This thesis describes the characterization of the particle size distribution of cellulose nanocrystals (CNC), the synthesis and characterization of fluorescent CNCs, and the development of a fluorescence microscopy method to probe the distribution of fluorescent CNCs in polymer composites. In this thesis, several methods are used to characterize the size of CNC particles. Size distribution measurements by single particle counting methods (Transmission electron microscopy, Atomic force microscopy) are compared to an ensemble method, Dynamic lighting scattering (DLS) and differences between the various methods will be discussed. The effect of sonication on the CNC size distributions measured by AFM and DLS is examined. Furthermore, a reliable and reproducible method for re-dispersing dry CNC powder will be explored in this chapter since CNC is often stored in a dry environment due to its stability. Rhodamine B isothiocyanate (RBITC) and 5-(4,6-dichlorotriazinyl) amino fluorescein (DTAF) were selected for labelling CNCs. These dyes have the advantage of being cheap and readily available and compatible with relatively simple synthetic chemistry. The photophysical properties of all dye labeled CNCs were studied in more detail than in previous studies. The focus is on understanding the most appropriate labeling efficiency to maximize the ability to detect individual CNCs while minimizing the amount of dye used to avoid modifying the CNC properties. The characterization methods include ensemble methods such as UV-Vis absorption and scattering measurements, fluorescence spectroscopy and single molecule methods such as Total internal reflection fluorescence microscopy (TIRFM), Atomic force microscopy (AFM) and correlated TIRFM/AFM measurements. All of these methods have their advantages and disadvantages. After characterization, the most suitable dye labeled CNC sample was selected for development of a fluorescence microscopy method to characterize CNC distribution in CNC/polymer composites. The dye labeled CNC has been incorporated into polyvinyl alcohol (PVA) films and studied by fluorescence microscopy. These experiments demonstrated that the level of CNC agglomeration varies significantly for different film preparation methods, indicating that fluorescence microscopy is a useful and easily accessible method for optimizing film preparation. The self-quenching of the dye in the film was also measured and discussed and is an important consideration for choice of the dye loading and CNC content in the films.

Cellulose nanocrystals (CNCs) are rod-shaped nanoparticles derived from cellulose, the most abundant polymer in the world. CNCs are as strong as Kevlar™, have a high aspect ratio (traditional nanoparticles are spherical) and thus, a higher surface area, which makes them ideal for use in nanocomposites. In addition, CNCs are considered the only safe nanomaterial according to Health Canada. In this thesis, CNCs were used to produce nanocomposites via in situ semi-batch emulsion polymerization. The target application for these nanocomposites was as pressure sensitive adhesives (PSAs). In the past, CNCs have been blended with polymers rather than added in situ. Emulsion polymerization is considered a more sustainable method to synthesize polymers compared to say, solution polymerization. However, adhesives synthesized using this method tend to have a lower shear strength due to poor gel network formation. As a result, conventional emulsion-based PSAs suffer from the inability to increase certain adhesive properties (e.g., tack and peel strength) while simultaneously increasing shear strength. In this thesis, we demonstrate how the use of CNCs via in situ emulsion polymerization overcomes this classic problem. Two polymer systems were tested: isobutyl acrylate (IBA)/n-butyl acrylate (BA)/methyl methacrylate (MMA) and 2-ethylhexyl acrylate (EHA)/BA/MMA. The use of CNC with IBA, a relatively hydrophilic monomer, rather than with EHA, a highly hydrophobic monomer, resulted in the simultaneous improvement of tack, peel strength and shear strength of the PSA films. Dynamic mechanical analysis (DMA) also indicated improved storage and loss moduli with increasing CNC content, further supporting the reinforcing effect of the CNCs within the PSA. EHA followed similar trends as IBA for conversion, particle size, viscosity, pH, glass transition temperature and gel content. On the other hand, the use of CNC with EHA yielded less improvement in adhesive properties due to poor dispersion of the CNCs because of the hydrophobic repulsion by the EHA.

Cellulose nanocrystals (CNCs) are an ideal reinforcing agent for polymer nanocomposites because they are lightweight, nano-sized, and have a high elastic modulus. To date, using cellulose nanocrystals in common matrices has been generally unsuccessful due to their hydrophilicity and incompatibility with hydrophobic polymers. To overcome the poor compatibility, we have grafted poly(methyl methacrylate) (PMMA) onto the surface of the nanocrystals for the first time using a one-pot, aqueous in-situ “grafting from” polymerization reaction with ceric ammonium nitrate initiator to produce poly(methyl methacrylate)-grafted-cellulose nanocrystals (PMMA-g-CNCs). We compared the compounding of CNCs and modified CNCs with PMMA using two processing methods; melt mixing and wet ball milling. We examined the morphological, mechanical and rheological behaviour of the nanocomposites and found that ball milled composites had lower mechanical and rheological performance compared to melt mixed composites for both CNCs and modified CNCs. Additionally, we found that high (>1 wt. %) loadings of CNCs had a positive effect on the performance of nanocomposites, while low loadings of CNCs and all loadings of PMMA-g-CNCs had no net effect on the performance of the nanocomposites compared to the control. The morphology of nanocomposites showed some agglomeration in the samples with CNCs, but more pronounced agglomeration in samples with PMMA-g-CNCs. This is consistent with the decreased rheological and mechanical behaviour of composites with PMMA-g-CNCs compared with CNCs. / Thesis / Master of Applied Science (MASc)

This thesis describes the investigation of the properties of cellulose nanocrystals (CNCs) in water and at interfaces in the presence of different water-soluble polymers and surfactants. The potential of producing hydrogels, emulsions, and foams using both CNCs and surfactants and polymers is extensively explored herein. Interactions between CNCs and polymers were studied by measuring adsorption of polymers on CNC-coated surface in quartz crystal microbalance with dissipation monitoring (QCM-D) and surface plasmon resonance (SPR) instruments. Hydroxyethyl cellulose, hydroxypropyl guar, and locust bean gum adsorbed onto CNC-coated surfaces, whereas dextran did not adsorb. Gelation of CNC dilute dispersions was found for the samples added with adsorbing polymers, whereas the introduction of non-adsorbing polymers showed no such change of rheological behaviors of CNC dilute dispersions. The further addition of negative surfactant SDS or non-ionic surfactant Triton X-100 disrupted the gels whereas cationic surfactant CTAB did not. These behaviors illustrate the complexities associated with including CNC dispersions in formulated water-based products where polymers and surfactants are commonly used as well. The adsorption of cationic surfactants on CNC particle surfaces and the associated change of CNC hydrophobicity were investigated. Surfactant-modified CNCs were then employed as emulsifying agents to determine the effects of stabilizing oil-water interface with CNCs after surfactant addition. Emulsion stability was substantially enhanced with the introduction of surfactants. Based on the chemistry of cationic surfactants, and the extent CNC surface hydrophobicity increases after surfactant binding, either oil-in-water or water-in-oil emulsions were successfully produced. This in situ surfactant adsorption method thus offers a simple way of modifying surface hydrophobicity of CNCs and allows fine tuning of CNC-based emulsion properties. Adsorbing polymers were used together with CNCs to prepare stable emulsions. The introduction of polymers facilitated the production of emulsion droplets with enhanced stability and smaller diameters. Both polymer-coated CNCs and the extra polymers partitioned at the interface and worked as the emulsifiers in a synergistic manner, leading to a reduction in CNC coverage on the emulsion droplet surfaces. Furthermore, reversible thermogelation of the emulsion was obtained when thermosensitive polymers were added. No noticeable emulsion coalescence occurred after multiple cycles of heating and cooling treatments of the emulsion gels. Freeze-drying and air-drying of these emulsion gels produced oil powders containing oil content as high as 94 wt. %. Finally, highly stable wet foams were successfully produced using CNCs and the water-soluble polymer, methyl cellulose. The effect of CNC and methyl cellulose concentration on the stability of air-water interfaces was elucidated. Both foamability and foam stability were greatly improved by adding CNCs to methyl cellulose solutions. The CNC particles helped to retain fluid in the films and plateau borders between bubbles, increasing bulk viscosity, and impeding water drainage. We also demonstrated that adding various monomers to CNCs- methyl cellulose wet foams did not lead to noticeable foam breaking. The successful production of macroporous structures with tailored chemistry and properties was achieved by subsequent polymerization of the monomers added to the foam. / Thesis / Doctor of Philosophy (PhD)

This thesis describes the investigation of the properties of cellulose nanocrystals (CNCs) in water and at interfaces in the presence of different water-soluble polymers and surfactants. The potential of producing hydrogels, emulsions, and foams using both CNCs and surfactants and polymers is extensively explored herein. Interactions between CNCs and polymers were studied by measuring adsorption of polymers on CNC-coated surface in quartz crystal microbalance with dissipation monitoring (QCM-D) and surface plasmon resonance (SPR) instruments. Hydroxyethyl cellulose, hydroxypropyl guar, and locust bean gum adsorbed onto CNC-coated surfaces, whereas dextran did not adsorb. Gelation of CNC dilute dispersions was found for the samples added with adsorbing polymers, whereas the introduction of non-adsorbing polymers showed no such change of rheological behaviors of CNC dilute dispersions. The further addition of negative surfactant SDS or non-ionic surfactant Triton X-100 disrupted the gels whereas cationic surfactant CTAB did not. These behaviors illustrate the complexities associated with including CNC dispersions in formulated water-based products where polymers and surfactants are commonly used as well. The adsorption of cationic surfactants on CNC particle surfaces and the associated change of CNC hydrophobicity were investigated. Surfactant-modified CNCs were then employed as emulsifying agents to determine the effects of stabilizing oil-water interface with CNCs after surfactant addition. Emulsion stability was substantially enhanced with the introduction of surfactants. Based on the chemistry of cationic surfactants, and the extent CNC surface hydrophobicity increases after surfactant binding, either oil-in-water or water-in-oil emulsions were successfully produced. This in situ surfactant adsorption method thus offers a simple way of modifying surface hydrophobicity of CNCs and allows fine tuning of CNC-based emulsion properties. Adsorbing polymers were used together with CNCs to prepare stable emulsions. The introduction of polymers facilitated the production of emulsion droplets with enhanced stability and smaller diameters. Both polymer-coated CNCs and the extra polymers partitioned at the interface and worked as the emulsifiers in a synergistic manner, leading to a reduction in CNC coverage on the emulsion droplet surfaces. Furthermore, reversible thermogelation of the emulsion was obtained when thermosensitive polymers were added. No noticeable emulsion coalescence occurred after multiple cycles of heating and cooling treatments of the emulsion gels. Freeze-drying and air-drying of these emulsion gels produced oil powders containing oil content as high as 94 wt. %. Finally, highly stable wet foams were successfully produced using CNCs and the water-soluble polymer, methyl cellulose. The effect of CNC and methyl cellulose concentration on the stability of air-water interfaces was elucidated. Both foamability and foam stability were greatly improved by adding CNCs to methyl cellulose solutions. The CNC particles helped to retain fluid in the films and plateau borders between bubbles, increasing bulk viscosity, and impeding water drainage. We also demonstrated that adding various monomers to CNCs- methyl cellulose wet foams did not lead to noticeable foam breaking. The successful production of macroporous structures with tailored chemistry and properties was achieved by subsequent polymerization of the monomers added to the foam. / Thesis / Doctor of Philosophy (PhD)

This project studies the generation of crystalline mesoporous structured titanium dioxide (TiO2) using cellulose nanocrystal (CNC) aerogel hard templates for photocatalytic and biomaterial applications. Suspensions of CNCs in water varying in solid loading from 20 mg/mL to 100 mg/mL were prepared and frozen at three different temperatures (-20 °C, -40 °C, or -80 °C) using four combinations of hollow cylindrical molds and mold plates with different thermal conductivities (stainless-steel or glass) placed on different heat conductive and insulative substrates (aluminum, polystyrene foam and cardboard). Frozen samples were then freeze dried to sublimate the ice and render a multiscale and mesoporous structure with a variety of microstructural features, including lamellar sheeting, flakes, ribbons, or striations. Ceramic green bodies are then produced by reacting Titanium isopropoxide with water through several different processes to generate amorphous TiO2 either in-situ in the CNC aerogel or as a suspension for infiltration under varying pressure. Green bodies are dried at room temperature, and the extent of ceramic coating of the template is visually determined using SEM imaging. Once dried, crystalline TiO2 are produced through a two-step heat treatment with a CNC burnout at 270 °C and crystallization and sintering at 500 °C, 600 °C, or 1000 °C. The final crystallinity and phase composition is examined using XRD, and the final porosity is determined using BET. Results have shown the ability to satisfactorily coat aerogels under 10 mm in one dimension with TiO2. These samples have been successfully heat-treated to produce both anatase and rutile phase TiO2 while maintaining the macrostructure of the CNC aerogel. Multiscale porosity has been achieved, and samples heat treated at 1000 °C have achieved structural integrity. / Master of Science / Titanium Dioxide (TiO2) is a common material in today's world used in a range of applications including pigments, sunscreens, and thin films. It is a chemically and physically stable material, making it ideal for some biomedical applications including bone and cell growth scaffolds. TiO2 is also photocatalytic and has been used in photovoltaic cells and water decontamination systems to take advantage of this property. While TiO2 has been effectively implemented in these applications, the multiscale, controllable porous structure required for these applications has proven complicated to generate. To help improve this process, cellulose nanocrystal (CNC) aerogels were investigated as tunable hard templates for porous TiO2. Controlled ice templating through alteration of the freezing conditions followed by freeze drying provided a reliable method for the production CNC aerogels with repeatable micro and macrostructures. Testing multiple methods for coating the template in TiO2 led to the successful replication of the template in a ceramic part. The final TiO2 exhibited multiscale porosity with micro and macrostructures matching those of the CNC aerogel template. These parts can be tailored to fit a desired application by controlling the structure of the aerogel.

Currently, many drugs are preclinically tested on two-dimensional cell cultures. However, this method does not adequately replicate the cellular interactions or diffusion gradient that occur in three-dimensional tissues, leading to poor indicators of how a drug may affect human tissues. The objective of this project was to use bioprinted pancreatic cancer cell cultures as a platform for three-dimensional drug testing. Various bioink formulations of cellulose, gelatin, and alginate were evaluated to determine which provided the best printability and cell viability. A cellulose nanocrystal and alginate hydrogel showed superior printability due to its shear thinning properties. Additionally, initial cell viability was nearly 80%, and it remained above 60% over four days. Use of a custom spinning bioreactor at 50 rpm resulted in no improvements to cell viability. Overall, the system shows potential as a drug testing platform to evaluate the effectiveness of various drug formulations on three-dimensional pancreatic cancer cell cultures.

A thesis submitted to the Faculty of Engineering and the Built Environment in fulfilment of the requirement for the Degree of Masters of Science, University of the Witwatersrand, Johannesburg, 2019 / Drilling Mud holds an important role in the drilling process in such a way that it is a determinant key to the success of the operation as well as the money spent throughout the process. Indeed the success and the cost of the operation can be severely impacted by some challenges experienced while drilling such as temperature and pressure conditions which leads to fluid loss, fluid deterioration...As a result there is a need to formulate a fluid with desirable rheological properties to withstand such undesirable parameters. Therefore this work was aimed to improve emulsion drilling fluids (EDFs) based nanoparticles with enhanced properties. Many investigations were performed to find a proper emulsion stability as well as a good drilling fluid performance. The stability of the prepared emulsion drilling fluids was done using surfactant with different concentrations for several days. After several days of preparation, the EDFs containing DTAB as surfactant have showed a better emulsion stabilizer compared to the Triton X-100 ones. In addition an investigation combining both NPs and surfactants confirmed the used of NPs to improve DF and revealed the effective use of ZnO NPs for drilling fluids application and preferentially with DTAB as surfactant. Following that result, the 2nd part of the work was based on the synthesis and characterization of CNCs as NPs to formulate EDF with DTAB as surfactant. The CNCs NPS were successfully obtained via the method of oxidation of microfibrillated cellulose through TEMPO-mediate and after characterization using TEM, spherical NPs with small size varying from 10-50nm were observed. The FANN® Model 35 viscometer served to display the behavior of the shear stress and viscosity of the prepared fluids against variable shear rate at variable NPs and temperature concentration. The rheological and filtration properties were increase with increase in CNCs content from 0.8 to 1.2% of fluid in room temperature and with an increase in temperature. / PH2021

Non-ionic surfactants are known to enhance the biochemical conversion of lignocellulosic (LC) biomass to bioethanol. Their mechanisms of action, however, are incompletely understood. This research was conducted to elucidate the effects of the non-ionic surfactant Tween 80 on the enzymatic hydrolysis of cellulose and LC substrates. Model cellulose substrates were prepared from cellulose nanocrystals (CNCs) obtained by sulfuric acid hydrolysis of wood pulp. Two methods were developed for the removal of the sulfate groups on the CNCs, resulting from the use of sulfuric acid in their preparation. The effect of sulfate groups, which may be introduced into LC biomass during pretreatment with sulfuric acid, on the enzymatic hydrolysis of cellulose was studied with model cellulose substrates prepared from CNCs with different sulfate group densities. Adsorption of cellulases onto sulfated substrates increased with increasing sulfate group density but their rate of hydrolysis decreased. The decrease indicated an inhibitory effect of sulfate groups on the enzymatic hydrolysis of cellulose, possibly due to non-productive binding of the cellulases onto the substrates through electrostatic interactions instead of their cellulose binding domains. The effect of Tween 80 on the adsorption of cellulases onto lignin, often present as residual lignin in pretreated biomass, was studied with model lignin substrates, prepared from kraft lignin, organosolv lignin, and milled wood lignin. Cellulases appeared to adsorb onto the lignin substrates via both hydrophobic and polar interactions. Tween 80 molecules on the lignin substrates seemed to hinder cellulase adsorption via hydrophobic interactions and reduced the adsorption rate. Finally, the effects of lignin and Tween 80 on the enzymatic hydrolysis of cellulose and LC substrates were studied. Lignin hindered both the adsorption of cellulases onto the substrates and the enzymatic hydrolysis of the substrates. Tween 80 was found to form surfactant–protein complexes with cellulases in solution without compromising cellulase activity. Either substrate-adsorbed or in solution, Tween 80 had no effect on the hydrolysis of cellulose by cellulases. Substrate-adsorbed Tween 80 increased the apparent enzymatic hydrolysis rates of LC substrates but the ability of Tween 80 to increase their apparent hydrolysis rate depended strongly on their structural properties and the chemical properties of the lignin. Hence, Tween 80 may be able to mitigate the inhibitory effect of lignin on the enzymatic hydrolysis of pretreated biomass. / Ph. D.

In recent years, there has been a significant amount of research into cellulose nanocrystals (CNCs). These materials are categorized as being between 5 and 10 nm wide and being 100-250 nm long. CNCs have several uses, but the most common is the reinforcement of polymer composites. Here I present 2 papers investigating CNC-based composites. By using standard bleaching procedures, pure cellulose was isolated from pistachio shells. Sulfuric acid was used to isolate cellulose nanocrystals from the purified cellulose. The obtained crystals were investigated by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The CNCs were also added to thermoplastic polyurethane (TPU) to observe the reinforcement effects by dynamic mechanical analysis. Pistachio shells offered a high yield source material for CNCs, with a high aspect ratio but a low crystallinity. They did offer significant reinforcement of the TPU, but less than the commercially available wood-based CNCs. Wood-based CNCs were also mixed with TPU in structured composites to create a film which actuates when exposed to water. The method of actuation is based on the different amounts of absorption of water in the composite as opposed to the pure TPU. The actuation was modeled based on the absorption of water and the modulus of two components. Mechanical properties of the CNC/TPU composites were evaluated via dynamic mechanical analysis, and water absorption was measured gravimetricaly. The tests helped us to evaluate our model which we compared to the composites. / Master of Science / Composites are a category of materials where two or more materials are used together to enhance each of their strengths. Such materials are often used in airplanes, spacecraft, sporting equipment, and many high-end products. Cellulose nanocrystals (CNCs) have been research with the goal of improving the environmental sustainability and performance of composite materials. This newly utilized material is found in plants and some animals to provide them with their strength. Researches have already shown that CNCs can improve the performance of many materials while reducing their lifetime environmental impact. In order to increase the market for CNCs, we are looking at cost-reducing methods of producing them as well as finding exciting new uses for them once they are made. Right now, most CNCs are isolated from wood or cotton, which already have existing markets. This thesis presents a method of using pistachio shells, which are a waste product in many parts of the world including the United States. By finding new sources of CNCs, we hope to add to the body of knowledge and reduce the price of CNC production. This thesis also lays the groundwork for a material that changes shape when exposed to water. By integrating CNCs into only part of a polymer, when water is added, the part with the CNCs will increase in size, causing it to push on the polymer. Our hope is to create a new use for CNC composites to help to increase the market for them. We discuss potential methods and proofs of concept on how to create a 3D-printed part using CNCs and polyurethane.