Emulsions, comprising dispersed oil or water droplets stabilized by surfactants, are widely employed across industries. However, conventional surfactants raise environmental concerns, and emulsions may encounter stability challenges during storage. A promising alternative lies in Pickering emulsions, where particles adhere irreversibly at the water-oil interface, providing enhanced stability. Recent research explores the use of natural bio-based particles as interfacial stabilizers for creating Pickering emulsions, offering improved stability and environmental friendliness. This significant change towards particle-stabilized emulsions addresses sustainability and efficacy concerns. This dissertation investigates the application of cellulose nanofibrils (CNFs) in stabilizing Pickering emulsions for the development of functional microcapsules with diverse applications. A novel CNF aerogel with a hierarchical pore structure was developed using n-hexane-CNF oil-in-water (O/W) Pickering emulsions as templates. These hollow microcapsule-based CNF (HM-CNF) aerogels demonstrated high oil absorption capacities of 354 grams per gram for chloroform and 166 grams per gram for n-hexadecane, without requiring hydrophobic modifications, highlighting their potential as environmentally sustainable and high-performance oil absorbents. Further, the research explored the microencapsulation of n-hexadecane, an organic phase change material (PCM), within a hybrid shell of CNFs and chitin nanofibers (ChNFs). This method significantly improved the thermal stability of the encapsulated n-hexadecane, with maximum weight loss temperatures increasing from 184 degrees Celsius to 201 degrees Celsius with ChNF loading. The char yield also increased with ChNF content, indicating enhanced thermal degradation resistance. These emulsions demonstrated stability in various ionic solutions and elevated temperatures, showcasing their potential for applications such as thermal energy storage, cosmetics, food, and pharmaceuticals. Additionally, the dissertation examined stable water-in-oil (W/O) inverse Pickering emulsions using TEMPO-treated cellulose nanofibrils (TCNF). These emulsions, stabilized by TCNF-oleylamine complexes, exhibited droplet sizes ranging from 27 micrometers to 8 micrometers depending on TCNF concentration. They maintained stability under varying pH, ionic strength, and temperature conditions and demonstrated the encapsulation of water-soluble components like phytic acid, highlighting their versatility for diverse encapsulation applications. Overall, the research presents significant advancements in the utilization of CNF-stabilized Pickering emulsions, employing them as templates for fabricating aerogels and microcapsules. This approach enhances oil absorption, thermal stability, and encapsulation capabilities, offering eco-friendly solutions for diverse applications.

<p dir="ltr">Food packaging plays a crucial part, yet the use of petroleum-based plastics has led to environmental concerns. Researchers have been exploring sustainable alternatives using CNMs. This dissertation includes three parts, each focusing on using CNF or CNC for packaging applications. In the first project, CNF/CMC coated MP trays were achieved via over-molding. Mechanical, Gurley air porosity and water vapor transmission rate testing showed that the coating improved the overall performance. Coated samples showed the highest oil and grease resistance level. Fresh fruit testing showed that the coating helps elongate the shelf life of fruits. In the second project study, to overcome the problem of relatively poor water barrier performance of CNF/CMC coatings in high humidity conditions, coatings were chemically modified by crosslinking with PAE and incorporated with Cloisite-Na⁺ nano-clay and PVA. The chemical modification enhanced both water and oxygen barrier performance and reduced Cobb value. The formulated CNF-coated MP trays maintained the same level of oil and grease resistance. Mechanical testing showed reduced Young’s modulus, similar UTS, and higher strain at break for formulated CNF-coated tray samples compared to the un-crosslinked samples. In the third project, a transparent tri-layer PLA-CNC/PVA-PLA film was successfully fabricated using blade coating and lamination. The CNC/PVA coating (~ 6μm) showed a high degree of CNC alignment and significantly enhanced the gas barrier properties. Furthermore, these laminates were formed into bags where a fruit storage test showed that the PLA-CNC/PVA-PLA could elongate the shelf life of fresh apple slices based on weight loss and enzymatic browning.</p>

Dans cette thèse, des particules de polymère fonctionnalisées en surface avec des groupes poly (éthylène glycol) (PEG) ont été synthétisées pour favoriser leur interaction avec les dérivés cellulosique via liaisons hydrogène intermoléculaires. Deux voies de synthèse ont été proposées pour obtenir ses composites cellulose/latex.La première voie est basée sur l'auto-assemblage induit par polymérisation (PISA) pour former des nanoparticules fonctionnalisées avant leur adsorption sur un substrat cellulosique. La PISA tire profit de la formation de copolymères blocs amphiphiles dans l'eau en combinant la polymérisation en émulsion avec les techniques de polymérisation radicalaire contrôlées (RDRP). Ces dernières sont utilisées pour synthétiser des polymères hydrophiles agissant à la fois comme précurseur pour la polymerization en émulsion d'un monomère hydrophobe, et comme stabilisant des particules de latex obtenues. Deux techniques de RDRP ont été étudiées : les polymérisations RAFT et SET-LRP. Des polymères hydrophiles à base de PEG de faible masse molaire ont été synthétisés en utilisant ses deux techniques qui sont ensuite utilisés pour la polymérisation d'un bloc hydrophobe dans l'eau. Le transfert de l'agent de contrôle au site de la polymérisation était difficile en utilisant la SET-LRP en émulsion, conduisant à la formation de larges particules. En utilisant la RAFT en émulsion, des particules nanométriques ont été obtenues, avec un changement morphologique observé en fonction de la taille du segment hydrophobe, puis adsorbées sur des nanofibrilles de cellulose (CNF).La seconde voie utilise la polymérisation en émulsion classique réalisée en présence de nanocristaux de cellulose (CNC) conduisant à une stabilisation Pickering des particules de polymère. L'interaction cellulose/particule est assurée grâce à l'ajout d’un comonomère à type PEG. Une organisation a été visualisé dans laquelle plusieurs particules de polymère recouvrent chaque CNC / In this thesis, polymer particles surface-functionalized with poly(ethylene glycol) (PEG) groups were synthesized to promote their interaction with cellulose derivatives via intermolecular hydrogen bond. Two synthetic routes were proposed to obtain such cellulose/latex composites.The first route was based on the polymerization-induced self-assembly (PISA) to form functionalized polymer nanoparticles prior to adsorption onto cellulosic substrate. PISA takes advantage of the formation of amphiphilic block copolymers in water by combining emulsion polymerization with reversible-deactivation radical polymerization (RDRP) techniques. The latter were used to synthesize well-controlled hydrophilic polymer chains, acting as both precursor for the emulsion polymerization of a hydrophobic monomer, and stabilizer of the final latex particles. Two RDRP techniques were investigated: reversible addition-fragmentation chain transfer (RAFT), and single electron transfer-living radical polymerization (SET-LRP). Low molar mass PEG-based hydrophilic polymers have been synthesized using both techniques, used for the polymerization of a hydrophobic block in water. The transfer of controlling agent at the locus of the polymerization was challenging for SET-LRP in emulsion conditions leading to surfactant-free large particles. Nanometric latex particles were obtained via RAFT-mediated emulsion polymerization, with morphology change from sphere to fibers observed depending on the size of the hydrophobic segment, which were then able to be adsorbed onto cellulose nanofibrils (CNFs).The second route used conventional emulsion polymerization performed directly in presence of cellulose nanocrystals (CNCs) leading to Pickering-type stabilization of the polymer particles. Cellulose/particle interaction was provided thanks to the addition of PEG-based comonomer. Original organization emerged where CNCs were covered by several polymer particles