Cellulose nanocrystals (CNCs) are crystalline nanoparticles that are extracted from renewable sources such as trees or bacteria through mechanical or chemical treatments of their source. CNCs are of interest to several research communities concerned with sustainable technologies. Specifically, CNCs have attracted great interest in the polymer composite community given their high theoretical specific strength and modulus. Two key obstacles surround the use of CNCs in polymer composites, namely their comparatively lower thermal stability and hydrophilicity render their dispersion, and therefore mechanical reinforcement, in polymer matrices challenging. This research considered a waterborne epoxy and a polyurethane elastomer for CNC/polymer composites since these composites are seldom reported in literature or often suffer from degraded mechanical properties. In the epoxy/CNC composites, samples were prepared by two methods, first an epoxy emulsion was mixed with an amine crosslinker and an aqueous based CNC suspension (1-step mixing), and second, the epoxy emulsion was premixed with the aqueous based CNCs and the amine crosslinker was added some time later (2-step mixing). Both composites were mixed by magnetic stirring, however the samples prepared by the 2-step mixing method exhibited enhanced dispersion and mechanical properties, specifically the storage modulus (E’), tensile strength, and work of fracture. Zeta potential measurements and chemical analysis by FTIR indicated that the dispersion mechanism was physical in nature, rather than chemical. In the second composite system, CNCs were chemically modified with an isophorone diisocyanate (IPDI) monomer having unequally reactive isocyanate groups. The goal of the modification step was to react only one isocyanate group with the CNC surface and have a free isocyanate group available for further modification. The chemical structure of one linked isocyanate (urethane bond) and one free isocyanate was confirmed by FTIR and 13C NMR. The particles modified by IPDI (m-CNC) and the neat particles (um-CNC) were incorporated into a polyurethane matrix based on IPDI and a triol crosslinker. Upon visual inspection of the cured composites, it was clear that the modification step produced homogeneously dispersed nanoparticles in the polyurethane while the um-CNCs were aggregated. When the mechanical properties were tested by uniaxial tensile testing, it was determined that the m-CNC composites resulted in improvements in the tensile strength and work of fracture without degradation of the elongation of break property when compared to the neat matrix. Overall the findings in this research highlight important considerations for designing CNC/thermoset composites with enhanced dispersion and mechanical performance.

The focus of this study was to explore process-structure-property relationships in biodegradable polymer nanocomposite films in order to eliminate the commonly used trial and error approach to materials design and to enable manufacturing of composites with tailored properties for targeted applications. The nanofiller type and concentration, manufacturing method and compounding technique, as well as processing conditions were systematically altered in order to study the process-structure-property relationships. Polylactic acid (PLA) was used as the polymer and exfoliated graphite nanoplatelets (GNP), carbon nanotubes (CNT), and cellulose nanocrystals (CNC) were used as reinforcement. The nanocomposite films were fabricated using three different methods: 1) melt compounding and melt fiber spinning followed by compression molding, 2) solution mixing and solvent casting, and 3) solution mixing and electrospinning followed by compression molding. Furthermore, the physical properties of the polymer, namely the crystallization characteristics were altered by using two different cooling rates during compression molding. The electrical response of the composite films was examined using impedance spectroscopy and it was shown that by altering the physical properties of the insulating polymer matrix, increasing degree of crystallinity, the percolation threshold of the GNP/PLA films is significantly reduced. Additionally, design of experiments was used to examine the influence of nanofiller type (CNT versus GNP), nanofiller content, and processing conditions (cooling rate during compression molding) on the elastic modulus of the composite films and it was concluded that the cooling rate is the primary factor influencing the elastic modulus of both melt compounded CNT/PLA and GNP/PLA films. Furthermore, the effect of nanofiller geometry and compounding method was examined and it was shown that the high nanofiller aspect ratio in the CNT/PLA films led to decreased percolation threshold compared to the GNP/PLA films. The melt compounded GNP/PLA films displayed a lower percolation threshold than the solution cast GNP/PLA films most likely due to the more homogeneous distribution and dispersion of GNP in the solution cast films. Fully biodegradable and biorenewable nanocomposite films were fabricated and examined through the incorporation of CNC in PLA. Through the addition of CNC, the degree of crystallinity of the matrix was significantly increased. Focusing the design space through investigation of process-structure-property relationships in PLA nanocomposites, can help facilitate nanocomposites with tailored properties for targeted applications.

Submitted in fulfillment of the academic requirements of the degree of Master of Applied Sciences in Chemistry, Durban University of Technology, Chemistry Department, Durban, South Africa, 2016. / Cellulose is a sustainable, abundant biopolymer derived from a variety of living species such as plants, animals, bacteria and some amoebas. An attractive source of cellulose for industrial uses is agricultural waste, as this use does not jeopardize food supplies and improves the local rural economy. Sugarcane bagasse (SCB) is one of the main biomass wastes from sugar production and represents 30–40 wt % of sugar production waste. In 2008, South Africa produced on average 22 million tons of sugar cane each season from 14 sugar mill supply areas which resulted in 7,9 million tons of “waste” bagasse. In this study cellulose nanocrystals were prepared from soda pulped sugarcane bagasse by acid hydrolysis followed by separation using centrifugation, ultrasonication and dialysis. Transmission Electron Microscopy (TEM) images showed nanocrystals of approximately 300 nm in length and 20 nm in width. Thermogravimetric Analysis and Differential Thermogravimetry (TGA and DTG) profiles of FD CNC, MCC and Pulped bagasse all had characteristic onset and decomposition temperatures indicating a change in the structure after chemical treatments. Particle size distribution measurements corroborated with the TEM and FE - SEM results and showed that the majority of the nanocrystals were in the 100 – 300 nm range. Attenuated Total Reflectance – Fourier Transform Infra Red (ATR - FTIR) analysis showed functional group changes as the amorphous regions of the polymer were removed revealing the ordered crystalline portions. These were further confirmed by an increase in the Lateral Orientation Index (LOI) of the samples as the nanocrystals were isolated. X - Ray Diffraction (XRD) Crystallinity Index (CrI) calculations showed a steady increase in the crystallinity of the materials from pulped bagasse to MCC to FD CNC. / M

Les travaux de cette thèse portent sur la formation et la polymérisation d'émulsions de Pickering stabilisées par des nanocristaux de cellulose (NCC). Tout d’abord, les NCC sont fonctionnalisés en surface de façon à modifier d'une part, leur balance hydrophile/hydrophobe et d'autre part, apporter des fonctions promoteurs de la polymérisation par ATRP de la phase interne ou externe. A l'aide de ces NCC, des émulsions directes, inverses et doubles de styrène et de monomères acryliques ont été stabilisées puis polymérisées. L'impact, de la fonctionnalisation des NCC, de la nature du monomère et de l’amorceur, de la présence ou pas de sel sur, la taille, la stabilité, la couverture des gouttes et la morphologie des objets obtenus, a été étudiée. Les latex issus de la polymérisation radicalaire d’émulsions directes de Pickering ont permis la préparation de composites aux propriétés mécaniques améliorées par rapport à celles de la matrice sans charge. Les émulsions stabilisées par des NCC réactifs ont conduit à la synthèse de capsules ou de billes pleines en fonctions de la nature du monomère polymérisé. Des matériaux poreux ont été obtenus par polymérisation des émulsions inverses de Pickering. Enfin, la polymérisation des émulsions doubles a permis l’obtention d’objets à morphologie tout à fait inédite avec l’encapsulation de capsules de polystyrène dans des capsules plus volumineuses de ce même polymère. / Pickering emulsions are based on amphiphilic particle stabilizers, which adsorb irreversibly at the liquid-liquid interface and form a rigid structure around the droplets. Amongst these particles, biosourced and biorenewable cellulose nanocrystals (CNCs) have demonstrated good performances as Pickering stabilizers for oil in water emulsions. In this thesis, a wide range of emulsions of monomers were stabilized by amphiphilic modified CNCs. These Pickering emulsions subsequently serve as vessel to perform radical polymerization. In a first step, the CNCs are modified to tailor the hydrophobic/hydrophilic balance and are used to efficiently stabilize direct (O/W), inverted (W/O) or double W/O/W Pickering emulsions of monomers. The different emulsions obtained were subsequently polymerized, by thermal radical polymerization or by SI-ATRP. The polymerization of the direct emulsions allowed producing either capsules or filled beads, depending on the monomer used, which we assigned to differences in monomer reactivity. Hence, the method offers the opportunity to tune the morphology of the polymerized spheres (empty or filled), by simply controlling the monomer conversion. The polymerization of the inverted emulsion on the other end, led to the formation of a porous material. The polymerization of the double W/O/W emulsions was also envisaged, leading original morphology such as small empty beads encapsulated into larger capsules.

Orientador: Nelson Eduardo Durán Caballero / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T20:45:34Z (GMT). No. of bitstreams: 1 Ridolfi_DanielaMissiani_D.pdf: 3264748 bytes, checksum: faea0a4fec50e345e79d3072a773bb48 (MD5) Previous issue date: 2014 / Resumo: Neste trabalho nanofibras de quitosana/poli (óxido de etileno) (PEO) (5:1) com nanocristais de celulose (NCC) foram produzidas com sucesso por eletrofiação e foi verificado o efeito da adição dos NCC nas propriedades das nanofibras obtidas. Os ensaios de eletrofiação foram realizados com amostras de NCC obtidas por hidrólise ácida. A eletrofiação de soluções de quitosana, sem e com NCC, resultaram na formação de muitas gotas (beads). Portanto, foi necessário adicionar o PEO nas soluções. Embora a adição de PEO tenha favorecido a formação de fibras, as soluções de quitosana/PEO sem NCC geraram também gotas enquanto que as soluções de quitosana/PEO contendo NCC resultaram em fibras uniformes. As soluções de quitosana/PEO com NCC apresentaram maior viscosidade em relação à solução sem NCC, o que pode ter favorecido a formação de fibras uniformes. As soluções de quitosana/PEO contendo 10% (m/m) de NCC produziram fibras mais finas em relação às soluções com 5% (m/m) de NCC provavelmente devido à maior condutividade da solução. Análises termogravimétricas mostraram que os NCC interferem na decomposição do PEO, mas sem prejudicar o desempenho do material. As nanofibras de quitosana/PEO contendo NCC apresentaram menor cristalinidade em relação às nanofibras sem NCC. Resultados de ensaios com células em culturas de fibroblastos 3T3 mostraram que as nanofibras de quitosana/PEO (com 10% de NCC) promoveram a adesão celular e mantiveram a morfologia celular característica o que sugere um potencial dessas nanofibras para aplicações em engenharia de tecidos / Abstract: In this work chitosan/ poly (ethylene oxide) (PEO) (5:1) nanofibers with cellulose nanocrystals (CNC) were successfully produced by the electrospinning technique and the effect of the addition of CNC on the nanofibers properties was evaluated. The electrospinning assays were performed with samples of CNC obtained by acid hydrolysis. The electrospinning of chitosan solutions, with and without CNC, resulted in the formation of many drops (beads). Therefore, it was necessary to add PEO on solutions. Although the PEO addition has favored the fiber formation, the chitosan/PEO solutions without CNC showed beads while chitosan/PEO solutions with CNC resulted in uniform fibers. The chitosan/PEO solutions with CNC showed higher viscosity compared to the solution without CNC, which may have favored the formation of uniform fibers. Solutions of chitosan/PEO containing 10% (w/w) of CNC produced thinner fibers compared to solutions containing 5% (w/w) of CNC probably due the higher solution conductivity. Thermogravimetric analysis (TGA) showed that the CNC has an effect on the PEO decomposition, however, it does not impair the performance of the material. The chitosan/PEO nanofibers with CNC showed lower crystallinity compared the nanofibers without CNC. Results from cell assay in cultures of 3T3 fibroblasts showed that the chitosana/PEO nanofibers (with 10% of CNC) promoted cell attachment and maintained the characteristic cell morphology which suggests potential applications of these nanofibers in cell tissue engineering / Doutorado / Físico-Química / Doutora em Ciências

Yes / Physical properties of scaffolds such as nanofibers and aligned structures have been reported to exert profound effects on the growth and differentiation of stem cells due to their homing-effect features and contact guidance. However, the biological function of aligned nanofiber utilized as bone-scaffold has not been rigorously characterized. In the present study, aligned electrospun cellulose/CNCs nanocomposite nanofibers (ECCNNs) loaded with bone morphogenic protein-2 (BMP-2) were used for the first time to investigate (1) in vitro osteogenic differentiation of human mesenchymal stem cells (BMSCs) and (2) in vivo collagen assembly direction and cortical bone regeneration. Aligned ECCNNs scaffolds loaded with BMP-2 possess good biological compatibility. The growth orientation of BMSCs followed the underlying aligned nanofibers morphology, accompanied with increased alizarin red stain, ALP activity and calcium content in vitro while, a rabbit calvaria bone defect model was used in an in vivo study. / This work was supported by Natural Science Foundation of China (NSFC) grants (31500789, 51433006, 51473100, 81870758 and 31871464), Chongqing Yuzhong District science and technology plan project grants (20170124), Chongqing Research Program of Basic Research and Frontier Technology (cstc2018jcyjAX0807, cstc2017jcyjBX0019 and cstc2017jcyjAX0020), Temple University Kornberg School of Dentistry research start-up funds, the RCUK China-UK Science Bridges Program through the Medical Research Council and the Engineering and Physical Sciences Research Council and Program for Innovation Team 1015 Building at Institutions of Higher Education (No. 1016 CXTDG201602006) funded by the Chongqing Municipal 1017 Education Commission of China in 2016

The objective of this thesis is to incorporate cellulose nanocrystals (CNCs) into polymer latexes prepared using various emulsion polymerization methods. CNCs are a promising new class of renewable materials with unique properties including nanoscale dimensions, a high aspect ratio, low density, and high strength. They show significant promise to enhance the properties of existing materials, but challenges often arise due to incompatibility and processing difficulties. This work investigates novel surface modification routes to improve the compatibility of CNCs with emulsion polymerization components, and aims to control the location and function of CNCs in latex systems in order to modify latex properties. Three approaches to incorporate CNCs into polymer latexes are presented: (1) exploiting CNC-surfactant interactions in order to promote CNCs as Pickering stabilizers or as “passive” additives in the water phase, (2) enhancing the surface activity of CNCs by adsorbing the surface active biopolymer methyl cellulose (MC) to act as Pickering co-stabilizers, or (3) hydrophobic modification of CNCs through polymer grafting in order to provide improved compatibility between CNCs and the monomer/polymer phase to incorporate CNCs into the latex core. First, the interactions between CNCs and surfactants were studied in suspension and at surfaces and the CNC-surfactant combinations were used to stabilize miniemulsion polymerization of methyl methacrylate (MMA), a model system used in this work. Oppositely charged CNCs and surfactants showed improved stability as Pickering stabilizers and the ability to co-stabilize the monomer/polymer-water interface. When like-charged CNCs and surfactants were used, the poly(methyl methacrylate) (PMMA) polymer particles were stabilized by surfactant only, while the CNCs remained in the water phase. Next, in order to avoid the use of surfactants, CNCs were coated with MC to provide improved surface activity. MC-coated CNCs were effectively used as Pickering stabilizers in the microsuspension polymerization of MMA, where a double morphology of PMMA particles was observed, and the morphology could be tuned based on the ratio of CNC to MC used. Finally, CNCs were modified with hydrophobic polymer via two different “grafting from” methods: free radical polymerization and atom transfer radical polymerization (ATRP). Free radical polymer grafting from CNCs resulted in polymer-grafted CNCs but the method lacked control over polymer graft length and graft density. To overcome this, CNCs were modified via surface initiated ATRP where considerably higher amounts of polymer were grafted from the CNCs in short reaction times and with simple purification steps. Furthermore, polymer-grafted CNCs were added to the monomer phase of the miniemulsion polymerization of MMA and latexes with CNCs inside the hydrophobic polymer particle core were prepared. Given the difficulties in characterizing polymer grafted CNCs, a novel solution state NMR method was used, whereby the modified CNCs were dissolved in ionic liquids and the polymer grafts were cleaved and collected to determine graft length and graft density. Overall, this work provides three approaches for the preparation of nanocomposite latexes with CNCs using PMMA as a model system. The results presented here may expand the use of CNCs in latex products such as adhesives, paints, coatings, and cosmetics. / Thesis / Doctor of Philosophy (PhD) / This research aims to prepare polymer latexes with tailorable properties using renewably-sourced particles and nanotechnology. Latexes are polymer particles dispersed in water, typically on the order of a few hundred to thousand nanometers (where a “nanometer” is one billionth of a meter), and are used in products such as adhesives, paints, and coatings. The field of nanotechnology takes advantage of nanomaterials where unique properties stem from the small size and high surface-area-to-volume ratio. In this work, we use cellulose, the most abundant natural polymer on earth, in the form of cellulose nanocrystals (CNCs). These nanoparticles are extracted from pulp, cotton, and other natural resources to yield nanometer-sized rigid rod-like particles. CNCs have recently gained attention in research and the media because of their new industrial production and “safe nanomaterial” designation in Canada. In this work, CNCs were chemically modified by the attachment of new molecules or by coating them with polymers and were subsequently added during the synthesis of the polymer latex. Incorporating CNCs imparted new properties and the ability to control latex size, shape, and surface topography. CNCs are also expected to improve the overall mechanical strength of the latex, and may enhance the stickiness of adhesive latexes in particular, leading to products that are more environmentally friendly and that show improved performance.

This thesis investigates new processing methods and bone tissue engineering applications of cross-linked cellulose nanocrystal (CNC) aerogels. Aerogels are highly porous, low-density materials that have been praised for their high surface area and interconnected pores, but criticized for their brittleness. This prompted a search for new aerogel “building blocks” to produce more flexible materials; CNCs meet this need and chemically cross-linked CNC aerogels have good compressive strength and shape recovery properties in air and liquid environments. CNCs are high aspect ratio, non-toxic and renewably-sourced nanoparticles. Literature has demonstrated CNC aerogel production using cryo-templating with controlled drying. In this work, we produce aerogels using a new scalable process called pressurized gas expansion (PGX) and compare them to conventional cryo-templated aerogels. PGX aerogels were found to have more expanded fibrillar morphology, a range of mesopore sizes and smaller macropores, in contrast to cryo-templated aerogels that had a sheet-like morphology surrounding larger macropores. Additionally, PGX aerogels had higher specific surface area and porosity, but lower compressive strength due to a lower cross-link density. While neither CNC aerogel type dispersed in water, PGX aerogels partially shrank whereas cryo-templated aerogels did not; this is attributed to their morphological differences. This work shows that new aerogel processing methods can introduce new properties and thus broaden the potential applications of CNC aerogels. One specific biomedical application was evaluated for CNC aerogels – their use as bone tissue scaffolds. Cryo-templated aerogels comprised of CNCs with different surface chemistries, either sulfate or phosphate groups, were found to have attractive chemical, physical and mechanical properties for bone tissue engineering. This work shows that both types of CNC aerogels can facilitate cell proliferation, favorable differentiation, and can nucleate uniform hydroxyapatite growth. These positive in vitro results and the bimodal pore morphology of CNC aerogels make them promising bone scaffolds for in vivo studies. / Thesis / Master of Applied Science (MASc) / Aerogels are light, porous, sponge-like materials that are essentially 99% air by volume. In this work, the aerogels are made from non-toxic plant-based nanoparticles called cellulose nanocrystals (CNCs). This thesis investigates: 1) new ways to control CNC aerogel properties and pore size through different processing methods and 2) the use of CNC aerogels to aid in the repair of damaged bones. High-resolution microscopy and nano-characterization tools show that CNC aerogels have tunable properties, which may extend their possible applications. The internal structure, sponge-like mechanical properties and biocompatibility of CNC aerogels allowed them to be successfully utilized to support bone cells and grow bone-like mineral.

Cellulose nanocrystal (CNC) has found application in a variety of novel products due to its spectrum of properties. Notably, the CNC-polymer systems have seen numerous applications in special materials like Pickering emulsions, foams and gels etc. CNC interacts with different polymers to a different extent. These interactions include molecular level and bulk interactions. Subsequently, they modify the interfacial properties. Though vibrant, the CNC-polymer molecular interaction is still unclear. We took this void in our understanding as our motivation to explore these interactions. In this work, we tried to understand why CNC interacts differently with different polymers and what drives the adsorption of polymer on CNC. Our work can also help us to understand the configurations and origins of CNC-polymer system properties. The broad range of length and time scales covered by this physical process requires a multiscale simulation approach. In this thesis, we start with the all-atom molecular simulation and focus on the specific energetic interactions between CNC surfaces and unrealistically short polymer chains. In future work, we will build on this model and develop a multiscale modeling approach for capturing the full scope of CNC-polymer interaction, including the configuration and dynamics of realistic long polymer chains around CNCs. We propose that there are two driving forces for adsorption based on the free energy difference values obtained via PMF (potential of mean force) calculations done on eight systems with different physical components. Overall, we conclude that the balance between polymer's ability to form hydrogen bonds with the surface and their interactions with the bulk solvent control the adsorption and desorption phenomenon. A larger coarse-grained model developed from our simulations will help to understand these systems better. This presented work deals with the specific energy interactions and information which we will need for the systematic coarse-graining of these systems. / Thesis / Master of Applied Science (MASc)

Nanoparticle usage continues to increase in everyday products, from cosmetics to food preservation coatings, drug delivery to polymer fillers. Their characterization and synthesis is of utmost importance to ensure safety and improved product quality. Nanoparticles can be sourced naturally or synthetically fabricated. Cellulose nanocrystals (CNCs) are rod-like nanoparticles that can be isolated from nature. Reliable methods of characterization are necessary to ensure quality control. However, their physical characteristics cause challenges for imaging under transmission electron microscopy (TEM) with a high enough resolution for dimensional analysis. Heavy metal staining such as radioactive uranyl acetate is often used to increase contrast and TEM sample substrate preparation techniques often use expensive equipment such as glow discharge in order to prevent CNC agglomeration. A method to reliably produce TEM images of CNCs without using radioactive stains or expensive glow discharge equipment was developed, using a vanadium-based stain branded NanoVan® and bovine serum albumin to keep CNCs dispersed while drying on the TEM substrate. Due to their aspect ratio, there is also concern of toxicity to the lungs. The concentration of CNCs in air in production facilities must be monitored, but there is currently no method tailored to CNCs. A method using UV-vis spectroscopy, dynamic light scattering, TEM, and scanning mobility particle sizer in conjunction with impinger collectors was developed for monitoring aerosolized CNC concentration. Synthetic nanoparticles are often used for controlled drug delivery systems. A new peptide drug termed αCT1 has been shown to interact with cell communication in a way that promotes wound healing, reduces inflammation and scarring, and aids in cancer therapy. However, the peptide's half-life in the body is estimated to be less than a day, which is not conducive to long-term treatments. Controlling its release into the body over several weeks can decrease the number of doses required, which is especially useful for glioblastoma treatment. Poly(lactic-co-glycolic acid) (PLGA) is often used for drug encapsulation since it hydrolyzes in the body and is biocompatible. Two methods of αCT1 encapsulation in PLGA were explored. It was found that flash nanoprecipitation increased loading of αCT1 in the particles by 1-2 orders of magnitude compared with the double emulsion method. Particles released αCT1 over three weeks and were non-cytotoxic. / PHD / Nanoparticle usage continues to increase in everyday products, from cosmetics to food preservation coatings, drug delivery to polymer fillers. Understanding the nature of nanoparticles is important to ensure safety and quality of commercial products, and production of particles allows for tailoring for specific applications. In this work, a technique to more easily create samples of cellulose nanocrystals (CNCs) for electron microscopy is developed. Electron microscopy can then be used to measure the size of these rod-like particles. Then, the technique is used to help develop a method to measure the concentration of CNCs in air. CNCs may irritate the lungs, so development of a way to measure their concentration in air is important to ensure safety of plant workers and consumers of CNCs. Characterization techniques of CNCs were used for synthesized particles used for brain cancer treatment. Synthesized particles contain the drug αCT1, which has been shown to reduce glioblastoma, or brain cancer, from becoming resistant to chemotherapy. These particles were made using poly(lactic-co-glycolic acid) (PLGA), a polymer that degrades in the body into lactic acid and glycolic acid. PLGA particles released αCT1 over three weeks and are of a size that is compatible with the brain. However, loading of the drug was low when using the first synthesis method. By switching particle synthesis methods, drug loading in the particles was increased by 1-2 orders of magnitude.