M.Sc. (Chemistry) / Polymer nanocomposites are a new class of composites in which at least one dimension of the particles dispersed in the polymer matrix is in the nanometer range. Recently, different types of zeolite minerals, either natural (Clinoptilolite, chabazite, modernite) or synthetic (A-type, X-type, Y-type) are being employed as particulate fillers into the polymer matrix. Owing to their unique ion exchange phenomenon, zeolites have been widely studied as heavy metal adsorbents, but very few researchers have focused on the sorption of heavy metal ions on zeolite-filled polymer nanocomposites...

M.Sc. (Chemistry) / The quality of fresh water is deteriorating due to pollution by a wide range of substances as a result of industrial, agricultural, domestic, mining and other anthropogenic activities. Even at trace levels in water, some pollutants are toxic to organisms through acute or chronic effects or through bioaccumulation. Conventional water treatment is often ineffective at removing pollutants to the ultra-low levels required by water quality standards and other technologies employed to remove toxic compounds from water have high capital and operating costs and other disadvantages. There is therefore an ongoing need to develop low-cost technologies that are effective for the removal of toxic pollutants from water. In our laboratories, iron and nickel (Fe/Ni) decorated carbon nanotube (CNT)/cyclodextrin polymers (β-CDs) showed promising results in previous studies carried out for the degradation and removal of toxic organic pollutants in water. However, the powder form of the polymer makes its direct application in water treatment difficult. The leaching of metal nanoparticles and carbon nanotubes from the polymer into the water being treated is also of concern due to their potential toxicity. In this study, alginate beads were investigated as supports for two kinds of nanocomposites, Fe/Ni decorated carbon nanotubes and Fe/Ni decorated carbon nanotube/cyclodextrin polymers. Alginate beads were selected as supports to render the nanocomposites more conducive towards water treatment applications since they are easy to handle and recover from water and are also stable supports that can prevent the leaching of nanomaterials into treated water.

D.Phil. (Chemistry) / Please refer to full text to view abstract

A range of inorganic nanoparticles/nanophosphors that act as ultraviolet radiation absorbers were characterised and assessed in this thesis. Iron doped lithium aluminate phosphor was synthesised using a solid state reaction and also by flame spray pyrolysis. The phosphors prepared by different synthesis methods were characterised to identify their crystal structures and morphologies. Downconverting photoluminescent properties of the phosphors both as pure powders and embedded in polypropylene by co-rotating twin screw extrusion are reported. Zinc oxide nanoparticles made by flame spray pyrolysis were also investigated. They were incorporated into polymers by means of three different approaches including co-rotating twin screw extrusion, spin coating and solvent casting. The resulted composite films were explored to understand the distribution of the zinc oxide nanoparticles. The transmittance and ultraviolet absorption of the nanocomposites were studied and are reported herein. Another set of nanophosphors studied were zinc rich luminescent zinc oxides. They were prepared from the zinc oxide nanoparticles by firing them in a reducing atmosphere. The as-prepared nanophosphors manifested good downconverting photoluminescent properties and maintained their functions when embedded into polystyrene by solvent casting. In this thesis a new route of synthesising aluminium doped zinc oxide nanoparticles was also established. This new approach was based on a series of unexpected results within some trials that were attempting to coat a layer of alumina on the zinc oxide nanoparticles. The concentration of the Al3+ in the final product could be adjusted by tailoring the amount of the Al3+ in the reactants during the synthesis procedures. It was also possible to coat various zinc oxide nanostructures with the aluminium doped zinc oxide.

The aim of this study was to prepare composite materials based on titanium dioxide (TiO2) and silicon dioxide (SiO2), and to evaluate their photo-catalytic and antimicrobial properties. Carbon and nitrogen doped TiO2nano-particles were prepared via a sol gel synthesis, which is a simple hydrolysis and condensation technique. In situ doping was carried out using glucose and urea as carbon and nitrogen sources respectively. Doping increased the spectral response of titanium dioxide photo-catalyst, allowing it to utilise the visible region which is much wider than the UV region (about 40 % of the solar spectrum), thus making it a more efficient photo-catalyst. The carbon and nitrogen doped TiO2-SiO2nano-particles were immobilized on glass support material to allow for easy separation of the spent photo-catalyst after the photo-degradation process. Tetraethyl orthosilicate (TEOS) was employed as both a binder and precursor for silicon dioxide. A mixture of TiO2 and TEOS in a 1:1 ratio was allowed to polymerize on a glass support which had been treated with hydrofluoric acid to introduce OH groups. The prepared photo-catalytic material was characterized by FT-IR, XRD, DRS, TEM, EDX, and BET analyses. Carbon was found to be more effective as a dopant than nitrogen. It brought about a band gap reduction of 0.30 eV and a BET surface area of 95.4 m2g-1 on the photo-catalyst as compared to a gap reduction of 0.2 eV and surface area of 52.2 m2g-1 for nitrogen doped TiO2. On the other hand, introduction of SiO2 allowed utilization of visible light by the TiO2-SiO2 nano-composite leading to an improved rate of photo-degradation of both methyl orange and phenol red. However, the immobilization of TiO2 on support material made it less effective towards inactivation of E. coli ATCC 25922 bacterial cells when compared to powdered TiO2 which was able to inactivate about 98 % of the bacterial cells within an hour of treatment.

The discovery of carbon nanotubes (CNTs) in 1991 by Iijima revealed the possibility of ultra-strong materials exploiting the properties of materials at smaller length scales. The superior strength, stiffness, and ability to perform under extreme conditions motivated researchers to investigate further on CNTs and similar materials at nanoscale. This resulted in discovery of various nanostructures such boron nitride nanotubes (BNNTs), graphene, hexagonal boron nitride sheets etc. Many of such nanostructures exhibited superior strength and stiffness comparable to that of CNTs. Out of these nanotubes, BNNTs have recently attracted attention from researchers due to their excellent mechanical properties similar to that of CNTs along with better chemical and thermal stability. Thus, BNNTs can be used for varieties of applications such as protective shield for nanomaterials, optoelectronics, bio-medical, nano spintronics, field-emission tips in scanning tunneling and atomic force microscope, and as reinforcement in composites. BNNTs are also used in other applications such as water cleansing, hydrogen storage, and gas accumulators. To exploit these ultra-strong materials, the mechanics of materials under different conditions of loading and failure need to be studied and understood. Also, to make use of the material in a nanocomposite or other applications, the material properties should be evaluated. The present work is focused on the computational study of the mechanics of nanotubes with special reference to BNNTs and CNTs. Note that the attention is not given to the material but to the nanostructure and mechanics. Hence depending on the state-of-the-art, BNNTs and CNTs are used wherever it is appropriate along with justifications. The chapter-wise outline of the present work is given below. The first chapter is an introduction along with a state-of-the-art literature review. The second chapter introduces the molecular simulation methodology in brief. The chapters from the third to the seventh present the work in detail and describe the major contributions. The final chapter summarizes the work along with a few possible directions to extend the present work. Chapter 1 In this chapter, the importance of computational techniques to study the mechanics at the nanoscale is outlined. A brief introduction to various nanostructures and nanotubes are also given. A detailed literature review on the mechanics of nanotubes with special attention to elastic properties, buckling, tensile failure, and as reinforcement in nanocomposites is presented. Chapter 2 In this chapter, the molecular simulation technique is outlined. The molecular dynamics (MD) simulation is one of the most common simulation techniques used to study materials at the nanoscale. A few interatomic potentials that are used in an MD simulation are explained. Theories linking continuum mechanics with the molecular dynamics are also explained here. Chapter 3 In this chapter, the elastic behavior of single-walled BNNTs under axial and torsional loading is studied. Molecular dynamics (MD) simulation is carried out with a tersoff potential for modeling the interatomic interactions. Different chiral configurations with similar diameter are considered to study the effect of chirality on the elastic and shear moduli. Furthermore, the effects of tube length on elastic modulus are also studied by considering different aspects ratios. It is observed that both elastic and shear moduli depend on the chirality of a nanotube. For aspect ratios less than 15, the elastic modulus reduces monotonically with an increase in the chiral angle. For chiral nanotubes the torsional response shows a dependence on the direction of loading. The difference between the shear moduli against and along the chiral twist directions is maximum for a chiral angle of 15◦, and zero for zigzag (0◦) and armchair (30◦) configurations. Chapter 4 Buckling of nanotubes have been studied using many methods such as MD, molecular mechanics, and continuum based shell theories. In MD, motion of the individual atoms are tracked under an applied temperature and pressure, ensuring a reliable estimate of the material response. The response thus simulated varies for individual nanotubes and is only as accurate as the force field used to model the atomic interactions. On the other hand, there exists a rich literature on the understanding of continuum mechanics based shell theories. Based on the observations on the behavior of nanotubes, there have been a number of shell-theory-based approaches to study the buckling of nanotubes. Although some of these methods yield a reasonable estimate of the buckling stress, investigation and comparison of buckled mode shapes obtained from continuum analysis and MD are sparse. Previous studies show that a direct application of shell theories to study nanotube buckling often leads to erroneous results. In this chapter, the nonlocal effect on the mechanics of nanostructures is studied using Eringen’s nonlocal elasticity. The buckling of carbon nanotubes is considered as an example to demonstrate and understand the nonlocal effect in the nanotubes. Single-walled armchair nanotubes with the radius varying from 3.4nm to 17.7nm are considered and their critical buckling stresses are predicted based on multiscale modeling techniques including classical and nonlocal continuum mechanics theories and MD simulation. Fitting nonlocal mechanics models to MD simulation yields a radius-dependent length-scale parameter, which increases approximately linearly with the radius of carbon nanotube. In addition, the nonlocal shell model is found to be a better continuum model than the nonlocal beam model due to its ability to include the circumferential nonlocal effect. Chapter 5 In this chapter, the effects of geometrical imperfections on the buckling of nanotubes are studied. The present study reveals that a major source of the error in continuum shell theories in calculating the buckling stress can be attributed to the geometrical imperfections. Here, geometrical imperfections refer to the departure of the shape of the nanotube from a perfect cylindrical shell. Analogous to the shell buckling in the macro-scale, in this work the nanotube is modeled as a thin-shell with initial imperfection. Then a nonlinear buckling analysis is carried out using the Riks method. It is observed that this proposed approach yields significantly improved estimate of the buckling stress and mode shapes. It is also shown that the present method can account for the variation of buckling stress as a function of the temperature considered. Hence, this turn out to be a robust method for a continuum analysis of nanotubes taking in the effect of variation of temperature as well. Chapter 6 In this chapter, the effects of Stone-Wales (SW) and vacancy defects on the failure behavior of BNNTs under tension are investigated using MD simulations. The Tersoff-Brenner potential is used to model the atomic interaction and the temperature is maintained close to 300 K. The effect of a SW defect is studied by determining the failure strength and failure mechanism of nanotubes with different radii. In the case of a vacancy defect, the effect of an N-vacancy and a B-vacancy is studied separately. Nanotubes with different chirality but similar diameter are considered first to evaluate the chirality dependence. The variation of failure strength with the radius is then studied by considering nanotubes of different diameter but same chirality. It is observed that the armchair BNNTs are extremely sensitive to defects, whereas the zigzag configurations are the least sensitive. In the case of pristine BNNTs, both armchair and zigzag nanotubes undergo brittle failure, whereas in the case of defective BNNTs only the zigzag ones undergo brittle failure. An interesting defect-induced plastic behavior is observed in defective armchair BNNTs. For this nanotube, the presence of a defect triggers mechanical relaxation by bond breaking along the closest zigzag helical path, with the defect as the nucleus. This mechanism results in a plastic failure. Chapter 7 In this chapter, the utility of BNNTs as reinforcement for nanocomposites with metal matrix is studied using MD simulation. Due to the light weight, aluminium is used as the matrix. The influence of number of walls on the strength and stiffness of the nanocomposite is studied using single-and double-walled BNNTs. The three body tersoff potential is used to model the atomic interactions in BNNTs, while the embedded atom method (EAM) potential is used to model the aluminium matrix. The van der Waals interaction between different groups — the aluminium matrix with the nanotube or the between the concentric tubes in double walled BNNT — is modeled using a Lennard Jones potential. A representative volume element approach is used to model the nanocomposite. The constitutive relations for the nanocomposite is also proposed wherein the elastic constants are obtained using the MD simulation. The nanocomposite with reinforcement shows improved axial stiffness and strength. The double-walled BNNT provides more strength to the nanocomposite than the single-walled BNNT. The BNNT reinforcement can be used to design nanocomposites with varying strength depending on the direction of the applied stress. Chapter 8 The summary of the work with a broad outlook is presented in this chapter. The major conclusions of the work are reiterated and possible directions for taking the work further ahead are mentioned.

Issues concerning mechanisms of durability of hydrated cement phases in aggressive environments were studied. The possibility of using organic compounds in order to modify the micro- and nanostructure of the calcium-silicate-hydrate (C-S-H) phases was also investigated. Pure cement-based hydrated phases were synthesized and characterized by several analytical techniques such as X-ray diffraction, thermal gravimetric analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. Compacted samples of the synthetic hydrated cement phases were also prepared and used for the assessment of durability and mechanical properties. This doctoral thesis is comprised of several research chapters which can be categorized into two main parts. The first part focuses on the development of novel organically modified C-S-H systems. The second part involves the mechanisms underlying the volume stability of phase pure sulfoaluminate and related phases. A brief description of each part is as follows: - development of novel organically modified C-S-H systems: The mechanisms of interaction of organic compounds with the nanostructure of C-S-H systems were studied. A model for the nanostructure of the resulting composite systems was proposed. In addition, the organically modified systems were tested for length-change, calcium-ion leaching and diffusion of isopropanol. Dynamic mechanical analysis and microindentation techniques were also used to determine the mechanical performance. Evidence of the superior engineering performance of the novel organically modified C S-H systems was provided. - mechanisms of the volume stability of sulfoaluminate and related phases: Volume stability and change in the microstructure of the synthetic ettringite, monosulfate and thaumasite was critically examined in de-ionized water as well as in highly concentrated gypsum- or lime-water. A new dissolution-based mechanism for the expansion of these phases was proposed. The volume stability of multicomponent systems comprised of the C-S-H-based system (prepared in part I) and these sulfate-based hydrated phases was also investigated. It was suggested that the systems containing the modified C-S-H rather than the phase pure C-S-H had better resistance to crack growth and disintegration originating from the presence of ettringite or thaumasite.

A Portuguese clay (BRN) from the North East city of Bragança was collected and characterized in terms of health treatment and applied towards the preparation of nanocomposites with Polylactide (PLA). The silt-clay fraction of BRN is mainly composed of smectite with less illite, kaolinite and other minerals. The physicochemical properties are applicable for the topical applications and are mainly influenced by smectite. With the hazardous elements present, further bioavailability tests should be conducted. PLA nanocomposites with BRN and Wyoming montmorillonite SWy-2 (MMT) were respectively prepared through the solution casting method with ultrasonic stirring and using cetyltrimethylammonium bromide (CTAB) as the surfactant. The X-ray diffraction patterns show the exfoliated structures in most samples. Thermal gravimetric analysis reveals the increased thermal stability of the nanocomposites. The complexes were also characterized by nitrogen adsorption, infrared analysis and nuclear magnetic resonance for comparing the differences between BRN and MMT.

Submitted in fulfilment of the requirements for the degree of Master of Engineering: Mechanical Engineering, Department of Mechanical Engineering, Faculty of Engineering and the Built Environment, Durban University of Technology, Durban, South Africa. 2017. / In this study, the fatigue life of fiber reinforced composite (FRC) materials system was investigated. A nano-filler was used to increase the service life of the composite structures under cyclical loading since such structures require improved structural integrity and longer service life. Behaviour of glass fiber reinforced composite (GFRC) enhanced with various weight percentages (1 to 5 wt. %) of Cloisite 30B montmorillonite (MMT) clay was studied under static and fatigue loading. Epoxy clay nanocomposite (ECN) and hybrid nanoclay/GFRC laminates were characterised using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The mechanical properties of neat GFRC and hybrid nanoclay/GFRC laminates were evaluated. Fatigue study of the composite laminates was conducted and presented using the following parameter; matrix crack initiation and propagation, interfacial debonding, delamination and S–N relationship. Residual strength of the materials was evaluated using DMA to determine the reliability of the hybrid nanoclay/GFRC laminates. The results showed that ECN and hybrid nanoclay/GFRC laminates exhibited substantial improvement in most tests when compared to composite without nanoclay. The toughening mechanism of the nanoclay in the GFRC up to 3 wt. % gave 17%, 24% and 56% improvement in tensile, flexural and impact properties respectively. In the fatigue performance, less crack propagations was found in the hybrid nanoclay/GFRC laminates. Fatigue life of hybrid nanoclay/GFRC laminate was increased by 625% at the nanoclay addition up to 3 wt. % when compared to neat GFRC laminate. The residual strength of the composite materials revealed that hybrid nanoclay/GFRC showed less storage modulus reduction after fatigue. Likewise, a positive shift toward the right was found in the tan delta glass transition temperature (Tg) of 3 wt. % nanoclay/GFRC laminate after fatigue. It was concluded that the application of nanoclay in the GFRC improved the performance of the material. The hybrid nanoclay/GFRC material can therefore be recommended mechanically and thermally for longer usage in structural application. / M

M.Sc. (Chemistry) / Please refer to full text to view abstract.