Experiments have been conducted to identify the fouling mechanism during the crossflow filtration of a model yeast fermentation broth of Vinyl Acetate particles suspended in a Bovine Serum Albumin (BSA) solution. These have been conducted with filter modules, to obtain quantitative data for the rate and the extent of flux decline due to membrane fouling, and with filter coupons, to obtain quantitative data for the build up of the fouling layer with each individual system and the mixed system. The data from the individual systems have been analysed and then used to determine their fouling mechanisms; this information has been used to predict the fouling mechanism for the mixed system. Finally, this prediction has been compared to the actual fouling mechanism determined by analysis of the mixed system data. For the model particulate suspension, the fouling was due to the build up of a cake layer, as with dead end filtration; however, fouling was limited by membrane scouring. For the model macromolecular solution, a four part fouling mechanism was identified: initially aggregates formed within the pores; the concentration at the membrane surface increased until protein came out of solution as strands; the strands disappeared causing increased aggregation in the pores; finally, a mesh formed on the membrane surface. For the mixed system, fouling was due to the formation of a particle cake on the membrane surface with protein aggregates forming in the pores. The fouling kinetics could be predicted by considering the results from the individual systems; however, the fouling mechanism could not be predicted without using visualisation experiments due to the interactions between the particles and the macromolecules.

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

The concept of a unique ceramifiable Ethylene vinyl acetate (EVA) based polymer composite was based on the incorporation of inorganic compounds such as aluminium hydroxide, calcium carbonate, muscovite mica, and calcined kaolinite within a 95 percent EVA/ 5 percent Polydimethylsiloxane (PDMS) polymer matrix such tha t upon heating to elevated temperatures of about 1000 oC, a solid end-product with ceramic-like properties would be formed. The ceramifiable EVA based polymer composite was developed to be used as electric cable insulation or sheath as the formation of a ceramic based material at elevated temperatures would provide flame retardant properties during fire situations. The flame retardant properties at elevated temperatures would ensure that the insulation remains at such temperatures due to some of the properties of the resultant ceramic such as reasonably high flexural strength, high thermal stability, non-reactivity and high melting point. During a fire this would ensure that flames would not be propagated along the length of the cable and also protect the underlying conducting wires from being exposed to the high temperatures of the fire. Its application as a cable insulation also required that the material functions as a cable insulator under ambient temperature conditions where the ceramifiable polymer composite should retain certain polymer properties such as the post-cure tensile strength (MPa), degree of polymer elongation (percent), thermal expansion, thermal slacking, limited oxygen index and electrical insulation. This study made use of a composite experimental design approach that would allow for the optimization of the amounts of the additives in the ceramifiable polymer composite giving both the desired mechanical properties of the material under normal operating temperatures as a polymer and also as a ceramic once exposed to elevated temperatures. The optimization of additives used in the ceramifiable polymer composite was done by using a D-optimal mixture design of experiments (DoE) which was analyzed by multiple linear regression.

Proper functioning of instruments requires precise calibration and routine quality assurance. In a clinical setting, this is achieved through the use of phantoms, which mimic the physical characteristics of tissues. Polyvinyl alcohol (PVA), a non-toxic, water-soluble polymer is well-suited for use as clinical phantom material. Through successive freezing and thawing, solutions of PVA in water can be solidified into rigid cryogels (PVA-C). The number of freeze-thaw cycles affects the properties of the material, including its optical characteristics. A double integrating sphere system was used in conjunction with the Inverse Adding Doubling (IAD) algorithm to characterize the optical properties of thin slab samples. The setup was evaluated using liquid phantoms. Liquid emulsion and food colouring were used to impart scattering and absorbing properties in the range characteristic of human tissue. Measured values of normalized reflectances and transmittances were entered into IAD, and a set of optical properties (μ′s,μa,g) retrieved. The reduced scattering coefficient was found to increase linearly with increasing lipid concentration, while a consistent overestimation of the absorption coefficient was observed. Measurements of PVA cryogels revealed a linear increase in the reduced scattering coefficient with an increasing number of freeze-thaw cycles up to five cycles. Scattering was also observed to increase with concentration up to PVA concentrations of 15%, and to spontaneously increase during the lifetime of the slab samples. These findings suggest it is possible to tune the optical scattering of PVA-C via different purely physical mechanisms. / Thesis / Master of Science (MSc)

No description available.

Supporting Information attached / <p> The development of a convenient route for the preparation of fluorous-tagged compounds for use with the fluorous labeling strategy (FLS) is described in this thesis. The FLS is a new and convenient method for the preparation of radiotracers and therapeutics in high effective specific activity (HESA) without the use of preparative HPLC. The objective of this thesis was to expand the general utility of the FLS by enabling the introduction of fluorous tags into molecules using a palladium-catalyzed cross-coupling reaction. To this end, a fluorous distannane, hexa(1H,1H,2H,2Hperfluorooctyl) distannane, was prepared from the corresponding fluorous tin hydride and used to produce trialkylarylstannanes from aryl and vinyl halides. Using the developed methodology, fluorous precursors for two radiopharmaceuticals, fialuridine (FIAU) and idoxuridine (IUdR), were prepared. The fluorous-tagged products were radiolabeled with iodine-125 to afford the desired compounds in high effective specific activity and in good radiochemical yield. </p> <p> Hexa(1H,1H,2H,2H perfluorooctyl)distannane was prepared from the corresponding tin hydride in nearly quantitative yield in the presence of Pd(PPh3)4. The distannane was combined with a series of seventeen aryl bromides and iodides and the appropriate palladium catalyst to afford trialkylarylstannanes in 15-59% isolated yield. </p> <p> The use of a phosphaadamantane ligand reported by Capretta et al. in the cross-coupling was also investigated, and the yields for the model compounds ranged from 13-67% Although no substantial change in yields was observed for aryl halides compared to the traditional catalyst Pd(PPh3)4, the phosphaadamantane ligands were more effective for the synthesis of precursors to [125I]fialuridine (FIAU) and [125I]idoxuridine (IUdR). Using this ligand system, the FIAU precursor was prepared in 38% overall yield from a dibenzoyl-protected vinyl bromide, and the IUdR precursor was prepared in 21% yield from a vinyl iodide. </p> <p> Following preparation of the FIAU and IUdR precursors, direct iodinolysis using a sub-stoichiometric amount of iodine was performed and the products isolated in excellent yield and purity using fluorous solid-phase extraction (FSPE). Following these experiments, the precursors were radiolabeled with [125I]NaI (50 – 500 μCi, 1.9 – 19 MBq) in the presence of Iodo-Gen® as an oxidant. Average radiochemical yields for three trials were 88% for FIAU and 94% for IUdR. The precursor was not observed in the FSPE-purified reaction mixture by UV-HPLC within the instrument’s detection limit. </p> <p> The fluorous labeling strategy allows molecular imaging and associated therapy agents to be produced in high effective specific activity in a rapid and convenient manner. With the development of the fluorous distannane and the associated coupling reactions reported here, the general utility of the fluorous labeling strategy has been greatly expanded. </p> / Thesis / Master of Science (MSc)

The thermally induced reaction of halogenated ethylenes on the α-Cr₂O₃ (101̅2) single crystal surface results in the formation of gas phase hydrocarbons including acetylene, ethylene, butadiene, and dihydrogen, and deposition of surface chlorine adatoms. No surface carbon or combustion products are observed in any reactions indicating no thermally induced C-C bond cleavage occurs and surface lattice oxygen is not incorporated into surface intermediates. Thermal desorption spectroscopy indicates that in all halogenated ethylene reactions acetylene is the major product, regardless of the reaction scheme. The surface reactions of halogenated ethylenes are proposed to proceed through C-X (X=halogen) bond cleavage to form surface halogen adatoms and surface C2 hydrocarbon fragments. Halogen adatom deposition affects reaction barriers to hydrocarbon formation, and eventually shuts down surface chemistry. Photoemission and near edge x-ray absorption fine structure spectra show that all studied reactants undergo some C-X bond cleavage upon low temperature adsorption forming adsorbed C2 fragments and halogen adatoms. Photoemission for each reaction system shows at least two C1s features (283.0-286.0 eV) and two Cl2p features (2p_3/2=198.0-201.0 eV) with higher binding energy features associated with molecularly intact halogenated ethylenes and lower binding energy features associated with dissociated surface species. Near edge x-ray absorption fine structure spectra taken, corresponding to photoemission spectra, indicate the occurrence of C1s→π∗ transitions, indicating intact π-systems are present. Heating the surface results in a reduction in intensity of higher energy photoemission and near edge x-ray absorption fine structure indicative of a decrease in surface C-X bonds. / Ph. D.

Building materials are a major source of indoor air contaminants. Volatile organic compounds (VOCs) are an important class of contaminants prevalent in indoor air. Attempts have been made to model the emission of VOCs from building materials. Diffusion has been shown to control the rate of mass transfer within certain types of building materials. The primary objective of this research is to develop a fundamental diffusion-based model for single and double layer building materials. The single-layer model considers a slab of material located on the floor of a chamber or room with the material acting either as a source or a sink for VOCs. The behavior of the model is governed by the material phase diffusion coefficient (D), the material/air partition coefficient (K), the concentration of VOC in the influent air stream, and the initial concentration within the material phase. The single-layer model extends a previously developed version, incorporating the non-uniform initial concentration inside the building material and a transient influent concentration. Experimental work is performed to check the validity of the model. A steel chamber housing a piece of vinyl flooring is used to simulate building material within a room. D and K values for two representative VOCs, n-dodecane and phenol, are available from earlier experiments. These parameters are used in the model to predict the VOC concentration inside the chamber. The predicted values compare very well to the observed experimental data. A double layer version of the model is developed and studied from a theoretical perspective. The model also permits a time dependent influent concentration and a non-uniform initial concentration profile within each of the two layers. A parametric analysis is performed varying the ratio of the diffusion coefficients, the partition coefficients and the thickness of the two layers. Three cases of practical interest are studied using the double-layer model. The use of a thin low-permeability barrier layer placed on top of a building material is shown to hold considerable promise for reducing the emission rate of VOCs into indoor air. / Master of Science

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: In papermaking, fillers and additives are used to enhance paper properties. In this study spherical modified poly(vinyl alcohol) (PVA) particles were prepared for use as fillers. In order to determine the mechanism of adhesion of additives to cellulose (paper) fibres, these particles were modified to have surface functionality, with cationic and anionic surface charges, similar to charged polyelectrolyte additives. Typically, retention aids used to improve the fibre–fibre and fibre–filler bonding are able to conform to the surface of the fibres and fillers. Oppositely charged components show strong affinity for each other, e.g. cationic polyelectrolyte groups adhere to anionic surface charges on the fibres. The spherical PVA particles were prepared by the saponification of spherical poly(vinyl pivalate) (PVPi) precursor particles. These PVPi particles, prepared via suspension polymerisation, were cross-linked with a divinyl ether comonomer. The vinyl pivalate (VPi) suspension polymerisation was successfully carried out and afforded relatively uniformly distributed PVPi particles, with diameters of 0.5–10 mm. The cross-linked PVPi particles were then saponified in tetrahydrofuran (THF) as swelling solvent, to afford PVA with various degrees of saponification (DS). The spherical shape was lost and fibrous material was obtained when uncross-linked PVPi particles were saponified. Cross-linking the spherical PVPi particles (PVA precursor) proved innovative, and essential in maintaining the spherical form during saponification to PVA/PVPi. By varying the saponification time periods, various DS were obtained, as characterised by solid state NMR spectroscopy. Surface modification of the PVA/PVPi particles was carried out with cationic and anionic groups via the Williamson ether synthesis. Ionic modification of these rigid spherical PVA/PVPi particles was carried out in order to study their adherence to cellulose fibres, compared to the adherence of similarly modified starches with cellulose fibres. Fluorescent labelling of the different modified particles was carried out using two complimentary coloured fluorescent markers. Fluorescence imaging and scanning electron microscopy (SEM) enabled the observation of particle– fibre and particle–particle interaction. Results indicated that the negative groups are sparse on the cellulose fibres, and therefore particles with low functionality but which are able change shape and conform and adhere to the surface of the cellulose fibres are required for effective adhesion. These modified spherical PVA/PVPi particles are unique as they mirror the chemistry of functionalised starch and cellulose particles, yet maintain their shape and have a fixed size, measurable by SEM and transmission electron microscopy (TEM). Field-flow fractionation was also used to characterise and measure these relatively large cross-linked and fixed diameter particles. / AFRIKAANSE OPSOMMING: In papierproduksie word vulstowwe en bymiddels gebruik om die eienskappe van papier te verbeter. In hierdie studie is sferiese poli(vinielalkohol) (PVA) partikels berei vir gebruik as vulstowwe. Om ten einde die meganisme van die bymiddelklewing aan die sellulose vesels (papier) te bepaal, is die oppervlakke van hierdie partikels gewysig met kationiese of anioniese groepe, om 'n oppervlak soortgelyk aan dié van funksionele poliëlektrolietbymiddels te verskaf. Die retensiemiddels wat gebruik word om die vesel–vesel en vesel–vulstof binding te verbeter is tipies in staat om te konformeer aan die oppervlak van die vesels en vulstowwe. Teenoorgesteldgelaaide komponente toon 'n sterk affiniteit vir mekaar, bv. kationiese poliëlektrolietgroepe is vasklewend aan die anioniesgelaaide oppervlakke van die vesel. Die sferiese PVA partikels is berei deur die verseping van sferiese poli(vinielpivalaat) (PVPi) partikels. Hierdie voorloper PVPi partikels, berei deur suspensiepolimerisasie, is gekruisbind met 'n divinieleter ko-monomeer. Die vinielpivalaat (VPi) suspensiepolimerisasie is suksesvol uitgevoer en relatief eenvormig verspreide sferiese PVPi partikels is berei, met deursnitte tussen 0.5–10 mm. Die gekruisbinde PVPi partikels is daarna gesaponifiseer in tetrahidrofuraan (THF) as oplosmiddel, om PVA met verskillende grade van verseping (DS) te berei. Die sferiese vorm raak verlore en veselagtige materiaal is verkry wanneer PVPi partikels met geen kruisbinding verseep is. Kruisbinding van die sferiese PVPi partikels (PVA voorloper) is voordelig en noodsaaklik om die sferiese vorm tydens die verseping tot PVA/PVPi te behou. Deur die tydsduur van verseping te verander, is verskeie grade van verseping verkry en bevestig deur vaste toestand KMR spektroskopie. Oppervlakwysiging van die PVA/PVPi partikels, om kationiese en anioniese groepe aan te heg, is uitgevoer via die Williamson etersintese. Ioniese wysiging van hierdie stram, sferiese PVA/PVPi partikels is uitgevoer om ten einde hul klewing met sellulose vesels te bestudeer en te vergelyk met die klewing van soortgelyk gewysigde stysels. Fluoressensie merking van die verskillende gewysigde partikels is uitgevoer met behulp van twee komplimentêre gekleurde fluoressensie merkers. Fluoressensie beeldvorming en SEM verskaf die waarneming van partikel–vesel en partikel–partikel interaksie. Die resultate dui daarop dat die negatiewe groepe van die sellulose vesels skaars is, en daarom is partikels met ‘n lae funksionaliteit, maar wat in staat is om van vorm te verander, aan te pas en te konformeer aan die oppervlak van die sellulose vesels, nodig vir effektiewe adhesie. Hierdie gewysigde sferiese PVA/PVPi partikels is uniek aangesien hulle die chemie van gewysigde stysel en sellulose partikels naboots, maar steeds hul vorm behou met 'n vaste grootte; meetbaar deur SEM en TEM. Veld-vloei-fraksionering is ook gebruik vir die karakterisering van hierdie relatief groot, stram, gekruisbinde partikels met bepaalde deursneë.

M.Sc. / Carbon nanotubes (CNTs) have been of utmost scientific interest since their discovery in 1991 by a Japanese physicist - Sumio Iijima. This is due to their extraordinary properties which make them one of the most promising options for the design of novel ultrahigh strength polymer nanocomposites. It is believed that the high aspect ratio, mechanical strength, and high electrical and thermal conductivity of these CNTs will enhance the performance of many polymer / CNT nanocomposites and open up new applications. However, poor dispersibility and lack of interfacial adhesion of the CNTs in the polymer matrix have remained a challenge towards fabrication of these nanocomposites. This has been due to the atomically smooth surface of the nanotubes and their intrinsic van der Waals forces which make them chemically inert. This study was aimed at exploring this concept by using novel phosphorylated multiwalled carbon nanotubes (p-MWCNTs) and polyvinyl chloride (PVC) polymer. Phosphorylation of MWCNTs has been successfully achieved in our laboratories, with the p-MWCNTs showing improvement in thermal stability. PVC on the other hand, is the world’s second largest thermoplastic material and has physical properties that are key technical advantages for its use in various and diverse fields such as building and construction, electronics, food packaging and in medical applications. A novel solvent-free method was used to synthesize p-MWCNTs / PVC nanocomposites. MWCNTs were synthesized by nebulized spray pyrolysis, a modification of catalytic vapour deposition and purified by soxhlet extraction using toluene. This method proved to be convenient and economical, producing a high yield of carbon nanotubes. The MWCNTs were phosphorylated with alkylazido phosphonate compounds through a 1,3-dipolar cycloaddition reaction between the phosphonate azides and the C=C bonds of the MWCNTs, with nitrogen loss occurring upon thermolysis. These p-MWCNTs were then melt compounded with PVC to form the p-MWCNTs / PVC nanocomposites. vii The phosphorylation of the MWCNTs and their dispersion in the PVC matrix were characterized by FTIR, SEM, TEM and Raman spectroscopy. Thermal analysis of the nanocomposites by TGA and DSC showed an enhanced thermal stability when comparing the nanocomposites with neat PVC. The modulus of the MWCNTs / PVC nanocomposites increased whilst there was a reduction in their tensile strength, indicating a decrease in polymer toughness.