Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2009. / Please refer to full text to view abstract.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2007. / Electrodialysis is a method of water desalination which involves the separation of TDS through an ion-exchange membrane under a potential gradient. In this study it was attempted to reverse engineer the composite carbon ion-exchange membrane used in a prototype plant and electrochemically evaluate a prototype desalination cell. The influence of applied potential on the capacitance of the various electrode surfaces and possible electrode reactions was investigated. A model was also suggested to describe the conductivity through the membrane. The composition of composite carbon membranes were determined by compositional analysis using various analytical tools. Elemental analysis, done with PIXE and EDS, showed that the membranes contained chloride, fluoride, oxygen, carbon, and possibly hydrogen. With LC-MS and IR it was established that the membranes consisted of two polymers with no carbonyl or aromatic functional groups. After further thermal analysis the following possible compounds remained: hexafluoropropylene tetrafluoroethylene copolymer, polychlorotrifluoroethylene (PCTFE), polyoxyethylene oxide (PEO) and polyethylene glycol (PEG). This assessment is in good agreement with the contents of US patent 4,153, 661, which describes the composite membrane.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2006. / Dyeing has an influence on the characteristic properties of wool fibres. This can result in changes in the final properties of the fibre including fibre elasticity, fibre strength and breaking elongation of the wool fibres, especially in the case of dark colours. Damage that occurs to the fibre surface due to the action of acid, alkali, dyestuff, water, heat, and mechanical stress during the dyeing process can thus have an affect on the fibre breaking elongation and the fibre strength. The aim of this project was to assess the effect of dyeing with different colours (ranging from light to dark) on the surface of wool fibres using atomic force microscopy (AFM). The results indicated that four different types of surface damage can be discerned: scale raising, scale chipping, fluting and pitting. The findings also indicate that the surface damage to the fibres was greater and more noticeable (especially the scale raising) on fibres dyed with dark colours than to fibres dyed with light colours. The same applied to the fibre strength and elongation, where generally the fibre breaking extension and the breaking load was smaller in the case of darker colours. The effect of dyeing with different colour shades on the fibre surface was observed with AFM. Several characteristic scale parameters of a statistical significant number of dyed and undyed fibres were measured in order to determine the surface damage caused by dyeing. The correlation between the surface damage, observed by AFM, and the loss in tensile strength and fibre elongation, determined by tensile tests, were investigated. This was done in order to determine the effect of the cuticle damage on the tensile stress/strain behaviour. The results show that AFM is a viable tool to study the effects of different dyes on the fibre surface and for detecting surface modifications with great accuracy. It was found that dyeing with dark colours caused greater damage to the surface than light colours, and it was possible to distinguish different lightness areas, which could be regarded as light and dark colours.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: Impact polypropylene copolymers (IPPC) are important commercial materials, but their morphology and molecular architecture are not yet fully understood. In this study the focus was on selectively removing specific fractions from the original IPPC, recombining the remaining fractions, and studying the properties of these recombined polymers. It was found that some properties of the samples changed remarkably, depending on the fraction of material that was removed before recombination. For example, the degree of phase separation and the crystalline morphology of the recombined materials varied noticeably. During the study an effective way of staining samples for transmission electron microscopy (TEM) was developed. Furthermore, a comparison of fourier transform infrared spectroscopy (FTIR), with TEM and scanning electron microscopy (SEM) results, revealed a hitherto unreported relationship between phase separation. Absorption bands appeared at 1100 cm-1 and 1080 cm-1 in the FTIR spectra and appear to be an indication of phase separation. It was further established that specific copolymer fractions present in the original polymer affect not only the morphology of the final polymer, but also the hardness and impact resistance. / AFRIKAANSE OPSOMMING: Impak polipropileen kopolimere (IPPK) is belangrike kommersïele materiale, maar die kennis met betrekking tot die morfologie en molekulere argitektuur van die materiale is nog gebrekkig. Tydens hierdie studie was die fokus op die selektiewe verwydering van spesifieke fraksies van die oorspronklike IPPK, herkombinering van die oorblywende fraksies, en die studie van die eienskappe van hierdie herkombineerde polimeriese materiale. Daar is gevind dat sommige van die eienskappe van die herkombineerde materiale daadwerklik verskil van die oorspronklike materiaal, en dat die verskille direk verband hou met die spesifieke fraksie wat uit die oorspronklike materiaal verwyder is. Die mate van fase-skeiding asook die kristal-morfologie van die herkombineerde materiaal het opmerklik verskil van die oorspronklike. Tydens die studie is n effektiewe manier ontwikkel om die materiale te vlek vir transmissie elektron-mikroskopie (TEM). Verder is daar ‘n verband tussen die resultate verkry deur Fourier Transform infrarooi spektroskopie (FTIS) en die verkry met TEM en skandeer elektron mikroskopie (SEM) vasgestel. Die verwantskap tussen FTIS en fase-skeiding is tot dusver nie in die wetenskaplike literatuur vermeld nie. Meer spesifiek is daar gevind dat absorbsie-bande sigbaar by 1100 cm-1 en 1080 cm-1 in die FTIS spektra ‘n aanduiding van fase skeiding kan wees. Dit was verder vasgestel dat spesifieke kopolimeer fraksies wat teenwoordig is in die oorspronklike IPPK, nie alleen die morfologie van die materiaal beinvloed nie, maar ook die hardheid en impak-weerstand van die materiaal.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2007. / This study comprises the synthesis, functionalization, and characterization of 1-butene oligomers, as well as the synthesis of oligobutene-based macro-RAFT agent. The directed oligomerization of 1-butene was carried out with a Cp2ZrCl2 as a catalyst, activated with MAO as a co-catalyst (10% in toluene), in the ratio Al/Zr =1000/1. Oligomers possessing vinylidene double bonds, with low molecular weight (Mw), ranging between 800 and 2000 g.mol-1 as confirmed by gel permeation chromatography, were obtained. The oligomers were successfully functionalized by adding hydroxyl functionality to the vinylidene double bond using oxymercuration-demercuration reaction, and as a result hydroxy-terminated oligobutenes were obtained. Characterization techniques such as 1H NMR, 13C NMR, GC-MS and FTIR confirmed the successful synthesis and functionalization of 1-butene oligomers. The hydroxy-terminated oligobutenes were used to prepare an oligobutene-based macro-RAFT agent. The synthesis of the macro-RAFT agent was carried out with an esterification reaction between the hydroxy-terminated oligobutenes and an acid functionalized RAFT agent. The successful synthesis of the macro-RAFT agent was confirmed by 1H NMR, 13C NMR, FTIR, and UV spectroscopy. The chain transfer ability of the macro-RAFT agent to induce living characteristics in free radical styrene polymerization was investigated with respect to molecular weight control and kinetic behaviour. The macro-RAFT agent was identified as suitable RAFT agent, yielding polystyrene-b-oligobutnes with low polydispersities and molecular weight ranging from 3000 to 40000 g/mol.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2006. / Cellulose, one of the most abundant organic substances on earth, is a linear polymer of D-glucose units joined through 1,4-β-linkages. Cellulose is however not easily processed without chemical modification. A number of techniques exist for the modification of cellulose, of which the viscose process is one of the most widely applied. Grafting of synthetic polymeric chains onto or from cellulosic materials is an useful technique that can be used to combine the strengths of synthetic and natural polymers dramatically, so changing the properties of cellulosic materials (pulp, regenerated cellulose, cellulose derivatives). In this study five model xanthate (Reversible Addition-Fragmentation chain Transfer (RAFT)/Macromolecular Design through Interchange of Xanthates (MADIX)) agents, namely, monofunctional, difunctional, trifunctional and tetrafunctional species of the form S=C(O-Z)-S-R, with different leaving groups and different activating moieties, were prepared and then studied to determine the feasibility of cellulose modification via addition fragmentation processes. These agents were characterized by Nuclear Magnetic Resonance spectroscopy (NMR), Fourier Transform Infrared spectroscopy (FT-IR) and Ultraviolet spectroscopy (UV). Polyvinyl acetates (PVAc) in the form of linear, three armed and four armed star shaped polymers were then successfully synthesized in reactions mediated by these xanthate RAFT/MADIX agents Xanthates were applied to polysaccharide materials using the viscose process (xanthate esters were formed directly on a cellulosic substrate, with subsequent alkylation) Grafting reactions were then conducted with the polysaccharides; cellulose was modified with vinyl acetate, [this is an example of a surface modification of natural polymers that is of interest in various industries, such as textiles and paper manufacture]. Analysis of the graft copolymers was conducted via Size Exclusion Chromatography (SEC), Liquid Adsorption Chromatography (LAC), Thermogravimetric Analysis (TGA), and FT-IR. Polyvinyl acetate was successfully grafted onto three polysaccharides (cellulosic materials), namely Hydroxyl Propyl Cellulose (HPC), Methyl Cellulose (MC) and cellulose. The study showed that the modification of cellulosic substrates with defined grafts of vinyl acetate can be easily achieved through minor modifications to existing industrial techniques.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2006. / Hydrophobic core/shell latex particles were synthesized for use in barrier coatings using the miniemulsion polymerization process. Particles with liquid or with hard cores were successfully synthesized using miniemulsion as a one-step nanoencapsulation technique. Different materials, including an oil (hexadecane, HD) and two different waxes (paraffin and microcrystalline wax), were used as the core of the particles. The shell of the particles was mainly made from a copolymer containing three relatively hydrophobic monomers, namely methyl methacrylate (MMA), butyl acrylate (BA) and vinyl neodecanoate (Veova-10). Before any further investigations could be carried out, it was important to determine the morphology of the synthesized core/shell particles at the nanometer level. Particle morphology was mainly determined by two different techniques: transmission electron microscopy (TEM) and atomic force microscopy (AFM). TEM was used to directly visualize the morphology of the investigated core/shell particles at the nanometer level, while AFM was used to confirm the formation of these core/shell particles. AFM was a powerful technique with which to study the particle morphology of the core/shell latices during the film formation process. As a second part of the study, the effect of various factors on the hydrophobicity and barrier properties of the resulting films produced from the synthesized core/shell latices to water and water vapour was investigated. This included the effect of: (i) the surfactant concentration, (ii) the wax/polymer ratio for both waxes, (iii) the molecular weight of the polymeric shell, (iv) the amount of the most hydrophobic monomer used (Veova-10), and (v) the degree of crosslinking in the polymeric shell. Results showed that all the above-mentioned factors had a significant impact on the water sensitivity of the resultant films prepared from the synthesized core/shell latices. It was found that the presence of wax materials as the cosurfactant, instead of HD, in the miniemulsion formulation could significantly improve the hydrophobicity and barrier properties of the final films to water and water vapour. In addition, increasing the amount of wax, Veova-10, and the molecular weight of the resultant polymeric shell, led to a significant increase in the hydrophobicity and barrier properties of the resultant latex films. In contrast, hydrophobicity and water barrier properties decreased drastically as the quantity of surfactant and degree of crosslinking increased in the final latex films.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2007. / Trans isomers are formed during the partial hydrogenation process of cis unsaturated fatty acids. The major source of trans fatty acids in the normal person's diet is from margarines and shortenings made from these partially hydrogenated plant and marine oils. In addition to influencing lipid risk factors for cardiovascular disease, trans fatty acids have also been implicated in breast cancer, and in poor fetal development and reduced early infant growth. In reality, trans fatty acids have been consumed for centuries, since they occur naturally in beef, mutton, butter, milk and other dairy products. Though it has been shown that these naturally occurring trans fatty acids have different effects on the health of humans. With the implementation of the new labelling law in South Africa, the trans fatty acids content of food items must be displayed on the food label. Therefore, it becomes necessary to optimise the analytical methodology for the determination of trans fatty acids in foods. Many publications have reported on the quantification of the total concentration of trans fatty acids in food samples, while less work has been done on the identification and quantification of the different cis and trans unsaturated fatty acid isomers found in foods made from partially hydrogenated oils. The objective of this study was to standardise and optimise an analytical technique to identify and quantify the different cis and trans mono-unsaturated fatty acid isomers in local margarines and bread spreads. Seeing that fatty acids are the group of lipids most commonly analysed by GLC and the availability of highly polar capillary columns bonded with cyanoalkyl polysiloxan phases, it was decided to use GLC for the identification and quantification of the different cis and trans isomers in a selected group of margarines. It was further decided to evaluate two BPX-70 capillary columns packed with cyanoalkyl polysiloxan phases. The one a 30 m BPX-70 capillary column, normally used for routine fatty acid analyses, and the other a 120 m BPX-70 capillary column.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2006. / Co-crystallization is the phenomenon by which chains of different crystallizabilities crystallize at the same temperature. Co-crystallization is frequently observed in the blends of different types of polyethylene. It is believed that co-crystallization can occur due to the thermodynamically miscible parts of two components in the blends having similar crystallization rate. The study focused on the phenomenon of co-crystallization in polyethylene blends and how by varying the crystallization conditions the co-crystallization region will change. Three techniques have been used in this study. TREF was used to fractionate the polymers and blends. Each of the TREF fractions was studied using both DSC and CRYSTAF to determine whether the fraction contained both types of materials. It is shown that the difference in the crystallization fractionation mechanisms between TREF, CRYSTAF and DSC can be utilize to study co-crystallization effects in polyethylene blends. Results also shows that by varying the heating and cooling rate profiles in DSC and CRYSTAF the co-crystallization fractions will appeared as a single fraction or as two separate fractions. Further, it was demonstrated how the co-crystallization area could be illustrated using a unique 3-dimensional plot where the data from the prep-TREF fractionation, and the DSC and CRYSTAF, were combined to give the “crystallization map” of the blend. These plots give a quiche visual illustration of any co-crystallization regions in the blends as well as how much the crystallization conditions effect the blend crystallization.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2006. / Please refer to full text for abstract