D.Phil. (Chemistry) / The application of dendritic-based materials has attracted great interest. For the first time this research has investigated the feasibility of poly (propyleneimine) (PPI) dendrimers and hyperbranched polyethyleneimine (HPEI) in combination with beta-cyclodextrin (β-CD) embedded in polysulfone (PSf) membrane for water treatment. The advantage of embedding these conjugates (β-CD-PPI and β-CD-HPEI) in PSf membranes is the presence of numerous nanocavities which can act as water channels allowing easy water passage through the membrane improving water permeability. Secondly, the presence of functional groups such as –OH and –NH greatly improves hydrophilicity of membranes. Commercial polysulfone (PSf) ultrafiltration membranes were crosslinked with β-cyclodextrin-poly (propyleneimine) (β-CD-PPI) and β-cyclodextrin-hyperbranched polyethyleneimine (β-CD-HPEI) using trimesoyl chloride (TMC) by interfacial polymerisation. These membranes were used in the rejection of Aldrich humic acid (molecular weight: 4.1 kDa) from synthetic water samples prepared in the laboratory. Moreover, β-cyclodextrin-poly (propyleneimine) (β-CD-PPI) was used as a host for the preparation of Fe/Ni nanoparticles. The new membranes were synthesised by crosslinking β-CD-PPI with trimesoyl chloride and subsequently loading Fe/Ni nanoparticles and this was supported on a commercial polysulphone (PSf) layer for the degradation of 2,4,6-trichlorophenol (2,4,6-TCP). The membrane surfaces were characterised using Fourier transform infrared/attenuated total reflectance (FT-IR/ATR) spectroscopy , scanning electron microscopy (SEM), atomic force microscopy (AFM), high resolution transmission electron microscopy (HR-TEM), water-contact angle, and water-intake capacity...

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Ochratoxin A is the most potent chlorinated derivative of the ochratoxin group, consisting of a 5'-chlorinated dihydroisocoumarin moiety linked by an amide bond to l-phenylalanine. Produced as a secondary fungal metabolite by several species of Aspergillus and Penicillium, ochratoxin A has been shown to readily contaminate a large variety of commodities including cereals, groundnuts, dried fruit, spices and coffee. This has led to widespread contamination of ochratoxin in wine, beer, milk and meat products. As ochratoxin A is a potent nephrotoxin exhibiting teratogenic and carcinogenic properties, the development of a rapid screening platform for the cost effective control of ochratoxin A content in foodstuffs is therefore required. The evaluation of metallophthalocyanine and carbon nanotube electrode modification toward the development of a nanostructured biosensor capable of enhancing the electrochemical detection of ochratoxin A in complex media is presented. Cyclic voltammetry at a glassy carbon electrode allowed for the optimization of detection parameters including pH and type of supporting electrolyte. Britton-Robinson buffer was found to be the most suitable supporting electrolyte in terms of sensitivity and reproducibility obtaining a LOD of 0.28 μM as determined by differential pulse voltammetry. Subsequent analysis determined the dependence of OTA oxidation on pH in acidic media which proceeds with the transfer of two electrons to form a quinone/hydroquinone couple shown to adsorb to the electrode surface. Passivation of the electrode through adsorption of oxidation products was shown to severely limit the detection of OTA upon successive detection cycles. Comparison of various metallophthalocyanine modifiers showed an increase in sensitivity toward the detection of OTA at phthalocyanine complexes with metal based redox processes. However with the exception of NiPc and CoTCPc complexes, phthalocyanine modification was limited by the increase in deviation of current response and extent of fouling. NiPc modification showed an increase in sensitivity by two fold with fouling characteristics comparable to an unmodified electrode while low improvements in fouling was observed at CoTCPc modified electrodes with sensitivity in detection comparable to an unmodified electrode.Modification of the electrode with multi- and single walled carbon nanotubes produced a significant increase in sensitivity toward the detection of ochratoxin A. The electrocatalytic activity of nanotube modifiers was attributed to the increase in surface area and to the addition of oxygenated functional groups upon acid treatment as confirmed by Raman spectroscopy. Acid functionalization of the carbon nanotubes for a period of two hours produced the greatest increase in sensitivity obtaining a respective LOD of 0.09 μM and 0.03 μM for analysis of ochratoxin A at multi- and single walled carbon nanotube modified electrodes. Centrifugal purification of carbon nanotubes was deemed necessary to improve the electrocatalytic activity of the nanotube modifiers through the removal of carbonaceous impurities as visualized by atomic force microscopy. Furthermore, a crude lipase preparation, lipase A, was investigated as a potential biological recognition element for selective detection of ochratoxin A in complex media. Lipase A enabled the hydrolysis of ochratoxin A to the electroactive species ochratoxin α as confirmed by thin layer chromatography and voltammetric analysis. Additional isolation of a pure hydrolase from the lipase A preparation is required prior to utilization within a nanostructured biosensor platform capable of detecting ochratoxin A in complex media.

The main goals in electroanalytical sensing are towards improved sensitivity and selectivity, or specificity, of an analyte. There are several approaches to achieving these goals with the main approach being modification of an electrode surface with synthetic or natural catalysts (enzymes), polymers and also utilisation of nanostructured materials. At present, there is a strong movement towards hybrid sensing which couple different properties of two or more surface modification approaches. In this thesis, a range of these surface modifications were explored for analysis and detection of two main analytes: the amino acid, tryptophan (Trp); and, the neurotransmitter, dopamine (DA). Specifically, this thesis aimed to utilise these methods to enhance the sensitivity and selectivity for Trp over an interferent, the indoleamine, melatonin (Mel); and, DA over the vitamin, ascorbic acid (AA). For Trp detection, immobilisation of an enzyme, Tryptophanase (Trpase) resulted in poor selectivity for the analyte. However, enhanced sensitivity and selectivity was achieved through pH manipulation of the electrolyte medium at a Nafion®-modified electrode surface for both Trp and Mel. At pH 3.0, the Mel and Trp anodic peak potentials were sufficiently resolved allowing for an LOD of 1.60 and 1.62 nM,respectively, and permitting the accurate analysis of Trp in a dietary supplement containing Mel. Multi-walled carbon nanotubes (MWCNTs) suspended in Nafion® exhibited further increases in the signal responses of these analytes at pH 3.0 and 7.4 with minimal change in the resolution of the anodic peaks. A lower sensitivity was, therefore, observed at the Nafion® and MWCNT modified electrode compared to the Nafion®-modified electrode at pH 3.0 with LODs of 0.59 and 0.80 nM exhibited for Trp and Mel, respectively. Enhanced selectivity for Trp in the presence of Mel can be achieved with MWCNTs in the presence of metallotetrasulphonated phthalocyanines (MTSPcs) particularly at pH 3.0, owing to cation exchange effects. However, the lack of sensitivity towards Trp, and even Mel, at this CoTSPc and MWCNT modified electrode remains a drawback. For DA, detection at the MWCNT and Nafion® surface resulted in improved sensitivity over that of both the bare electrode (613.0 nM) and the Nafion® modified electrode (1045.1 nM) with a calculated LOD of 133.9 nM at this layer. Furthermore, improvements in the selectivity of DA were achieved at the Nafion® and MWCNT modified electrode as exclusion of AA (150 μM) was achieved. At the MWCNT and CoTSPc surface, AA was excluded up to 130 μM with sensitivity for DA extending as low as 14.3 nM, far greater than observed for Trp and Mel. These concentrations are well within physiological concentration ranges and represent the most significant solution yet in terms of AA exclusion and enhanced sensitivity for DA. An examination of the surface layering by impedance spectroscopy and atomic force microscopy indicates that the success of the hybrid sensor utilising CoTSPc and MWCNTs lay in improved dispersion of MWCNTs and improved electron transfer kinetics, facilitated by the net charge of the materials present. This thesis, thus, showed the utility of a judicious selection of synthetic and biological catalysts, polymers and carbon nanomaterials towards a hybrid approach to the electrochemical sensing of Trp, Mel, DA and AA with focus on sensitivity and selectivity of these analytes.

This dissertation focuses on the investigation of the microstructures of two nuclear grade matrix graphites. These graphites were intended for use in the core components of a high temperature test reactor (HTTR) of the pebble bed modular reactor (PBMR) design. The graphites were provided in the form of fuel spheres and a reflector block. The techniques used in the analysis of the materials include fracturing, etching, scanning electron microscopy (SEM), nano-indentation, x-ray diffraction (XRD) and transmission electron microscopy (TEM). The microstructures of the materials were characterized successfully. The fuel sphere material consisted of a high concentration of curved graphite flakes and grains in contact with turbostratic matrix graphite. The well graphitized flakes and grains were polycrystalline in nature. Delamination cracks were prevalent in the graphite crystallites. There was no significant difference in the microstructures of the center, interior and surface regions of the fuel sphere material. No evidence of amorphous carbon or resin residues was found. The reflector material consisted of a low concentration of graphite crystallites embedded within turbostratic matrix graphite. Delamination cracks were observed within the graphite crystallites, and many cavities were present in the material. TEM observation also revealed the presence of diamond crystallites. It was concluded that the fuel sphere graphite was most probably suitable for use as is, provided that the material also possessed other required properties for use in a HTTR. The reflector material however was considered to be unsuitable for use in a HTTR. It was thus suggested that the reflector material could be made more suitable by sufficient graphitization of the turbostratic graphite which formed the bulk of the material.

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

Nanoindentation is a widely used technique to measure the mechanical properties of films with thickness ranging from nanometers to micrometers. A much better understanding of the contact mechanics is obtained mostly through finite element modeling. The experiments were modeled using the software package Nano SP1 that is based on COSMOSM™ (Structural Research & Analysis Corp, www.cosmosm.com), a finite element code. The fundamental material properties affecting pile-up are the ratio of the effective modulus to yield stress Eeff/σ and the work hardening behavior. Two separate cases of work hardening rates were considered; one with no work hardening rate and other with a linear work hardening rate. Specifically, it is observed that pile up is large only when hf/hmax is close to one and degree of work hardening rate is small. It should also be noted that when hf/hmax < 0.7 very little pile-up is observed no matter what the work-hardening behavior of the material. When pile-up occurs the contact area is greater than that predicted by the experimental methods and both the hardness and modulus are overestimated. In this report the amount by which these properties are overestimated are studied and got to be around 22% approx. Bluntness of the tip often leads to the misinterpretation of the load-displacement data. Further analysis was done in order to find out the amount of deviation from the ideal tip due to tip bluntness. Radius of the tips were also calculated for cubecorner (41.35 nm) and conical indenter (986.05 nm).

The barrier properties of polymers are a significant factor in determining the shelf or device lifetime in polymer packaging. Nanocomposites developed from the dispersion of nanometer thick platelets into a host polymer matrix have shown much promise. The magnitude of the benefit on permeability has been different depending on the polymer investigated or the degree of dispersion of the platelet in the polymer. In this dissertation, the effect of density changes in the bulk and at the polymer-platelet interface on permeability of polymer nanocomposites is investigated. Nanocomposites of nylon, PET, and PEN were processed by extrusion. Montmorillonite layered silicate (MLS) in a range of concentrations from 1 to 5% was blended with all three resins. Dispersion of the MLS in the matrix was investigated by using one or a combination of X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Variation in bulk density via crystallization was analyzed using differential scanning calorimetry (DSC) and polarized optical microscopy. Interfacial densification was investigated using force modulation atomic force microscopy (AFM) and ellipsometry. Mechanical properties are reported. Permeability of all films was measured in an in-house built permeability measurement system. The effect of polymer orientation and induced defects on permeability was investigated using biaxially stretched, small and large cycle fatigue samples of PET and nylon nanocomposites. The effect of annealing in nylon and nanocomposites was also investigated. The measured permeability was compared to predicted permeability by considering the MLS as an ideal dispersion and the matrix as a system with concentration dependent crystallinity.

abstract: There are increasing demands for gas sensors in air quality and human health monitoring applications. The qualifying sensor technology must be highly sensitive towards ppb level gases of interest, such as acetylene (C2H2), hydrogen sulfide (H2S), and volatile organic compounds. Among the commercially available sensor technologies, conductometric gas sensors with nanoparticles of oxide semiconductors as sensing materials hold significant advantages in cost, size, and cross-compatibility. However, semiconductor gas sensors must overcome some major challenges in thermal stability, sensitivity, humidity interference, and selectivity before potential widespread adoption in air quality and human health monitoring applications. The focus of this dissertation is to tackle these issues by optimizing the composition and the morphology of the nanoparticles, and by innovating the structure of the sensing film assembled with the nanoparticles. From the nanoparticles perspective, the thermal stability of tin oxide nanoparticles with different Al dopant concentrations was studied, and the results indicate that within certain range of doping concentration, the dopants segregated at the grain surface can improve the thermal stability by stabilizing the grain boundaries. From the sensing film perspective, a novel self-assembly approach was developed for copper oxide nanosheets and the sensor response towards H2S gas was revealed to decrease monotonically by more than 60% as the number of layers increase from 1 to 300 (thickness: 0.03-10 μm). Moreover, a sensing mechanism study on the humidity influence on H2S detection was performed to gain more understandings of the role of the hydroxyl group in the surface reaction, and humidity independent response was observed in the monolayer film at 325 ℃. With a more precise deposition tool (Langmuir-Blodgett trough), monolayer film of zinc oxide nanowires sensitized with gold catalyst was prepared, and highly sensitive and specific response to C2H2 in the ppb range was observed. Furthermore, the effect of surface topography of the monolayer film on stabilizing noble metal catalyst, and the sensitization mechanism of gold were investigated. Lastly, a semiconductor sensor array was developed to analyze the composition of gases dissolved in transformer oil to demonstrate the industrial application of this sensor technology. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2020