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The excellent in-plane strength and stiffness to-weight ratios, as well as the ease of manufacturing have made the carbon fiber reinforced polymer composites (CFRPs) suitable structural materials for variety of applications such as aerospace, automotive, civil, sporting goods, etc. Despite the outstanding performance of the CFRPs along their fibers direction (on-axis), they lack sufficient strength and performance in the out-of-plane and off-axis directions. Various chemical and mechanical methods were reported to enhance the CFRPs' out-of-plane performance. However, there are two major drawbacks for utilizing these approaches: first, most of these methods induce damage to the carbon fibers and, therefore, deteriorate the in-plane mechanical properties of the entire CFRP, and second, the methods with minimal deteriorating effects on the in-plane mechanical performance have their own limitations resulting in very confined mechanical performance improvements. These methods include integrating nano-sized reinforcements into the CFRPs' structure to form a hybrid or hierarchical CFRPs. In lieu to all the aforementioned approaches, a relatively novel method, referred to as graphitic structures by design (GSD), has been proposed. The GSD is capable of grafting carbon nanotubes (CNTs) onto the carbon fibers surfaces, providing high concentration of CNTs where they are most needed, i.e. the immediate fiber/matrix interface, and in-between the different laminae of a CFRP. This method shows promising improvements in the in-plane and out-of-plane performance of CFRPs. Zinc oxide (ZnO) nanorods are other nano-sized reinforcing structures which can hybridize the CFRPs via their radially growth on the surface of carbon fibers. Among all the reported methods for synthesizing ZnO nanorods, hydrothermal technique is the most straightforward and least destructive route to grow ZnO nanorods over carbon fibers. In this dissertation, the GSD-CNTs growth method and the hydrothermal growth of ZnO nanorods have been utilized to fabricate hybrid CFRPs. The effect of different ZnO nanorods growth morphologies, e.g. size distribution and alignment, on the in-plane tensile performance and vibration attenuation capabilities of the hybrid CFRPs are investigated via quasi-static tension and dynamical mechanical analysis (DMA) tests, respectively. As a result, the in-plane tensile strength of the hybrid CFRPs were improved by 18% for the composite based on randomly oriented ZnO nanorods over the carbon fibers. The loss tangent of the CFRPs, which indicates the damping capability, increased by 28% and 19% via radially and randomly grown ZnO nanorods, respectively. While there are several studies detailing the effects of dispersed nanofillers on the fracture toughness of FRPs, currently, there are no literature detailing the effect of surface GSD grown CNTs and ZnO nanowire -on carbon fiber- on the fracture toughness of these hybrid composites. This dissertation probes the effects of surface grown nano-sized reinforcements on the fracture toughness via double cantilever beam (DCB) tests on hybrid ZnO nanorod or CNT grafted CFRPs. Results show that the surface grown CNTs enhanced the Mode I interlaminar fracture toughness (GIc) of the CFRPs by 22% and 32%, via uniform and patterned growth morphologies, respectively, over the reference composite based on untreated carbon fiber fabrics. The dissertation also explains the basis of the improvements of the fracture toughness via finite element method (FEM). In particular, FEM was employed to simulate the interlaminar crack growth behavior of the hybrid CFRPs under Mode I crack opening loading conditions embodied by the DCB tests. These simulations revealed that the hybrid CFRP based on fibers with uniform surface grown MWCNTs exhibited 55% higher interlaminar strength compared to the reference CFRPs. Moreover, via patterned growth of MWCNTs, the ultimate crack opening resistance of the CFRPs improved by 20%. To mimic the experimental behavior of the various CFRPs, a new methodology has been utilized to accurately simulate the unstable crack growth nature of CFRPs. Several investigations reported the effects of adding nanomaterials-including CNTs- as a filler phase inside the matrix material, on the impact energy absorption of the hybrid FRPs. However, the impact mitigation performance of CFRPs based on ZnO nanorod grafted carbon fibers has not been reported. The dynamic out-of-plane energy dissipation capabilities of different hybrid composites were investigated utilizing high velocity (~90 m/s) impact tests. Comparing the results of the hybrid MWCNT/ZnO nanorod/CFRP with those of reference CFRP, 21% and 4% improvements were observed in impact energy absorption and tensile strain to failure of the CFRPs, respectively. In addition to elevated stiffness and strength, CFRPs should possess enough tolerance not only to monotonic loadings, but also to cyclic loadings to be qualified as alternatives to traditional structural metal alloys. Therefore, the fatigue life of CFRPs is of much interest. Despite the promising potential of incorporating nano-sized reinforcements into the CFRPs structure, not many studies reported on the fatigue behavior of hybrid CFRPs so far. In particular, there are no reported investigations to the effect of surface grown CNTs on the fatigue behavior of the hybrid CFRPs, due to fact that almost all the CNT growth techniques (except for the GSD method) deteriorated the in-plane performance of the hybrid CFRPs. The hybrid ZnO nanorod grafted CFRPs have not been investigated under fatigue loading as well. In this dissertation, different hybrid CFRPs were tested under tension-tension fatigue to reveal the effects of the different nano-reinforcements growth on the fatigue behavior of the CFRPs. A remarkable fatigue damage tolerance was observed for the CFRPs based on uniform and patterned grown CNT fibers. Almost two decades of fatigue life extension was achieved for CFRPs based on surface grown MWCNTs. / Ph. D.

Thesis submitted in fulfilment of the requirements for the degree DOCTOR TECHNOLOGIAE: ENGINEERING: CHEMICAL in the FACULTY OF ENGINEERING at the CAPE PENINSULA UNIVERSITY OF TECHNOLOGY 2014 / Several authors have reported on the use of alcohols – water /or mixed solvents to synthesise metal oxide nanoparticles. However, no systematic study has been carried out to evaluate the effect of mixed solvent on the particle characteristics, although considerable research has been reported, a gap still exists with regard to the effect of the alcohols as solvents on the growth kinetics of nanoparticles. To address these issues, four different alcohols, namely, methanol (MeOH), ethanol (EtOH), propanol (PrOH) and butanol (BuOH) were used as solvents in the synthesis of β-FeOOH particles. The effect of organic solvents on the growth kinetics of β-FeOOH nanorods has been evaluated for the first time in this study. Two-stage growth of akaganeite nanorods has been observed in BuOH and PrOH. The first growth stage follows a typical power law representing Ostwald ripening (OR) kinetic. The second stage was found to be asymptotic and obeyed oriented attachment (OA) kinetic. The proof of the OA kinetic also comes from the HRTEM images of the synthesised particles. Simultaneous occurrence of the two mechanisms was observed in the growth of the particles synthesised in EtOH and MeOH. The rate constants for OR kinetic, KOR, was found to be higher than the rate constant for OA kinetic, KOA, for different solvents used. Preamble The use of a mixed solvent is a new approach in the synthesis and processing of materials. Various researchers have stated that the surface tension of the solvent plays an important role in the formation of uniform nanorods. However, the effect of surface tension was not correlated with the particle growth, earlier, though the dielectric properties of the mixed solvents were only taken into account. Additionally, no quantitative or qualitative relationship was presented between surface tension and particle growth in the literature. In this work an attempt to correlate these two parameters (surface tension and particle growth) with the concentration of the precursor and temperature was made, resulting in an exponential relationship between KOR for the particle growth and surface tension of the alcohols. Furthermore, the relationship between surface tension and particle growth was validated by an independent study using statistically designed experiments to account for the influence of various process variables on the particle growth. The findings in this study obtained from both theoretical and experimental work provides an insight into the relationship between solvent surface tension and particle growth interactions, producing a new piece of information that will further promote our understanding of the formation mechanisms of β- FeOOH growth. The transformation temperature of akaganeite (β-FeOOH) nanorods to hematite (α-Fe2O3) particles was found to be solvent dependent. Thermogravimetric analysis and differential scanning calorimetry were performed to evaluate the effect of alcohol on the thermodynamic stability of the particles. Alcohol as solvent played a significant role in the dehydration property of the synthesised particles. The percentage mass loss of the particles at 300°C decreases linearly with increasing carbon number in the linear alkyl chain of the solvent. The effect of alcohol type on the particle morphology was found to be more pronounced at higher FeCl3 concentrations (>0.5M). Splitting of β-FeOOH nanorods was observed at FeCl3 concentration of 0.7M in BuOH. In PrOH, rectangular morphologies were obtained whereas nanoribbons resulted in surfactant-free conditions. It was found that the nature of anions (chloride vs. nitrate and sulphate) in the precursor salt also influenced the morphology.

L'oxyde de zinc (ZnO) est un matériau semi-conducteur qui présente des caractéristiques très intéressantes telles que : un gap directe à 3.3 eV à température ambiante, une forte énergie excitonique (60 meV à température ambiante) associé à un caractère piézoélectrique. Ces propriétés permettent de considérer le ZnO parmi les nanomatériaux prometteurs, dans une grande variété d'applications : dans le domaine de l'optoélectronique, de l'énergie photovoltaïque ou de l'environnement. Pour que ces dispositifs deviennent exploitables à l'échelle industrielle, certaines conditions doivent être satisfaites comme le contrôle de la taille des nanostructures ainsi que de leur forme, l'impact de la technique de synthèse sur l'environnement, l'économie de l'énergie utilisée dans la production du matériau. C'est dans ce cadre que nous nous sommes intéressés à l'étude de la croissance des micro / nanostructures de ZnO, en particulier à une dimension (1D). Nos échantillons sont obtenus par la synthèse hydrothermale. Cette méthode nous a permis de réaliser des nanostructures de ZnO de très bonnes qualités cristallines sous pression contrôlée (inférieur ou égal à 15 bar) et à basse température (inférieur à 250 °). Ces conditions de préparation ont l'avantage de limiter la consommation en énergie. D'autre part, nous avons utilisé l'eau comme solvant dans la préparation des solutions, ce qui présente un effet positif pour l'environnement (démarche d'éco-conception ou « green chemistry »). Dans la première partie de ce travail, nous avons étudié l'influence d'un ensemble de paramètres expérimentaux tels que : le temps, la quantité de base, la température… sur la croissance de nanorods afin de déterminer les conditions optimales pour l'obtention de nanorods homogènes, plus denses et avec une faible distribution de tailles. Dans la deuxième partie, nous nous sommes intéressés à l'étude de l'influence induite par les cations présents dans les solutions suite à l'hydrolyse des bases sur la morphologie des micro / nanostructures de ZnO. Enfin, les échantillons obtenus ont fait l'objet d'une caractérisation à la fois structurale et morphologique afin d'exploiter au mieux la richesse des géométries et les tailles des micro / nanocristaux élaborés / Zinc oxide (ZnO) is a material that belongs to the family of transparent conducting oxides (TCO) materials. Because of its important physical and chemical properties, ZnO is widely studied since the elaboration to application. It is considered as semiconductor material which has very interesting features such as a direct gap 3.37 eV at room temperature, a strong exciton energy (60 meV at room temperature) assigned to a character piezoelectric. ZnO thin films are elaborated using different techniques including physical and chemical methods. For our part, we are interested in studying the growth of micro / nanostructures of ZnO, especially one-dimensional (1D) using hydrothermal synthesis. This method allowed us to achieve ZnO nanostructures with very good crystalline qualities under controlled pressure (< 15 bar) and low temperature (<250 ° C). These preparation conditions have the advantage to limit the energy consumption. On the other hand, we have used water as solvent in the preparation of solutions which has a positive effect on the environment (eco-design or “green chemistry”). In the first part of this work, we have studied the influence of some experimental parameters such as time, the amount of base, temperature… on the growth of nanorods in order to determine the optimal conditions of the growth of the nanorods forms and their distributions. In the second part, we are interested to study the influence of the cations present in the solution on the morphology of the micro / nanostructures of ZnO. Finally, the obtained samples were characterized by XRD and SEM for the structure and the morphology and by Raman for optical properties. The different analysis of the results obtained from different techniques show a good compromise

Materials science today is a multidisciplinary effort comprising an accelerated convergence of diverse fields spanning the physical, applied, and engineering sciences. This diversity promises to deliver the next generation of advanced functional materials for a wide range of specific applications. In particular, the past decade has seen a growing interest in the development of nanoscale materials for sophisticated technologies. Aqueous colloidal microgels have emerged as a promising class of soft materials for multiple biotechnology applications. The amalgamation of physical, chemical and mechanical properties of microgels with optical properties of nanostructures in hybrid composite particles further enhances the capabilities of these materials. This work covers the general areas of responsive polymer microgels and their composites, and encompasses methods of fabricating microgel-based drug delivery systems for controlled and targeted therapeutic applications. The first part of this thesis is devoted to acquainting the reader with the fundamental aspects of the synthesis, functionalization and characteristic properties of stimulus-responsive microgels constructed from poly(N-isopropylacrylamide) (poly(NIPAm)) and other functional comonomers. In particular, the role of electrostatics on the swelling-deswelling transitions of polyampholyte microgels upon exposure to a range of environmental stimuli including pH, temperature, and salt concentration are discussed. The templated synthesis of bimetallic gold and silver nanoparticles in zwitterionic microgels is also described. The latter part of this thesis focuses on the rational development of microgel-based drug delivery systems for controlled and targeted drug release. Specifically, the development of a biofunctionalized, pH-responsive drug delivery system (DDS) is illustrated, and shown to effectively suppress cancer cells when loaded with an anticancer agent. In another chapter, the design of tailored hybrid particles that combine the thermal response of microgels with the light-sensitive properties of gold nanorods to create a DDS for photothermally-induced drug release is discussed. The photothermally-triggered volume transitions of hybrid microgels under physiological conditions are reported, and their suitability for the said application evaluated. In another component of this work, it is explicitly shown that electrostatic interactions were not needed to deposit gold nanorods on poly(NIPAm)-derived particles, thereby eliminating the need for incorporation of charged functional groups in the microgels that are otherwise responsible for large, undesirable shifts and broadening of the phase transition.