering costs. As a result, sustainable changes to protective coating systems have been under heavy investigation as market demands shift from petrochemicals to renewable materials. This research focuses on the development of unique thermoset coating systems and sustainable improvements. The first study explores the hydrolytic stability between a silanol and an isocyanate, a frequently used reaction that has been relatively understudied. Incorporation of potential hydrolytically unstable silyl carbamates into polyurethane systems may decrease the crosslinking efficiency of the overall network, negatively impacting coating performance. As a result, investigation into the stability of silyl-carbamates may prevent further inefficiencies by eliminating use of this chemistry within polyurethane systems. The second study focuses on the development of alkoxysilane sol-gel consolidants for the protection of stone materials. Sustainable approaches to consolidant formulation include the reduction and elimination of solvent while improving consolidating properties through material selection. The last two studies focus on the incorporation of lignin-derived vanillin into epoxy thermosets and melamine formaldehydes, increasing the overall biobased content of each system. / Office of Naval Research (FAR0025712) / National Center For Preservation Technology and Training, NCPTT (FAR0028305) / EPSCoR/NSF (FAR0030160)

Master of Science / Department of Grain Science and Industry / Sajid Alavi / There is a renewed focus on biodegradable polymers in packaging applications due to environmental concerns associated with conventional plastics. Melt extrusion was used to synthesize nanocomposites from poly (lactic acid) (PLA) or poly (butylene succinate) (PBS) blended with natural nanofillers — chitin whiskers (CHW, 1-5%), nanocrystalline cellulose (NCC, 1-5%) or lignin-coated nanocrystalline cellulose (LNCC, 3%). Transmission electron microscopy and x-ray diffraction indicated that the natural nanofillers were uniformly dispersed in the polymer matrix. For PLA based nanocomposites, differential scanning calorimetry showed a decrease in change of heat capacity at glass transition (ΔCp) with increased nanofiller addition, indicating greater confinement of polymer chains. For PBS based nanocomposites, nanofillers acted as nucleating agents and promoted recrystallization of polymer as reflected in increase of degree of crystallinity (Xc) from 65.9-66.8 to 75.6%. By addition of NCC and CHW, tensile strength (TS) of PLA based films increased from 50.2 MPa to 70.9 MPa and 52.1 MPa, respectively, while TS of PBS increased from 23.2-24.9 MPa to 32.9 MPa and 43.6 MPa, respectively. Elongation at break (E%) of nanocomposite films ranged from 9.1 to 15.3, and in general decreased with addition of nanofillers. LNCC did not significantly improve mechanical properties of PBS and PLA films. Additionally, 3% NCC addition reduced oxygen transmission rate (OTR) of PLA from 209.9 to 180.8 cc/m[superscript]2/day, which further reduced to 109.3 cc/m[superscript]2/day by adding compatibilizer methylene diphenyl diisocyanate (MDI, 4%). Water vapor transmission rate (WVTR) of PLA also reduced from 44.4 to 28.6 g/m[superscript]2/day with 3% NCC and 4% MDI addition. Similarly OTR and WVTR of PBS decreased from 737.7 to 280 cc/m[superscript]2/day and 83.8 to 49.4 g/m[superscript]2/day, respectively with 3% NCC. Use of 4% MDI further reduced OTR and WVTR to 23.8 cc/m[superscript]2/day and 30.8 g/m[superscript]2/day, respectively. Use of starch can potentially reduce the costs of bio-based nanocomposites films. Up to 40% starch was incorporated during synthesis of PLA and NCC nanocomposites using solution mixing method. Addition of starch decreased TS from 35.8 MPa to 18.4 MPa and E% from 8.3% to 6.0%. Use of NCC (1%) and MDI (4%) improved the mechanical properties to a certain extent.

Les matériaux de protection thermique ablatifs sont largement utilisés dans le domaine de l’aérospatial afin d’isoler les systèmes exposés à de fortes températures. Les résines phénoliques issues de la polymérisation du phénol et du formaldéhyde sont les polymères organiques les plus utilisés à ce jour. Cependant, le profil hygiène, sécurité et environnemental de ces monomères est critique et entraîne un risque d’obsolescence réglementaire fort pour les matériaux élaborés à partir de ces précurseurs. Deux voies ont alors été développées afin de proposer des polymères thermodurcissables de substitution qui soient pérennes et susceptibles de conduire à des améliorations techniques. La première option proposée est un grade commercial de poly(alcool furfurylique) qui réticule thermiquement en catalyse acide. L’alcool furfuylique présente l’avantage d’être un précurseur biosourcé obtenu depuis des ressources renouvelables. La fabrication et la caractérisation de matériaux composites obtenus à partir de ce type de résine ont permis de démontrer la pertinence de cette voie. La deuxième voie a été développée à partir de monomères phénoliques potentiellement biosourcés sur lesquels ont été introduits des fonctions propargyle. La sélection du monomère le plus prometteur, sa pré-polymérisation et son association à des réactifs porteurs de fonctions thiol ont conduit à des résines très prometteuses potentiellement utilisables pour la fabrication de matériaux ablatifs : faible viscosité, émission limitée de composés organiques volatils par rapport au résines phénoliques et furaniques, rendement en coke élevé lors de la pyrolyse de la matrice polymérisée (taux de coke). / Ablative thermal protection materials are key components of aerospace engineering. They provide insulation to vehicles exposed to severe heating conditions. Phenolic resins are widely used in such composite materials due to their outstanding thermal properties attributed to the three-dimensional network of aromatic structures arising from polycondensation reactions between phenol and formaldehyde. However, such chemicals exhibit a negative health, safety and environment profile which induces a high risk of obsolescence for any material involving such precursors. Therefore, highly processable ablative thermosetting polymers leading to char yields higher than 50 % (at 900 °C under inert atmosphere) were developed based on environmentally more favorable chemicals. Two solvent-free resins are proposed. The first option is a commercially available grade of poly(furfuryl alcohol). The manufacturing of composite materials demonstrated the high potential of the proposed formulations. The second option was obtained at the lab scale from the introduction of propargylic functions onto aromatic precursors which can be obtained from biomass conversion processes. The optimization of the formulations led to highly promising thermal and thermomechanical properties. The manufacturing of composite materials is required to demonstrate the ablative behaviour of the proposed new thermosetting formulations.

Lactic acid based thermoset were synthesised by reacting lactic acid with glycerol andfunctionalizing lactic acid branches by methacrylic anhydride. Resins with different chainlength were prepared and their thermo mechanical properties were examined through DMAanalysis and their molecular structures were analyzed by NMR method and their viscositywere investigated through rheometry analysis and three monomers were selected as the bestchain length. Degree of reaction in different reaction times was evaluated by a modifiedtitration method and bulk preparation of resin was performed by optimal process condition.DSC analysis was conducted in order to evaluate curing behaviour of resin with benzoylperoxide as cross-linking initiator. TGA analysis was performed to check thermo stability ofthe resin. Bio composites by viscose unidirectional and bidirectional knitted fabrics and alsonon woven viscose fiber with different fiber loads were prepared by ordinary hand layupimpregnation followed by compress moulding and their mechanical and thermo mechanicalproperties were characterized by tensile, flexural, charpy and DMA analysis and optimumfiber loads were identified for each fiber type. Ageing properties of prepared composites wereexamined by placing samples in climate chamber to simulate long time ageing and ageingexperiment was followed by tensile and flexural test to evaluate mechanical properties afterageing simulation. Composite`s swelling properties for water and some other solvents wereinvestigated and also their chemical resistance were evaluated by immersing them in 1M HCland KOH. The resin was also compared with a commercial oil based thermoset by preparingglass fiber reinforced composites and also effect of adding styrene to the resin were evaluated.Results of this work demonstrated that the novel synthesised have very high mechanical andthermo mechanical properties surpassing commercial oil based poly esters but ageingbehaviour is not very good however adding styrene can improve ageing properties. Also theresin is compatible with cellulosic natural fibers and forms strong composites. / Program: Masterutbildning i energi- och material

Au niveau académique et industriel, les nanocelluloses connaissent un engouement toujours grandissant. Ce projet de thèse explore la modification chimique des nanofibrilles de cellulose (CNF) pour des applications médicales. Des drogues et prodrogues de principes actifs (PA) ont été liées de manière covalente ou adsorbées sur des films ou des suspensions de CNF. Pour l’immobilisation covalente, une première stratégie d’estérification en milieu aqueux a été utilisée sur des films de CNF. Les propriétés antibactériennes contre des bactéries à gram positif et à gram négatif, ainsi que l’activité par contact prolongée de ces films, ont été démontrés. La seconde stratégie a porté sur la modification des suspensions de CNF au travers d’une procédure multi-étape (amidation puis chimie click), à nouveau en phase aqueuse. Des outils de caractérisation innovants comme la résonance magnétique nucléaire (RMN) dopée par polarisation dynamique nucléaire (PDN), ont permis de compléter les techniques classiques pour prouver le succès du greffage chimique. L’adsorption de PA sur les films et suspensions de CNF a été menée en parallèle de l’immobilisation covalente. Ensuite, les films de CNF avec des PA greffés ou adsorbés ont été utilisés pour développer des dispositifs médicaux pour application cutanée. Quant aux suspensions de CNF avec PA greffé ou adsorbé, elles ont été intégrées à des matrices de collagène pour créer de nouveaux prototypes de réparation pariétale. Leur activité antibactérienne et leurs propriétés de relargage contrôlé confirment l’intérêt de ces composites pour le design de dispositifs médicaux innovants.Mot-clés: nanocellulose, nanofibrilles de cellulose, fonctionnalisation, dispositif médical, activité antibactérienne, relargage contrôlé / In line with the ever-increasing academic and industrial interest for wood derived nanocellulose, the present work investigated the chemical surface modification of cellulose nanofibrils (CNFs) for biomedical application. Drugs and pro-drugs of active principle ingredients (APIs) were covalently immobilized or adsorbed onto CNFs films or suspensions. For covalent immobilization, the first strategy selected calls for water-based and single step esterification of CNF films. The resulting materials demonstrated antibacterial activity against both gram-positive and gram-negative bacterial strains, with a prolonged contact-active effect. In the second strategy, CNFs suspensions were modified through a multistep reaction, involving amidation and click chemistry, still water-based. Highly innovative characterization tools, such as dynamic nuclear polarization (DNP) enhanced nuclear magnetic resonance (NMR), complemented well-established techniques to confirm the success of grafting. In parallel to covalent immobilization, an adsorption strategy was also adopted, on both CNFs films and suspensions. Then, the CNF films with grafted or adsorbed APIs were used for preparing 100% CNF medical devices for topical applications. Another component of this work used CNF suspensions with grafted or adsorbed APIs were embedded in collagen matrices to prepare model medical device of soft tissue repair implants. Antibacterial activity against both aerobic and anaerobic bacteria, together with controlled release properties were assessed confirming that such composites present the expected active properties, and can be used for the design of innovative medical devices.Key words: nanocellulose, cellulose nanofibrils, functionalization, medical devices, antibacterial activity, drug release

Les polyuréthanes forment une importante famille de polymère ; ils sont obtenus industriellement à partir d’isocyanates, des dérivés du phosgène. Dans l’optique de s’affranchir de ces composés toxiques et de promouvoir l’utilisation de la biomasse, cette thèse s’intéresse à la synthèse de dispersions aqueuses de polyuréthanes sans isocyanates et dérivés d’huiles végétales. Deux voies de synthèse de polyuréthane sans isocyanate sont étudiées : la transuréthanisation et l’aminolyse des carbonates cycliques. Des synthons biscarbamates et bis-carbonates cycliques dérivés d’acides gras ont ainsi été développés, et leur polymérisation en masse avec des diols ou diamines étudiée. Les deux voies de synthèse permettent d’obtenir des polyuréthanes pour des températures de 20 à 130°C en quelques heures ; le méthanolate de sodium est identifié comme un catalyseur efficace lors de la transuréthanisation tandis que l’aminolyse des carbonates cycliques ne nécessite pas de catalyse. Les masses molaires (Mn) obtenues sont de l’ordre de 5-17kg.mol-1, ces résultats sont cohérents avec la littérature. La polymérisation en mini-émulsion (aqueuse) a alors été utilisée pour la synthèse de polyuréthanes par aminolyse des carbonates cycliques. De nombreuses expériences de formulation des mini-émulsions ont permis d’aboutir à des mini-émulsions et latex de polyuréthanes stables. / Polyurethanes are a major polymer family; they are industrially obtained from phosgene derivatives: isocyanates. In order to avoid the use of such toxic compounds and to promote the use of biomass, this thesis investigates the synthesis of aqueous dispersions of nonisocyanate polyurethanes derived from vegetable oils. Two synthesis pathways have been studied; transurethanization and aminolysis of cyclic carbonates. Bis-carbamates and biscyclic carbonates were synthesized from fatty acids, and their polymerizations with diols or diamines were studied in bulk. The two routes allow the production of polyurethanes in a few hours at 20-130°C. Sodium methoxide is used as catalyst for transurethanization reactions while the other synthesis pathway does not require catalysts to proceed. Polyurethanes obtained have molar mass (Mn) around 5-17kg.mol-1, which is in accordance with the literature. The polymerization in aqueous miniemulsion was then investigated for the synthesis of polyurethane by aminolysis of cyclic carbonates. Many formulation experiments were necessary to achieve stable miniemulsion and latex; aqueous dispersions of bio-based non-isocyanate polyurethanes were then obtained.

Jusqu'à récemment, l'industrie chimique se contentait de développer des produits en répondant exclusivement à des contraintes de prix et de performance sans accorder d'importance à l'origine et à la toxicité des matières premières utilisées. Cependant, face à la diminution des ressources pétrolières et aux enjeux environnementaux, le développement de produits durables a connu un fort essor au cours des dernières années et confronte dorénavant les chimistes à de nouvelles contraintes sanitaires et environnementales. Dans ce contexte, la vieille chimie des peintures alkydes a été remise à l’ordre du jour, puisqu'utilisant un liant issu d'une polycondensation entre des matières premières renouvelables. Le séchage d’une peinture alkyde implique à l’heure actuelle un mécanisme oxydatif nécessitant d'être catalysé par des sels de Cobalt pour se produire en moins de 6 h. Ces catalyseurs sont potentiellement cancérogènes et soumis au règlement REACH. Après un état de l'art sur les alkydes et les alternatives aux sels de cobalt, trois mécanismes de réticulation ont été proposés afin d'offrir une alternative viable au séchage oxydatif. Ces trois mécanismes reposent sur une réaction chimique à température ambiante entre deux groupements fonctionnels. Plusieurs résines alkydes biosourcées et ainsi fonctionnalisées ont été synthétisées et caractérisées par mesures physico-chimiques. Leurs performances de séchage ont ensuite été évaluées et comparées au séchage oxydatif d'une résine alkyde conventionnelle par mesure de leur dureté Persoz, leur jaunissement dans le temps, leur brillance ou encore par mesure d'angle de contact. / Up to recently, the origin and toxicity of raw material were not a major concern for the chemical industry, the main drivers of innovation being cost and performance. Increasing awareness of sustainability, supported by both public opinion and governments, is now adding a new constraint for chemists to take into account the origin of the raw materials used. In this context, alkyd coatings are making a huge comeback, because based on a binder obtained by polycondensation reactions of renewable raw materials. Conventional alkyd paints chemically dry through an oxidative mechanism, which requires cobalt salt to occur in less than 6 h. Chemical regulations such as REACH tend to limit the use of colbalt salts, because of their potentially carcinogenic effect. After reviewing the current state-of-the-art regarding conventional alkyd resins and cobalt salts alternatives, we proposed three new non-oxidative drying mechanism, each involving a chemical reaction between two key functional groups. Several biobased alkyd resins bearing these chemical groups were synthesized and characterized by physico-chemical analysis. Their drying performances were evaluated by following over time the Persoz hardness, the gloss, the yellowing or the contact angles. These non-oxidative crosslinking mechanisms were then compared with the oxidative drying of a conventional alkyd binder.

Consumers put higher demands on low environmental impact from the products they use, and the materials they consist of. As a result, more research is being made on finding environmentally friendly production techniques and materials. Hydrothermal carbonization (HTC) is a relatively environmentally friendly method that has been used in this study. Cellulose and pine, the latter, one sample with and one without bark, were carbonized at 220 °C and 240 °C for two hours. This generated solid carbon products that could be used in composites with the biopolymer Polylactide (PLA). The composites were thereafter extruded as filaments and used for 3D printing. X-ray powder diffraction (XRD), Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) showed that HTC of all precursors generated an amorphous carbon material, with carbon microspheres and increased aromaticity. Three different composites were produced from PLA and 0.1 wt% of the solid carbon products from all three precursors carbonized at 240 °C. Composites were also made from PLA and 1 wt% non-carbonized pine with bark, and 1 wt% of pine with bark carbonized at 240 °C. Filaments were extruded from neat PLA, as well as the composites of 0.1 wt% carbonized cellulose and 0.1 wt% carbonized pine with bark mentioned above. The filaments were used to 3D print six dog bones per filament according to the ISO standard ISO 527-2 1BA. There was one instance of clogging for each filament from the composite materials, but it was easily solved. No mechanical tests could be performed, although the 3D printed models’ physical properties were visually observed, and no deficiencies were found. Both extrusion and 3D printing were successful. / Konsumenter ställer högre krav på att material och produkter de använder har liten påverkan på miljön. Till följd av detta lägger forskningen mer resurser på att hitta miljövänliga tillverkningsmetoder och material. Hydrotermisk karbonisering (HTC) är en relativt miljövänlig process som har använts i denna studie. Tall (ett prov med och ett utan bark) samt cellulosa karboniserades vid 220 °C och 240 °C i två timmar, för att på detta vis producera en fast kolprodukt som kunde användas i en komposit med biopolymeren Polylaktid (PLA). Kompositen extruderades sedan till filament som användes vid 3D printing. Röntgenpulverdiffraktion (XRD), Svepelektronmikroskopi (SEM) och Fourier-transform infraröd spektroskopi (FTIR) visade på att HTC hade genererat amorfa kolmaterial, med mikrosfärer och ökad aromaticitet från både cellulosa och båda tallproverna. Samtliga produkter från karbonisering vid 240 °C användes för att göra tre olika kompositer med vardera 0,1 vikt% kolmaterial. Kompositer tillverkades även från PLA och 1 vikt% tall med bark, samt 1 vikt% tall med bark karboniserad vid 240 °C. Filament extruderades av ren PLA samt ovan nämnda kompositer med 0.1 vikt% karboniserad cellulosa och 0.1 vikt% karboniserad tall med bark. Dessa användes vid 3D printing för att skriva ut sex hundben per filament, enligt ISO standarden ISO 527-2 1BA. Vid ett tillfälle för vardera av de två kompositerna täpptes mynningen till 3D skrivaren igen av partiklar i filamenten. Detta löstes dock enkelt. Mekaniska tester kunde tyvärr inte utföras på hundbenen, men inga fysiska brister beskådades på dem. Både extrudering och 3D printing var lyckade.

Phenolic adhesives are widely used in the production of engineered wood products due to their exceptional moisture and thermal resistance, chemical stability, and bonding strength. The phenolic adhesive is currently produced through condensation polymerization of two fossil fuel-derived compounds: phenol and formaldehyde. However, due to fluctuations in the price of phenol and formaldehyde with the price of oil, environmental and health issues associated with using these compounds, there is a strong interest in finding alternative renewables feedstocks. Lignin is a natural polyphenolic compound with excellent potential to substitute phenol in phenolic adhesive formulations. Lignin is produced as byproducts during pulp and bioethanol processes. On the other hand, biobased aldehydes such as glyoxal have recently gained a lot of attention for replacing the toxic formaldehyde in production of environmentally friendly wood products. In this study, a wide range of lignin samples from different resources (hardwood, softwood, wheat straw, and corn stover), and isolated via various processes (kraft, organosolv, soda, sulfite, and enzymatic hydrolysis), were used to formulate 100% lignin-based phenolic adhesives. In a separate work, formaldehyderee phenolic adhesives were also developed using either glyoxal or gossypol (a dialdehyde from cotton seed) in combination with phenol. Chemical, physical, and thermal properties of lignin samples and developed phenolic resins and adhesive were measured using advanced analytical techniques and appropriate ASTM standard test methods. Based on two-way ANOVA analysis results of shear strength data, a biorefinery corn stover lignin that had the highest p-hydroxyphenyl and p-coumaric acid content was the most suitable lignin for replacing 100% of phenol in phenolic adhesive formulation. In addition, the developed lignin-based adhesive (formulated with biorefinery corn stover lignin) showed similar dry and wet adhesion strengths as that of commercially formulated phenol resorcinol formaldehyde (PRF) adhesive. On weight basis, the formaldehyde consumption in the developed lignin-based adhesive was 50% lower than the formaldehyde used in phenol formaldehyde (PF) resin. Moreover, two formaldehyderee formulated adhesives using glyoxal and gossypol (renewable feedstocks) had very similar physico-chemical properties to phenol formaldehyde adhesive.