Dissertations / Theses on the topic 'Dissertations – Polymer science'

Thesis (PhD)--Stellenbosch University, 2000.<br>ENGLISH ABSTRACT: The objective of this research was to produce discrete, nano-shaped polymeric structures on the same length scale as, or one to one copies of, templates, deformable templates or structure-directing hosts. Polymerisation of hydrophobic organic monomers in high concentration surfactant solutions, leads to the formation of shaped particles (rod-like, plank-like and ribbon-like particles) in the micrometer size range. The origin of these regularly shaped particles was investigated. It is proposed that they were not polymeric in nature, but formed by the crystallisation of the surfactant in the presence of electrolytes and ethanol as solvent. The polymeric particles that were formed were found to be of spherical shape, and no directing of the shape was detected. Mesostructured hosts were then investigated for their possible use as structure-directing agents. A series of polyelectrolyte-surfactant complexes of polydiallylammonium chloride with sodium sulphate surfactants (ranging from C10 to C16) were synthesised and characterised in terms of their thermal, mechanical and structural properties. The complex of polydiallylammonium chloride and sodium dodecyl sulphate was selected as an appropriate self-assembled model system for investigations into the structure-directing properties of these new materials. The polymerisation of hydrophobic organic monomers, such as styrene and the di-functional monomer m-diisopropenylbenzene (m-DIB), within the above mesoscopically structured polyelectrolyte-surfactant complex as host, lead to the formation of unconventionally shaped polymeric particles. The influence of the presence of monomers and guest polymers on the phase morphology of the host was investigated by small angle X-ray analyses (SAXS) and dynamic mechanical analyses (DMA). SAXS analyses showed that these new, stable hosts can hold up to 17 % guest polymer before phase disruption is encountered. These findings were supported by changes in the mechanical properties, as determined by DMA. The transmission electron microscopy (TEM) images of particles obtained after polymerisation showed very clearly that the poly-(m-DIB) did not form a continuous copy of the 3D hexagonal structure of the host, but rather colloidal copies of a part of the host structure that swelled the most. The shapes of the polymer mesostructures were dictated by the morphology of the phase of the structure-directing host, to produce nanosized wires (dimensions 4 by 100 nm), cigar-shaped particles (dimensions 8 by 50 nm) and fibrillar bent shapes (larger than 200 nm), as revealed by TEM. According to literature these are the first shaped, polymer nano-particles produced in a soft, selfassembled, organic templating host.<br>AFRIKAANSE OPSOMMING: Die doel van hierdie navorsing was om diskrete, nano-gevormde polimeriese partikels van dieselfde lengteskaal as, of direkte een tot een kopië van, 'n templaat, 'n vervormbare of struktuur-rigtende gasheersisteem te produseer. Die polimerisasie van hidrofobiese organiese monomere in seep oplossings van hoë konsentrasie, het gelei tot die produksie van gevormde partikels. Die oorsprong van hierdie partikels is ondersoek. Dit word voorgestel dat die partikels nie polimeries van aard is nie, maar gevorm is deur die kristallisasie van die seep in die teenwoordigheid van elekotroliete en etanol as oplosmiddel. Die polimeriese partikels wat wel geproduseer is, was sferies in vorm, en geen rigtende invloed op die vorm van die partikels is waargeneem nie. Meso-gestruktureerde gasheersisteme is ook ondersoek vir moontlike gebruik as struktuur-rigtende agente. 'n Reeks poliëlektroliet-seep komplekse van polidiallielammoniumchloried en natriumsulfaat sepe (van C10 tot C16) is gesintetiseer en gekarakteriseer in terme van hul termiese, meganiese en strukturele eienskappe. Die kompleks van polidiallielammoniumchloried en natrium dodekielsulfaat is gekies as 'n toepaslike self-organiserende modelsisteem vir die ondersoeke na die struktuur-rigtende eienskappe van hierdie nuwe materiale. Polimerisasie van hidrofobiese organiese monomere, soos byvoorbeeld stireen en die di-funksionele monomeer m-di-isopropenielbenseen (m-DIB), in hierdie mesoskopies-gestruktureerde poliëlektroliet-seep kompleks, het gelei tot die vorming van nie-konvensionele gevormde polimeriese partikels. Die invloed van die teenwoordigheid van monomere en gaspolimere op die fasemorfologie van die gasheersisteem is ondersoek d.m.v. kleinhoek X-straal diffraksie (Eng. SAXS) en dinamiese meganiese analise (DMA). SAXS analises het aangetoon dat hierdie nuwe, stabiele gasheersisteem tot 17 % gaspolimeer kan inkorporeer voordat fasevernietiging plaasvind. Hierdie resultate is verder ondersteun deur veranderinge in die meganiese eienskappe soos waargeneem deur DMA. Transmissie elektronmikroskopie (TEM) afbeeldinge van partikels geïsoleer na polimerisasie het baie duidelik gewys dat, in die geval van poli-(m-DIB), die gaspolimeer nie 'n kontinue kopie van die drie dimensionele heksagonale struktuur van die gasheersisteem produseer nie. Daar word eerder 'kolloïdale kopieë' van dele van die gasheersisteem wat die meeste swel gevorm. Die vorms van die polimeer mesostrukture word dus bepaal deur die morfologie van die fase van die struktuur-rigtende gasheer, om nanogrootte draadjies (dimensies 4 x 100 nm), sigaarvormige partikels (8 x 50 nm) en fibrillêre gebuigde vorms (groter as 200 nm) te vorm, soos waargeneem met TEM. Volgens die literatuur is hierdie die eerste geval van gevormde polimeer nanopartikels geproduseer in 'n self-organiserende templaat gasheersisteem.

Thesis (PhD)--Stellenbosch University, 2002.<br>ENGLISH ABSTRACT: Most polypropylene copolymers commercially available have ethylene, and to a lesser degree t-butene as comonomers. Commercially available higher a-olefins, mostly even-numbered, are seldom used for the production of pp copolymers, probably due to cost. Sasol's Fischer- Tropsch oil-from-coal process produces many linear and branched a-olefins as by-products that can be isolated and purified by a relatively cheap refinery process, including the odd-numbered 1- pentene olefin. Sasol's gas-phase Novolen pp plant at Secunda, South Africa is ideally suited to the manufacture of high quality pp random copolymers. As such an opportunity was identified to research the use of higher a-olefins, and more specifically 1-pentene, in the gas-phase production of pp random copolymers. Different methods to produce propylene / 1-pentene random copolymers in the slurry phase on bench-scale were investigated. A procedure was subsequently developed to produce propylene / 1-pentene random copolymers in the gas-phase in 10 litre autoclaves. It was found that commercially available fourth generation supported catalysts successfully incorporated the bulky 1-pentene monomer into the propylene backbone, both during slurry and gas-phase polymerisations. Software modelling was employed to determine the dew points of selected gas mixtures typically found during the production of pp random copolymers. The results indicated that typical process conditions could be employed during the gas-phase polymerisation of propylene and 1-pentene without the risk of condensation taking place inside the reactor. Propylene / 1-pentene random copolymers were subsequently successfully produced on the 800 litre BASF pilot plant in Germany followed by the first commercial production of the copolymer on Sasol's 50m3 Novolen gas-phase plant at Secunda. Using commercially available software the impact of introducing 1-pentene as comonomer during the production of random copolymers on the condenser cooling capacity was evaluated. Feasible and safe plant operating conditions were established for the production of propylene / 1-pentene random copolymers. The relationship between operating pressure and powder morphology was investigated to optimise process conditions. Operating at higher pressure in the gas-phase increases the monomer concentration in the reactor and as such improves the space/time/yield ratio of the 50m3 reactors. It was shown that higher operating pressures could be employed through the introduction of 1-pentene as comonomer during the production of PP random copolymer. The dramatic increase in catalyst productivity observed during the 800 litre pilot plant trials, up to a comonomer ratio of about 5%, supported the results obtained from a kinetic study carried out in bench-scale autoclaves. A comprehensive study was undertaken to compare the rheological, thermal, crystallisation, physical and mechanical properties of propylene / 1-pentene random copolymers with those of commercially available pp random copolymers. A series of propylene homo- and random copolymers with 1-pentene and ethylene as comonomers respectively, was prepared. NMR and IR techniques were developed to facilitate the determination of copolymer composition for the new family of 1-pentene random copolymers. The effect of comonomer content, molecular weight and temperature on the properties of the series of polymers was investigated. The propylene / 1-pentene random copolymers show unique rheological behaviour associated with the short propyl branches in the polymer backbone with minimum zero shear viscosity at about 2% 1-pentene content. The effect of molecular structure changes with comonomer content were analysed by the calculation of square average end-toend distance, packing length, tube diameter, molecular mass between entanglements and critical molecular mass. The viscosity of the 1-pentene random copolymers shows higher shear and temperature sensitivity compared to propylene homo- and ethylene random copolymers. The thermodynamic melting point of the propylene / 1-pentene random copolymers showed a significant decrease with increasing comonomer content in the 0 to 5% range. A wider melting range and higher peak melting point depression rate was observed compared to ethylene random copolymers at similar and increasing comonomer content measured on a weight % basis. It was found that the crystal structure of the propylene / 1-pentene random copolymers contains both the Q- and the y-modifications with the ratio of the respective crystal forms a function of both comonomer content and crystallisation temperature. The glass temperature decreased slightly with increasing comonomer (1-pentene) content. It is proposed that the short branch (propyl) "defects" in the polymer backbone are .incorporated into the crystal lattice resulting in increased rate of melting point depression with increasing (wt%) comonomer content compared to other random copolymers while maintaining relative high stiffness. The propylene / 1-pentene random copolymers exhibit the lowest haze values compared to all commercially available pp random copolymers at corresponding levels of comonomer content on a wt% basis. The stiffness to haze ratio of propylene / 1-pentene random copolymers are unique for all the members of the pp family. An inverse relationship between comonomer content and the measured tensile yield strength and modulus is observed. Application studies conducted on the propylene / 1-pentene random copolymers highlighted several interesting characteristics. Films produced from these copolymers exhibited very low haze and xylene soluble values while maintaining mechanical integrity. In the BOPP application the combination of processability and premium film properties presents a unique opportunity for the family of propylene / 1-pentene random copolymers. Blow moulding and injection moulding trials highlighted several advantages of product properties manufactured with propylene / 1-pentene random copolymers if compared to other commercially available random copolymers. The 1-pentene randoms presented lower in-mould as well as total shrinkage than ethylene based random copolymers. Stabilisation and nucleation studies conducted on the propylene / 1-pentene random copolymers showed that a typical combination antioxidant package and nucleating agent, at normal loading levels, could be used. In the larger pp random copolymer family 1-pentene imparts a better balance of properties than other comonomers. The combination of low melting point and xylene solubles with high stiffness and clarity is unique to propylene / 1-pentene random copolymers.<br>AFRIKAANSE OPSOMMING: Die oorgrote meerderheid van kommersieel beskikbare polipropileen (PP) kopolimere het etileen, en tot 'n mindere mate buteen, as komonomeer. Die relatief hoë koste van kommersieel beskikbare hoër alfa-olefiene is moontlik die rede waarom hulle selde gebruik word vir die vervaardiging van PP kopolimere. Die Sasol Fischer-Tropsch proses, waartydens olie uit steenkool vervaardig word, lewer verskeie liniêre en vertakte alfa-olefiene as neweprodukte wat geïsoleer en gesuiwer kan word in 'n relatiewe goedkoop rafineringsproses. Dit sluit ook die onewe-koolstofgetal 1-penteen-olefien in. Sasol se gasfase Novolen PP aanleg in Secunda, Suid-Afrika, is besonder geskik vir die vervaardiging van hoë standaard PP statistiese kopolimere. Voortvloeiend hieruit is die geleentheid geidentifiseer om die gebruik van hoër alfa-olefiene, en meer spesifiek 1-penteen, na te vors tydens die gasfaseproduksie van PP statistiese kopolimere. Verskeie metodes om propeleen / 1-penteen statistiese kopolimere in 'n koolwaterstofoplosmiddel op laboratoriumskaal te produseer, is ondersoek. 'n Prosedure is daarna ontwikkel om propileen / 1-penteen statistiese kopolimere ook in die gasfase te vervaardig in 10-liter drukvate. Die bevinding was dat kommersieel beskikbare vierde-generasie ondersteunde kataliste die swaarder 1-penteenmonomeer suksesvol geïnkorporeer het in die propileenketting tydens beide die koolwaterstof oplosmiddel- en gasfase polimerisasiereaksies. Rekenaargebaseerde modellering is gebruik om die kondensasiekondisies van tipiese gasmengsels, teenwoordig tydens die produksie van PP statistiese kopolimere, te bepaal. Die resultate het aangedui dat normale proseskondisies tydens die gasfasepolimerisasie van propileen en 1-penteengeen risiko van kondensasie in die reaktor inhou nie. Propileen / 1-penteen statistiese kopolimere is gevolglik met groot sukses vervaardig by die 800-liter BASF loodsaanleg in Duitsland, gevolg deur die eerste kommersiële vervaardiging van die kopolimeer op die Sasol50m3 Novolen gasfase-aanleg in Secunda. Deur gebruik te maak van kommersieel beskikbare sagteware, is die impak van 1-penteen as komonomeer tydens die vervaardiging van statistiese kopolimere op die verkoelingskapasiteit van die kondensator bepaal. Veilige en uitvoerbare aanlegkondisies is uitgestip vir die vervaardiging van propileen /1-penteen statistiese kopolimere. Die verhouding tussen die reaktordruk en poeiermorfologie is ondersoek om die prosestoestande te optimiseer. Vervaardiging van kopolimere in die gasfase by hoër drukke lei tot verhoogde monomeerkonsentrasie in die reaktor en gevolglik hoër produksiedeursette. Daar is bewys dat tydens die produksie van PP statistiese kopolimere, met 1-penteen as komonomeer, hoër reaktordruk ingespan kan word. Die dramatiese toename in katalisproduktiwiteit waargeneem tydens die 800- liter loodsaanleg proefloop, tot en met 'n komonomeer inhoud van ongeveer 5%, word ondersteun deur die resultate van 'n kinetiese studie uitgevoer in laboriumskaal drukvate. 'n Omvattende studie, om die reologiese, termiese, kristallyne, fisiese en meganiese eienskappe van propileen / 1-penteen statistiese kopolimere te vergelyk met kommersieel beskikbare PP statistiese kopolimere, is uitgevoer. 'n Reeks propileen homo- en statistiese kopolimere, met 1-penteen en etileen as komonomere onderskeidelik, is berei. KMR- en IR- tegnieke is ontwikkel om die bepaling van komonomeersamestelling vir die nuwe familie van 1- penteen statistiese kopolimere te fasiliteer. Die invloed van komonomeersamestelling, molekulere gewig en temperatuur op die eienskappe van die reeks polimere is ondersoek. Die propoleen / 1- penteen statistiese kopolimere toon unieke reologiese eienskappe wat geassosieer kan word met die propielsykettings in die polimeerruggraat. Die viskositeit van die propileen / 1-penteen statistiese kopolimere toon 'n hoër wrywings- en temperatuursensitiwiteit in vergelyking met propileen homo- en etileen statistiese kopolimere. 'n Drastiese verlaging in die termodinamiese smeltpunt van die propileen / 1- penteen statistiese kopolimere met 'n toename in komonomeerinhoud is waargeneem tot en met 'n 5% komonomeerinhoud. Die propileen / 1-penteen statistiese kopolimere toon 'n breër smeltgebied en 'n hoër tempo in die piek smeltpuntafname in vergelyking met etileen statistiese kopolimere met soortgelyke komonomeer inhoud, gemeet op 'n massabasis. Daar is bewys dat die kristalstruktuur van die propileen / 1-penteen statistiese kopolimere beide die alfa en gamma modifikasies bevat. Die verhouding van die onderskeie kristalvorms is 'n funksie van komonomeerinhoud en kristalisasietemperatuur. 'n Afname in die glastemperatuur met verhoogde komonomeer inhoud is waargeneem. Die aanname dat die kort propielsykettings in die polimeerruggraat in die kristalstruktuur geïnkorporeer word, is gemaak. Dit verklaar die hoë afname in die tempo van die smeltpunt met toenemende komonomeer inhoud relatief tot ander statistiese kopolimere, met die handhawing van hoë moduluswaardes. Die besondere deursigtigheid van die propileen / 1-penteen statistiese kopolimere tesame met relatief hoë modulus waardes is uniek. 'n Omgekeerde verhouding tussen komonomeer inhoud en treksterkte asook moduluswaardes is waargeneem. 'n Toepassingstudie uitgevoer met die propileen / 1-penteen statistiese kopolimere het verskeie interessante resultate gelewer. Films vervaardig van hierdie kopolimere toon besonderse deursigtigheid en lae waarde van xileenoplosbaarheid, terwyl meganiese integriteit gehandhaaf word. Voordele in die vervaardigingsproses van BOPP-films asook bogemiddelde filmeienskappe hou unieke moontlikhede vir propileen / 1-penteen statistiese kopolimere in. Verskeie voordele tydens blaas- en spuitvormingsprosesse is waargeneem relatief tot ander beskikbare statistiese kopolimere. Die 1-penteen statistiese kopolimere toon 'n laer in-vorm sowel as totale krimping relatief tot etileen- gebaseerde kopolimere. 'n Studie het aangetoon dat tipiese bymiddelpakette by normale toevoegingsvlakke geskik is vir propileen / 1-penteen statistiese kopolimere. Gesien in die groter pp statistiese kopolimeer familie toon 1-penteen 'n beter balans van eienskappe as ander komonomere. Die kombinasie van laer smeltpunt en xileen-oplosbares met hoë moduluswaardes en helderheid is uniek aan propileen /1-penteen statistiese kopolimere.

Dissertation (PhD)--Stellenbosch University, 2002.<br>ENGLISH ABSTRACT: The kinetics of drying and film formation of different polymeric latices were studied. Various theoretical models predict a strong dependency of the film formation characteristics on the particle size and morphology. This could be confirmed by experimental studies. The influence of particle size and morphology of differently structured latices on the film formation process was investigated by Atomic Force Microscopy (AFM) and Ultrasonic shear wave reflection. These two methods allow a comprehensive characterization of the drying and film formation process of emulsions. The studies confirmed the theoretical model, that the film formation behavior is influenced by the particle size and particle morphology. Furthermore the influence of different additives, such as coalescent solvents and rheology modifiers on the film formation behavior was investigated. As a second part of the studies, a novel technique was developed to measure thermal transitions of polymers with the AFM in the non-contact mode, using it as a Dynamic Mechanical Analyzer (DMA) on a local scale. The resonance frequency of the AFM cantilever was measured as a function of the temperature and thermal transitions of a polymer were clearly visible as changes in the resonance frequency / temperature response curve. Using the AFM in this mode allows the determination of the thermal properties of a material at a specific position on a sample, thereof on a macromolecular scale. A simple model was developed to explain the response of the cantilever caused by the transitions in the polymer and the related form of the frequency/temperature curves. This new technique adds a new dimension to standard thermal analysis techniques. It is now possible to resolve the individual thermal transitions of different polymer phases, for example in structured multiphase polymers.<br>AFRIKAANSE OPSOMMING: Die kinetika van droging en filmvorming van verskeie polimeriese lateksverbindingse is ondersoek. Verskeie teoretiese modelle voorspel 'n sterk afhanklikheid tussen die filmvormingseienskappe, partikelgrootte en morfologie. Hierdie afhanklikhede is eksperimenteel bevestig. Die invloed van partikelgrootte en morfologie van verskillende lateksstrukture op die filmvormingsproses is deur atoominteraksiemikroskopie (Eng: Atomic Force Microscopy, AFM) sowel as ultrasoniese skuifweerstandgolfrefleksie ondersoek. Hierdie twee metodes bied 'n deurslaggewende karakterisering van die droging en filmvormingsproses van emulsies. Resultate bevestig die teoretiese model, nl. dat filmvorming deur partikelgrootte en morfologie beïnvloed word. Die invloed van verskillende bymiddels, insluitend reologie-modifiseerders op filmvorming, is ook ondersoek. Vervolgens is 'n nuwe tegniek ondersoek om die termiese oorgange van polimere met behulp van die AFM in nie-kontak modus (deur dit as 'n dinamiese meganiese analiseerder (DMA) te gebruik) te bestudeer. Die resonansie-frekwensie van die AFM-hefboom is bepaal as 'n funksie van temperatuur. Termiese oorgange van 'npolimeer is duidelik waarneembaar as veranderinge in die resonansfrekwensie/ temperatuur responskurwe. Deur gebruik te maak van die AFM in hierdie modus kan die termiese eienskappe van 'n materiaal by 'n spesifieke posisie op die monster op molekulêre skaal bepaal word. 'n Eenvoudige model is ontwikkel om die oorgange in die polimeer, en gevolglik die vorm van die frekwensie/temperatuur kurwes, dmv. die respons van die hefboom, te verduidelik Hierdie nuwe tegniek gee 'n nuwe dimensie tot die standaard tegnieke van termiese analise tegnieke. Dit is nou moontlik om individuele termiese oorgange van verskeie polimeerfases, byvoorbeeld in gestruktureerde multifase polimere, te ondersoek en op te los

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2011.<br>ENGLISH ABSTRACT: Positron annihilation lifetime spectroscopy (PALS) is well established as a novel method currently available for the study of polymers at a molecular level because of its sensitivity to the microstructural changes in the polymer matrix. The technique provides unique, but limited, information of the solid state structure – primarily on the nature of the free volume (or unoccupied space) in the polymer due to the less dense packing of polymer chains relative to in other solid materials. In the case of completely homogeneous polymer materials the measurement and interpretation of the positron annihilation parameters is relatively simple. However, in the case of polymers with more complex morphologies the situation becomes less clear. This is due to the possibility of the formation, localization and subsequent annihilation of o-Ps (ortho-positronium) within different areas of the complex morphology. This can result in more than one o-Ps lifetime component being present, and each of the different components corresponds to areas with differing types and amounts of 'open spaces'. In this study a detailed and systematic approach was taken to study the positron annihilation parameters in various semi-crystalline polymers and to correlate these to the chain structure and morphology of the materials. The study focused specifically on polyolefin polymers as these are the most widely used semi-crystalline materials, but more importantly, they offer the possibility to produce a variety of morphological complexity by simple manipulation of the chain structure – while there is essentially no difference in the chemical composition of the materials. The copolymers were selected to study the influence of short-chain branching (amount and length), short-chain branching distribution and tacticity on the morphology, and subsequent positron annihilation lifetime parameters. Three separate topics were addressed. First, preparative temperature rising elution fractionation was used to isolate polymer samples that are homogeneously crystallisable and to produce a series of polymers with differing chain structure and resultant morphologies. Second, additional series were produced by removing specific crystallisable fractions from the bulk materials. Third, the temperature variation of the samples as they approach and go through the crystalline melting point was studied. All the raw positron data were found to be best fitted with a four-component positron annihilation lifetime analysis. The longest lifetime (which is attributed to annihilation of o-Ps in the amorphous phase of the materials) showed systematic variations with the degree and nature of the short-chain branding, tacticity variation, a combination of both short-chain branching and tacticity, and changes in the amorphous phase as a result of heating. The third lifetime component (which is attributed to o-Ps annihilation in or around the crystalline areas of the materials) showed less variation across the sample series. Typically, greater variations were observed in the propylene copolymers than in the ethylene copolymers, which are reflective of the more complex chain structure and corresponding morphology in the propylene copolymer series. Direct evidence for a contribution from the nature of the amorphous phase to the bulk microhardness of the sample was also found.<br>AFRIKAANSE OPSOMMING: Positronvernietigingsleeftydspektroskopie (PALS) is goed gevestig as ‘n nuwe metode vir die studie van polimere op molekulêrevlak agv die sensitiwiteit van die metode vir mikrostrukturele veranderings in die polimeermatriks. Hierdie tegniek verskaf unieke, maar beperkte, inligting aangaande die vastetoestandstruktuur – veral aangaande die aard van die vryevolume (of onbesette spasie) in die polimeer as gevolg van die minder digte verpakking van polimeerkettings relatief tot in ander vastestowwe. In die geval van volledig homogene polimeriese materiale is die meet en interpretasie van die positronvernietigingsparameters relatief eenvoudig. Maar in die geval van polimere met meer komplekse morfologieë is die situasie minder duidelik. Die rede hiervoor is die moontlikheid vir die formasie, lokalisering en gevolglike vernietiging van o-Ps (orto-positronium) in die verskillende areas van die komplekse morfologie. Dit kan tot gevolg hê dat meer as een o-Ps komponent teenwoordig is en waar elk van die verskillende komponente ooreenstem met areas met verskillende tipes en hoeveelhede 'oop spasies'. In hierdie studie is ‘n sistematiese, in-diepte benadering gebruik om die positronvernietigingsparameters in verskeie semikristallyne polimere te bestudeer en hulle te korreleer met dié van die kettingstruktuur en die morfologieë van die materiale. Hierdie studie het spesifiek gefokus op poliolefiene aangesien hulle die mees algemene semikristallyne materiale is wat gebruik word en, nog meer belangrik, hulle bied die geleentheid om verskeie komplekse morfologieë te lewer dmv eenvoudige manipulasie van die kettingstrukture – terwyl daar basies geen verandering in die chemiesesamestelling van die materiale is nie. Die kopolimere is gekies om die invloed van kort-ketting vertakking (lengte en hoeveelheid), kort-ketting vertakking verspreiding en taktisiteit op die morfologie en vervolgens die positronvernietigingsleeftyd parameters te bestudeer. Drie onderwerpe is aangespreek. Eerstens, preparatiewe temperatuurstygingelueringsfraksionering (prep-TREF) is gebruik om polimeermonsters wat homogeenkristalliseerbaar is te isoleer om sodoende 'n reeks polimere met verskillende kettingstrukture, en gevolglike morfologieë, te lewer. Tweedens, 'n addisionele reekse monsters is berei deur die verwydering van spesifieke kristalliseerbare fraksies vanaf die grootmaatmonsters. Derdens, die temperatuurverandering van die monsters wanneer die monsters naby aan die kristallyne smeltpunt is en wanneer hulle deur die kristallyne smeltpunt gaan is bestudeer. Daar is bevind dat alle rou positrondata ten beste gepas het in 'n vier-komponent positronvernietigingsleeftydanalise. Die langste leeftyd (wat toegeskryf is aan vernietiging van o-Ps in die amorfe fase van die materiaal) het sistematiese variasies getoon met die volgende: hoeveelheid en aard van die kort-kettingvertaking, verandering in taktisiteit, 'n kombinasie van beide kort-kettingvertakking en taktisiteit en veranderings in die amorfiesefase as gevolg van verhitting. Die derde leeftyd komponent (wat toegeskryf is aan die o-Ps vernietiging in of rondom die kristallyne areas van die materiale) het minder variasie in hierdie reeks monsters getoon. Daar is tipies meer variasie waargeneem in die propileenkopolimere as in die etileenkopolimere, wat ’n weerspieëling is van die meer komplekse kettingstruktuur en ooreenstemmende morfologie in die propileenkopolomeerreeks. Direkte bewys vir 'n bydrag van die aard van die amorfe fase tot die grootmaat mikrohardheid van monsters is ook bevind.

Thesis (MSc)--Stellenbosch University, 2002.<br>ENGLISH ABSTRACT: Multimedia was the buzzword of the previous decade. Electronic learning is the buzzword of this decade. Both concepts changed, and are still changing the way educators present knowledge and information to students, both locally and worldwide. South Africa, also standing in the midst of these technological changes, has its own unique opportunities regarding the teaching environment. Different factors are currently changing the educational scene in South Africa. With Curriculum 2000 and the Outcome-Based Education concept (OBE) came the opportunity to choose and incorporate relevant science and technology programmes into school curriculums. The introduction of Technology as a subject in junior secondary school, opened the door to bring students in contact with, for example, the vast world of material science. Senior secondary students, on the contrary, have little or no exposure to teaching programmes on modern materials; materials that rule their lives! There is a need for high quality, easily accessible and informative material science programmes. This provided the initiative to create this programme. Depending on the standard of students, "Fun with Polymers" can be used as: • a lecturing tool for teachers and lecturers • an encyclopeadia which students can interactively navigate to learn more about polymer science • a source of information to anyone curious about the interesting world of plastic materials. The name "Fun with Polymers" indicates that learning science can be fun (after ali!). The programme contains easy to use navigation buttons, helpfiles, hypertext, sound, animations and pictures to teach synthetic polymer material science. Content consists of the history of the development of polymer materials, basic polymer chemistry principles, information on the building of macromolecules, facts on synthetic polymer materials, and some questions and answers to test the student's knowledge. Practical experiments, with plastic materials, complement the theoretical information and provide students with hands-on experience.<br>AFRIKAANSE OPSOMMING: Multimedia was die gonswoord van die vorige dekade. Elektroniese leer is die gonswoord van die nuwe dekade. Beide hierdie konsepte het, en is nog steeds besig, om die wyse hoe kennis en inligting, plaaslik en wêreldwyd, aan studente oorgedra word, te verander. Suid-Afrika, as deel van hierdie tegnologiese veranderinge, bied unieke en uitdagende geleenthede op die gebied van onderwys. Verskillende faktore beïnvloed, op die oomblik, die plaaslike onderwys scenario. Die koms van Kurrikulum 2000 en Uitkomsgebaseerde Onderwys het die deur vir toepaslike wetenskap- en tegnologie programme, as deel van skoolleerplanne, geopen. Die toevoeging van Tegnologie, as vakgebied, tot die junior sekondêre fase, skep die geleentheid om studente in aanraking te bring met, byvoorbeeld, die enorme wêreld van materiaalkunde. Senior sekondêre studente het egter min tot geen blootstelling aan materiaalkunde leerprogramme ten spyte van die feit dat hul lewens daagliks deur moderne materiale beïnvloed en beheer word! Daar bestaan 'n behoefte aan hoë kwaliteit, maklik bekombare inligting oor moderne materiale en vandaar die dryfveer om hierdie program te skep. Afhangende van die standaard van die studente, kan hierdie program gebruik word as: • 'n onderrigprogram vir onderwysers en lektore • 'n bron van inligting wat studente interaktief kan navigeer om meer van polimeeerchemie te wete te kom • 'n bron van inligting vir enigiemand wat nuuskierig is oor die interessante wêreld van plastieke. Die naam van hierdie program: "Fun with Polymers" dui daarop dat die wetenskapleerproses pret kan wees! Die program bestaan uit maklik navigeerbare instruksies, hulplêers, hiperteks, klank, animasies, en foto's om lig te werp op die onderwerp van plastiek. Die inhoud beslaan die geskiedenis van die ontwikkeling van plastiek= materiale, basiese polimeerchemie beginsels, inligting oor die vorming van makro= molekules, feite oor sintetiese polimeermateriale, en vrae en antwoorde om die gebruiker te toets oor sy/haar kennis. Maklik uitvoerbare en toepaslike praktiese eksperimente komplimenteer die teoretiese inhoud van die multimedia program.

Thesis (PhD (Chemistry and Polymer Science))--Stellenbosch University, 2008.<br>The research presented in this dissertation was concerned with the living radical polymerization (LRP) of an amphiphilic, water-soluble, bi-substituted and biologically compatible acrylamide derivative, namely n-acryloylmorpholine (NAM). The primary objective of this research was the synthesis of novel block copolymers containing poly(dimethylsiloxane) (PDMS) and various chain lengths of poly(acryloylmorpholine) (polyNAM) using a LRP technique, namely reversibleaddition fragmentation chain transfer (RAFT) polymerization. This is the first report on the synthesis of these block copolymers using RAFT polymerization. These novel siloxane block copolymers were synthesized using a monohydroxyterminated PDMS material which had to first be modified into a thiocarbonylthiocontaining moiety in order for it to be used as macromolecular chain transfer agent (macroCTA) in the RAFT copolymerization with NAM. Suitable reaction conditions for the synthesis of these novel block copolymers had to, firstly, be determined, and secondly, optimized. In order to determine suitable reaction conditions, a series of homopolymerizations with NAM were first performed in order to compare which chain transfer agent (CTA), solvent, temperature etc. could possibly be best suited for the block copolymerizations of PDMS-b-polyNAM. Reported in this work is the first account of the homopolymerization of NAM and 2-(dodecylsulfanyl)thiocarbonylsulfanyl-2-methyl propionic acid (DMP) as CTA using RAFT polymerization. The resulting novel siloxane block copolymers are amphiphilic in nature and the existence of these structures was confirmed by size exclusion chromatography/multiangle light scattering (SEC/MALS), proton nuclear magnetic resonance (1H-NMR) spectroscopy, gel elution chromatography (GEC) and transmission electron microscopy (TEM). Interesting phase behaviour was observed in the latter technique.

Thesis (MSc)--Stellenbosch University, 2000.<br>ENGLISH ABSTRACT: This work involves the study of the effects of Reversible Addition-Fragmentation Chain Transfer (RAFT) agents on the emulsion polymerization of styrene. The feasibility of RAFT as a method for obtaining controlled radical polymerizations in emulsion systems is also investigated. Both seeded and ab initio systems were studied with three RAFT agents of varying structure. Inhibition and retardation effects on addition of various amounts of the RAFT agents to the emulsion systems were observed and the trends noticed. The effect of the RAFT agents on the average number of radicals per latex particle was calculated from reaction rates. The effect of the RAFT agent on the molecular weight and the molecular weight distribution was monitored by gel permeation chromatography. Exit of free radicals from the latex particles proves to be a major feature in the studied RAFT emulsion systems. Fragmentation of the RAFT agent in the latex particles, gives rise to free radical species that can exit from the particle and enter other particles where they can either terminate instantaneously or propagate. The exit and termination processes presumably result in both the inhibition and retardation of the emulsion polymerizations. A linear increase in Mn with conversion is observed, however the low concentration of RAFT agent in the latex particles is responsible for the obtained number average molecular weights being much higher than predicted. The low concentrations of RAFT agents in the latex particles is also responsible for the broad molecular weight distributions that are obtained. Reaction conditions for RAFT experiments should to be chosen so that the effects of exit processes are minimized and that the RAFT agent is primarily situated in the latex particles. These conditions must be met if the RAFT process is to be successful as a method of controlled radical polymerization in emulsions.<br>AFRIKAANSE OPSOMMING: Hierdie navorsing behels die studie van die effek van In bygevoegde addisie-fragmentasie kettingsoordragsreagent (RAFT1) op die emulsie polimerisasie van stireen. Die uitvoerbaarheid van RAFT as 'n metode om gekontroleerde radikale polimerisasies in emulsiesisteme te verkry is ook ondersoek. Eksperimente met drie RAFTkettingoordragsreagente van gevarieerde strukture is uitgevoer in beide seeded en ab initia sisteme. Die effek van die RAFT-reagent op die inhibisie en vertraging van die emulsie polimerisasie is waargeneem en die invloed van RAFT op die gemiddelde aantal radikale per partikel is bepaal. Die ontwikkeling van die molekulêre massa en die molekulêre massadistribusie is waargeneem deur middel van gel permeasie- kromatografiese tegnieke. Die ontsnapping van vrye radikale vanuit die partikels was 'n belangrike faktor in RAFT emulsiesisteme wat ondersoek is. Hierdie radikale is gegenereer deur die fragmentasie van die oorspronklike RAFT-reagent. Fragmentasie van die RAFT-reagent in die lateks partikels lei tot die vorming van vrye radikale spesies wat uit een partikel kan ontsnap en ander partikels kan binnedring waar dit onmiddellik kan termineer of propageer. Die ontsnappings- en terminasieprosesse van vrye radikale lei oënskynlik tot die inhibering en vertraging van die emulsie polimerisasie. 'n Lineêre verhoging in die gemiddelde molekulêre massa tydens konversie is waargeneem, alhoewel die Mn-waardes baie hoër was as wat verwag is. Die verskil kan toegeskryf word aan die klein hoeveelhede van die RAFT-reagent wat in die partikels teenwoordig is. Hierdie lae RAFT-konsentrasies is ook verantwoordelik vir die breë molekulêre massa distribusie wat waargeneem is. Vir die RAFT-proses om suksesvol te wees in gekontroleerde radikale polimerisasies in emulsies, moet reaksie kondisies so gekies word dat die ontsnapping van vrye radikale tot 'n minimum beperk word en die RAFT-reagent hoofsaaklik in die lateks partikels teenwoordig is.

Thesis (PhD)--Stellenbosch University, 2012.<br>ENGLISH ABSTRACT: Antimicrobial fibers are very useful in various fields such as air and water purification, wound dressings and protective bandages, where sterile environments are essential. The nonwoven nanofiber mats or membranes are able to filter out microorganisms and potentially kill several threatening pathogenic bacteria. In this thesis, a variety of styrene-maleimide copolymer derivatives were prepared based on the modification of poly(styrene-co-maleic anhydride with various primary amine compounds. All prepared copolymer derivatives were electrospun to nanofiber mats using the needle electrospinning technique. For the characterization, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to study the thermal properties of the electrospun fiber mats. Scanning electron microscopy (SEM) was carried out to observe fiber dimensions and morphology. The antibacterial activity of electrospun fiber mats was evaluated against different bacteria including Staphylococcus aureus (Gram-positive), Escherichia coli and Pseudomonas aeruginosa (Gram-negative). The evaluation study utilized different tools to test for antibacterial activity and mode of cell death, including bioluminescent imaging, fluorescence imaging and the viable cell counting method. Excellent antimicrobial activity was obtained against the different strains especially against Staphylococcus aureus. Fiber mats containing tertiary amino groups, phenol or quaternary ammonium groups had the strongest antimicrobial properties.<br>AFRIKAANSE OPSOMMING: Antimikrobiese vesels is baie nuttig in verskeie toepassingsgebiede, soos lug- en watersuiwering, wondbedekkings en beskermende verbande, waar ‘n steriele omgewing noodsaaklik is. Die ongeweefde nanovesel matte of membrane is in staat om mikroorganismes te verwyder deur filtrasie, maar kan ook verskeie patogeniese bakterieë doodmaak. In hierdie proefskrif is ‘n verskeidenheid stireen-maleimied kopolimeer afgeleides gesintetiseer, gebaseer op die modifikasie van poli(stireen-ko-maleïne anhidried) met verskeie primêre amien verbindings. Nanovesel matte van al die gesintetiseerde kopolimeer afgeleides is gemaak deur gebruik te maak van die naald-elektrospin tegniek. Die termiese eienskappe van hierdie nanovesel matte is bestudeer deur gebruik te maak van differensiële skandeer kalorimetrie (DSK) en termogravitasie analiese (TGA) as karakteriseringsmetodes. Die vesel dimensies en morfologie is bestudeer deur skandeer elektronmikroskopie as karakteriseringsmetode te gebruik. Die antibakteriële aktiwiteit van die gespinde vesel matte is geëvalueer teen verskillende bakterieë, naamlik Staphylococcus aureus (Gram-positief), Escherichia coli en Pseudomonas aeruginosa (Gram-negatief). Die evalueringstudie het verskillende instrumente gebruik om vir antibakteriële aktiwiteit en meganisme van seldood te toets, insluitend bioluminiserings beelding, fluoressensie beelding en die lewensvatbare sel tellingsmetode. Uitstekende antimikrobiese aktiwiteit is verkry teen die verskillende rasse, veral teen Staphylococcus aureus. Vesel matte met tersiêre aminogroepe, fenol of kwaternêre ammoniumgroepe het die sterkste antimikrobiese eienskappe gehad.

Thesis (PhD)--Stellenbosch University, 2012.<br>ENGLISH ABSTRACT: The primary aim of this study was to investigate the feasibility of the amphiphilic block copolymer poly((vinylpyrrolidone)-b-poly(vinyl acetate)) (PVP-b-PVAc) as a vehicle for hydrophobic anti-cancer drugs. PVP-b-PVAc block copolymers of constant hydrophilic PVP block length and varying hydrophobic PVAc block lengths were synthesized via xanthate-mediated controlled radical polymerization (CRP). The methodology consisted of growing the PVAc chain from a xanthate end-functional PVP. In an aqueous environment the amphiphilic block copolymers selfassembled into spherical vesicle-like structures consisting of a hydrophobic PVAc bilayer membrane, a hydrophilic PVP corona and an aqueous core. The self-assembly behaviour and the physicochemical properties of the self-assembled structures were investigated by 1H NMR spectroscopy, fluorescence spectroscopy, transmission electron microscopy (TEM) and dynamic and static light scattering. Drug loading studies were performed using a model hydrophobic drug, clofazimine, and a common anti-cancer drug paclitaxel (PTX) to evaluate the potential of the PVP-b-PVAc block copolymers for drug delivery,. Clofazimine and PTX were physically entrapped into the hydrophobic domain of the self-assembled PVP-b-PVAc block copolymers via the dialysis method. The drug-loaded PVP-b-PVAc block copolymers were characterized regarding particle size, morphology, stability and drug loading capacity in order to assess their feasibility as a drug vehicle. The polymer vesicles had a relatively high drug loading capacity of 20 wt %. The effect of the hydrophobic PVAc block length on the drug loading capacity and encapsulation efficiency were also studied. Drug loading increased with increasing the hydrophobic PVAc block length. The effect of the drug feed ratio of clofazimine and PTX on the drug loading capacity and encapsulation efficiency were also investigated. The optimal formulation for the drug-loaded PVP-b-PVAc was determined and further investigated in vitro. The size stability of the drugloaded PVP-b-PVAc block copolymers was also assessed under physiological conditions (PBS, pH 7.4, 37 °C) and were stable in the absence and presence of serum. PVP-b-PVAc block copolymers were tested in vitro on MDA-MB-231 multi-drug-resistant human breast epithelial cancer cells and normal MCF12A breast epithelial cells to provide evidence of their antitumor efficacy. In vitro cell culture studies revealed that the PVP-b-PVAc drug carrier exhibited no cytotoxicity towards MDA-MB-231 and MCF12A cells, confirming the biocompatibility of the PVP-b-PVAc carrier. In vitro cytotoxicity assays using clofazimine-PVPb- PVAc formulations showed that when MDA-MB-231 cells were exposed to the formulations, an enhanced therapeutic effect was observed compared to the free drug. Cellular internalization of the PVP-b-PVAc drug carrier was demonstrated by fluorescent labeling of the PVP-b-PVAc carrier. Fluorescence microscopy results showed that the carrier was internalized by the MDAMB- 231 cells after 3 hours and localized in the cytoplasm and the perinuclear region. Overall, it was demonstrated that PVP-b-PVAc block copolymers appear to be promising candidates for the delivery of hydrophobic anti-cancer drugs.<br>AFRIKAANSE OPSOMMING: Die studie is gebaseer op die gebruik van amfifieliese blokkopolimere van poli((Nvinielpirolidoon)- b-poli(vinielasetaat)) (PVP-b-PVAc) as potensiële geneesmiddeldraers. PVP-b-PVAc blokkopolimere van konstante hydrofiliese bloklengte en verskillende hydrofobiese bloklengte is voorberei via die RAFT/MADIX-proses. Blokkopolimere met vinielasetaat is vanaf poli(N-vinielpirolidoon) met ‘n xantaatendfunksie voorberei. In ‘n wateromgewing vorm die PVP-b-PVAc blokkopolimere vesikel strukture met ‘n hydrofobiese membraan en ‘n hydrofiliese mantel. Die fisies-chemiese eienskappe van die PVP-b-PVAc blokkopolimere is gekarakteriseerd met gebruik van KMR spektroskopie, fluoresent spektroskopie, transmissie elektronmikroskopie (TEM) en dinamiese en statiese lig verstrooiing. Die potensiaal van PVP-b-PVAc as ‘n geneesmiddeldraer is ondersoek deur gebruik te maak van die hydrofobiese geneesmiddel, clofazimine, en ‘n anti-kanker geneesmiddel, paclitaxel. Clofazimine en paclitaxel is ge-inkapsuleer in die hydrofobiese gedeelte van die blokkopolimere via die dialise-metode. Clofazimine-PVP-b-PVAc en paclitaxel-PVPb- PVAc blokkopolimere is gekarakteriseerd met betrekking tot die partikel grootte, morfologie, stabiliteit en laai kapasitiet om die PVP-b-PVAc blokkopolimere as geneesmiddeldraers te evalueer. Die PVP-b-PVAc geneesmiddeldraer het ‘n relatiewe hoë laai kapsiteit van 20 gew % aangetoon. Die invloed van die bloklengte op die laai kapasitiet is ook ondersoek en beskryf. ‘n Toename in die laai kapasitiet is gesien met ‘n toename in die hydrofobiese bloklengte. Die invloed van die hoeveelheid geneesmiddel op die laai kapasitiet en die inkapsuleer doeltreffendheid is ook ondersoek. Die optimale formulasie is gevind en verder gebruik vir in vitro studies. Die stabiliteit van die geneesmiddeldraer in fisiologiese omstandighede (pH 7.4, 37 °C) is ook beskryf. Resultate toon aan dat die sisteem stabiel is onder hierdie omstandighede in die afwesigheid en aanwesigheid van serum. In vitro eksperimente is op MCF12A epiteel-borsselle en MDA-MB-231 epiteelborskankerselle getoets om die anti-tumoraktiwiteit te ondersoek. Resultate toon aan dat die PVP-b-PVAc geen sitotoxiese effek op die selle het nie, wat aandui dat die polimere bioverenigbaar is. Verder is dit bewys dat die PVP-b-PVAc geneesmiddel formualsie ’n hoër sitotoxisiteit besit as die vry-geneesmiddel. Fluoresent studies het aangetoon dat die geneesmiddeldraer na 3 uur opgeneen word deur MDA-MB231 selle en gelokaliseerd is in die sitoplasma en in die omgewing van die kern van die selle. In die algemeen is dit aangetoon dat PVP-b-PVAc blokkopolimere potensiële kandidate vir die lewering van hydrofobiese geneesmiddels is.

Thesis (PhD)--Stellenbosch University, 2012.<br>ENGLISH ABSTRACT: In materials chemistry, surface-initiated reversible deactivation radical polymerisation (SI-RDRP) has emerged as one of the most versatile routes to synthesising inorganic/organic hybrid materials consisting of well-defined polymers. The resultant materials often exhibit a remarkable improvement in bulk material properties even after the addition of very small amounts of inorganic modifiers like clay. A novel cationic reversible addition–fragmentation chain transfer (RAFT) agent with the dual purpose of modifying the surface of Laponite clay and controlling the polymerisation of monomer therefrom, was designed and synthesised. Its efficiency to control the polymerisation of styrene was evaluated and confirmed through investigating the molar mass evolution and chain-end functionality. The surface of Laponite clay was modified with the cationic chain transfer agent (CTA) via ion exchange and polymerisation performed in the presence of a free non-functionalised CTA. The addition of the non-functionalised CTA gave an evenly distributed CTA concentration and allowed the simultaneous growth of surface-attached and free polystyrene (PS). Further analysis of the free and grafted PS using analytical techniques developed and published during the course of this study, indicated that the free and grafted PS chains were undergoing different polymerisation mechanisms. For the second monomer system investigated n-butyl acrylate, it was apparent that the molar mass targeted and the monomer conversions attained had a significant influence on the simultaneous growth of the free and grafted polymer chains. Additional analysis of the grafted polymer chains indicated that secondary reactions dominated in the polymerisation of the surface-attached polymer chains. A new approach to separating the inorganic/organic hybrid materials into their various components using asymmetrical flow field-flow fractionation (AF4) was described. The results obtained not only gave an indication of the success of the in situ polymerisation reaction, but also provided information on the morphology of the material. Thermogravimetric analysis (TGA) was carried out on the polymer-clay nanocomposite samples. The results showed that by adding as little as 3 wt-% of clay to the polymer matrix, there was a remarkable improvement in the thermal stability.<br>AFRIKAANSE OPSOMMING: Oppervlakgeïnisieerde omkeerbare deaktiveringsradikaalpolimerisasie (SI-RDRP) is een van die veelsydigste roetes om anorganiese/organiese hibriedmateriale (wat bestaan uit goed-gedefinieerde polimere) te sintetiseer. Die produk toon dikwels ʼn merkwaardige verbetering in die makroskopiese eienskappe – selfs na die toevoeging van klein hoeveelhede anorganiese modifiseerders soos klei. ʼn Nuwe kationiese omkeerbare addisie-fragmentasie kettingoordrag (RAFT) middel met die tweeledige doel om die modifisering van die oppervlak van Laponite klei en die beheer van die polimerisasie van die monomeer daarvan, is ontwerp en gesintetiseer. Die klei se doeltreffendheid om die polimerisasie van stireen te beheer is geëvalueer en bevestig deur die molêre massa en die funksionele groepe aan die einde van die ketting te ondersoek. Die oppervlak van Laponite klei is gemodifiseer met die kationiese kettingoordragmiddel (CTA) deur middel van ioonuitruiling en polimerisasie wat uitgevoer word in die teenwoordigheid van ʼn vrye nie-gefunksionaliseerde CTA. Die toevoeging van die nie-gefunksionaliseerde CTA het ʼn eweredig-verspreide konsentrasie CTA teweeggebring en die gelyktydige groei van oppervlak-gebonde en vry polistireen (PS) toegelaat. Verdere ontleding van die vrye- en geënte PS met behulp van analitiese tegnieke wat ontwikkel en gepubliseer is gedurende die verloop van hierdie studie, het aangedui dat die vry- en geënte PS-kettings verskillende polimerisasiemeganismes ondergaan. n-Butielakrilaat is in die tweede monomeer-stelsel ondersoek en dit was duidelik dat die molêre massa wat geteiken is en die geënte polimeerkettings. ʼn Nuwe benadering tot die skeiding van die anorganiese/organiese hibriedmateriale in hulle onderskeie komponente met behulp van asimmetriese vloeiveld-vloei fraksionering (AF4) is beskryf. Die resultate wat verkry is, het nie net 'n aanduiding gegee van die sukses van die in-situ polimerisasiereaksie nie, maar het ook inligting verskaf oor die morfologie van die materiaal. Termogravimetriese analise (TGA) is uitgevoer op die polimeer-klei nanosaamgestelde monsters. Die resultate het getoon dat daar 'n merkwaardige verbetering in die termiese stabiliteit was na die toevoeging van so min as 3 wt% klei by die polimeermatriks.

Thesis (PhD)--Stellenbosch University, 2008.<br>ENGLISH ABSTRACT: This study concerns the synthesis, properties and quantitative analysis of polydiallyldimethylammonium chloride (polyDADMAC), a water-soluble polymer used world-wide for potable water purification. The special interest in this polymer is the result of its widespread use and the current lack of adequate analytical methods for it. This is especially important for water treatment organisations. A novel gel permeation chromatography (GPC) method was developed and evaluated for polymer analysis. The scope was extended to determine the presence of unreacted monomer (DADMAC) as well as the percentage active polymer. polyDADMAC was first prepared using a known synthesis method. The product was purified and characterized by GPC and 13C-NMR spectroscopy. New and conclusive evidence of the existence of a five-member pyrrolidine ring system was obtained. A proposed mechanism of polymerization was determined. The activity of the synthesized polyDADMAC was evaluated and it was found to perform effectively as a coagulant. The physical and chemical properties of polyDADMAC were then studied under simulated water treatment conditions. The polymer reaction with chlorine revealed the formation of trihalogenated methane compounds (THMs). Gas chromatography–mass spectrometry (GC–MS) was used to conclusively identify the formation of chloroform. The polymer stability under different conditions of heat exposure, UV radiation and pH variations was studied. GPC results indicated that polyDADMAC is a very stable polymer and undergoes structural change only when subjected to extremes of pH, temperature and UV conditions. Results of a short study on microbial degradation indicated growth of the cultures, and subsequent polymer degradation. Reactions of polyDADMAC were concluded with a study of the impact of ozone on polyDADMAC. GPC results indicated a significant change in the ozonated polymer peak profile. Analytical methods to determine polyDADMAC residues in water were reviewed and critically evaluated. Methods based on complex formation/spectroscopy suffered from severe limitations and produced no meaningful results, contrary to claims made by previous researchers. Colloid titration based on an established method was promising but required extensive modification for quantitative analysis. Finally four novel methods were developed, including: solid phase extraction, membrane filtration-GPC, the HACH complexation method, and a GPC method with indirect UV detection. The study is concluded with a chemical risk assessment that indicated minimal human health risks associated with the production and use of polyDADMAC.<br>AFRIKAANSE OPSOMMING:Hierdie studie behels die sintese, eienskappe en kwantitatiewe analise van polidiallielmetielammoniumchloried (polyDADMAC), 'n wateroplosbare polimeer wat wêreldwyd vir drinkwatersuiwering gebruik word. Die belangstelling in hierdie spesifieke polimeer is as gevolg van die wydverspreide gebruik daarvan en die feit dat daar tans onvoldoende eenvoudige analitiese metodes daarvoor bestaan. Dit is veral belangrik vir waterbehandelingsorganisasies. 'n Nuwe gelpermeasiechromatografie (GPC) metode is ontwikkel en geevalueer vir die analise van hierdie polimeer. Die omvang van die studie is later uitgebrei om die teenwoordigheid van ongereageerde monomeer (DADMAC) asook die persentasie aktiewe polimeer te bepaal. polyDADMAC is eers volgens 'n bekende sintesemetode berei. Die produk is gesuiwer en gekarakteriseer m.b.v. GPC en 13C-KMR. Nuwe bewyse vir die bestaan van 'n vyflid pirollidoonringsisteem is verkry. 'n Meganisme vir hierdie polimerisasie metode is vasgestel. Die aktiwiteit van die bereide polyDADMAC is geevalueer en daar is bevind dat dit effektief as koaguleermiddel optree. Daarna is die chemiese en fisiese eienskappe van polyDADMAC onder gesimuleerde waterbehandelingskondisies bepaal. polyDADMAC het met chloor gerageer om trihalogeneerde metaanverbindings (THMs) te vorm. Gaschromatografie–massa-spektrometrie (GC–MS) is gebruik om die ontstaan van chloroform te bevestig. Daarna is die stabiliteit van die polimeer onder verskei reaksiekondisies bepaal: hitte, UV-bestraling, en pH. GPC-resultate het aangeduiui dat polyDADMAC baie stabiel is en ondergaan strukturele veranderings slegs onder uiterste kondisies van pH, temperatuur en UV. 'n Kort studie van die effek van mikro-organismes op polyDADMAC het egtermikrobiese kultuurgroei met die gevolglike afbreek van die polimeer getoon. Resultate van 'n studie van die impak van osoon op polyDADMAC het getoon dat daar 'n groot verandering in die GPC-profiel van die ge-osoneerde vorm van die polimeer was. Verdere analitiese metodes wat al gebruik is om polyDADMAC residue in water te bepaal, is uitgevoer en krities geevalueer. Metodes gebasseer op kompleksvorming/ spektroskopie het erge beperkings gehad en het nie betekenisvolle resultate gelewer nie. Dit was in teenstelling met wat voorheen deur ander navorsers bevind is. 'n Kolloiedtitrasie gebasseer op 'n bestaande metode het goeie resultate gelewer maar het omvattende veranderings benodig om kwantitatiewe resultate te lewer. Ten slotte is vier nuwe metodes ontwikkel: soliede fase-ekstraksie, membraanfiltrasie-GPC, die HACH-komplekseringsmetode, en 'n GPC-metode met indirekte UV-waarneming.. Die studie is afgesluit met 'n bepaling van die chemiese risiko wat poly DADMAC vir die gesondheid van die mens inhou. Daar is tot die gevolgtrekking gekom dat die produksie en gebruik van poly DADMAC slegs‘n minimum gesondheidsrisiko inhou.

Thesis (PhD)--Stellenbosch University, 2013.<br>ENGLISH ABSTRACT: Solution electrospinning is a technique used to produce polymer micro- or nanofibres. Recently a great deal of research has been done on the application of polymer nanofibres produced by this method. The solution electrospinning of polyolefins have not been researched in-depth mainly due to the difficulty in dissolving these polymers in suitable electrospinning solvents. We managed to electrospin polypropylene copolymers at room temperature, obtaining both polymer micro- and nanofibres. A suitable solvent system was developed (cyclohexane/DMF/acetone) that allowed for the room temperature solution electrospinning of these crystalline polypropylene copolymers. It was also shown that using propylene-1-alkene copolymers with a low comonomer content was a facile way of producing crystalline polyolefins nano – and microfibers. Similar attempts to electrospin isotactic polypropylene were unsuccessful, even though lower molecular weight materials were used than in the case of the copolymers. This lead to an investigation of solution melting temperature by SCALLS. The copolymers showed great variance in their solution melting temperatures despite the fact that they all had more or less the same crystallinity and amount of comonomer, indicating that the type of comonomer played an important role in the solubility of the copolymer. The effect of different collectors was investigated, but in the end it was found that between spinning unto ice, foil on ice of just foil, foil still seemed to be the best collector. Comparing crystallinity of the polymer powders with that of the polymer fibres by DSC and WAXD, it was found that there is a difference in the crystallinity of the fibres and the powders. EVOH is a polymer with excellent properties and electropspinning of this polymer is relatively easy due to the fact that it dissolves quite easily in conductive solvents. DMF, Isopropanol/water and DMSO were all tested as suitable solvents and the morphology was compared through the use of SEM. The morphology of the fibres indicated that DMSO was the best solvent. The influence of the spinning parameters was determined for both systems of DMF and DMSO. These nanofibres were used as reinforcement in LDPE matrix and the mechanical properties of the LDPE matrix was improved with the addition of both aligned and unaligned fibres. The next step was the electrospinning of EVOH fibres containing MWCNT. TEM, FE-SEM and TGA were used to confirm the presence of the MWCNT as well as determine the distribution of the MWCNT inside the nanofibres. The nanotubes were distributed through the fibres; however agglomeration of the nanotubes did still take place. The nanofibres containing MWCNT were also used to make composites where the fibres were melted, leaving the MWCNT behind in the polymer matrix. This was done in both LDPE and EVOH matrices. The LDPE/MWCNT composites did not give positive results, on the other hand the EVOH/MWCNT composite showed an improvement in the mechanical properties compared to pure EVOH. The attachment of fluorescent dye molecules to the surface of the MWCNT was attempted and through fluorescent microscopy and the dispersion of the nanotubes inside the fibres as well as the composite could be seen. This study proved that polyolefin nanofibres could be obtained, giving rise to more applications for these versatile polymers. It also confirmed the importance of nanofibres as reinforcement and the use of nanofibres as a way to incorporate MWCNT in a polymer matrix.<br>AFRIKAANSE OPSOMMING: Elektrospin in ‘n oplosmiddel is ‘n tegniek wat gebruik word om polimeer mikro- en nanovesels te produseer. Die afgelope tyd word baie navorsing gedoen oor die aanwending van polimeer nanovesels wat geproduseer word op hierdie manier. Daar is nog min navorsing gepubliseer wat handel oor die elektrospin van poliolefiene uit ‘n oplosmiddel, deels oor hoe moeilik dit is om ‘n geskikte elektrospin oplosmiddel te vind vir hierdie polimere. In hierdie studie het ons mikro- en nanovesels verkry deur polipropileen kopolimere te elektrospin by kamertemperatuur. Die polimere is opgelos in ‘n oplosmiddel sisteem wat bestaan uit sikloheksaan/dimetielformamied/asetoon, by hoë temperatuur en het toegelaat dat die polimere in oplossing bly by kamertemperatuur. Hierdie diverse kopolimere het verskillende resultate gegee, sommige polimere het mikrovesels produseer, waar ander nanovesels geproduseer het. Die vessel morfologie is ondersoek deur die gebruik van Skandering Elektron Mikroskopie (SEM) en daar is gevind dat die vesels nie ‘n gladde voorkoms het nie, maar dat daar kraalvormige morfologie gesien kon word. Om dit te voorkom is sout by die oplosmiddel sisteem gevoeg. Die invloed van die verskillende parameters op die vesels se deursnit is ondersoek vir al die kopolimere. Die byvoeging van sout het gelei tot ‘n meer gladde vesel morfologie. Die effek van die gebruik van verskillende oppervlaktes om die vesels op te vang is ondersoek en die die kristalliniteit van die polimeer poeiers is vergelyk met die kristalliniteit van die polimeer vesels met die hulp van DSC en WAXD. ‘n Poging is aangewend om isotaktiese polipropileen te elektrospin uit oplossing, maar ons kon nie daarin slag om die polimeer op te los nie, al was die molekulêre gewig minder as die van die kopolimere. Dit het gelei tot die ondersoek van die smeltpunt temperatuur in oplossing deur die gebruik van oplossing kristallisasie-analise deur laser lig verstrooing (SCALLS). Al die kopolimere het min of meer dieselfde kristalliniteit en hoeveelheid komonomer bevat, tog het hulle smeltpunt temperatuur in oplossing baie verskil. Dit het gedui op die feit dat die tipe komonomeer ‘n groot rol speel in die oplosbaarheid van die kopolimeer. Die elektrospin van etileen-ko-vinielalkohol (EVOH) is ook ondersoek. DMF, Isopropanol/Water en Dimetielsulfoksied (DMSO) is getoets as geskikte oplosmiddels en die morfologie van die vesels is vergelyk deur die gebruk van SEM. Die tyd wat die polimeer in oplossing gebly het asook die morfologie van die vesels, het aangedui dat DMSO die mees geskikte oplosmiddel was. Die invloed van die elektrospin parameters was vasgestel vir beide DMF en DMSO sisteme. Hierdie nanovesels is gebruik as versterking in ‘n LDPE matriks en die meganiese eienskappe van die LDPE matriks is verbeter deur die toevoeging van beide nie-geweefde en gerigte veselsopppervlakte. Die volgende stap was die elektrospin van EVOH vesels wat multi-ommuurde koolstof nanobuisies (MWCNT) bevat. TEM, FE-SEM en TGA was gebruik om te bevestig dat die vesels wel MWCNT bevat asook om die verspreiding van MWCNT in die vesels aan te dui. Die nanobuisies was versprei deur die vesels, maar bundels nanobuisies het tog voorkom in sommige plekke. Die nanovesels wat MWCNT bevat is ook gebruik om nanosamestellings te maak, waar die vesels gesmelt is om net MWCNT agter te laat in die polimeer matriks. Hierdie was gedoen in beide LDPE en EVOH matrikse. Geen positiewe resultate is verkry vir die LDPE/MWCNT nanosamestelling nie, maar die EVOH/MWCNT nanosamestelling het aan die anderkant ‘n groot verbetering getoon in die meganiese eienskappe in vergelyking met EVOH sonder MWCNT. ‘n Poging was aangewend om fluoreseerende molekules aan die oppervlak van MWCNT te voeg en deur fluoresensie mikroskopie kon die verspreiding van die MWCNT in die vesels asook in die nanosamestellings gesien word. Hierdie studie het bewys dat poliolefien nanovesels gemaak kan word wat lei tot die aanwending van hierdie polimere in nog meer toepassings. Dit het ook die belangrikheid van die gebruik van nanovesels as versterking in nanosamestellings bevestig asook die gebruik van nanovesels as ‘n manier om MWCNT in ‘n matriks te plaas.

Thesis (MSc) -- Stellenbosch University, 1999.<br>ENGLISH ABSTRACT: A free-radical polymerisation process, which has characteristics of a living polymerisation system, as it is capable of producing polymers of pre-determined molecular masses with a narrow molecular mass distribution, is discussed. It is also possible to make blockcopolymers by adding adding different monomers. The basic objective was to describe, discuss and explain the results of the effects of alkyl iodides as chain transfer agents on the seeded emulsion homo- and co-polymerisation of styrene and butyl acrylate. lodoacetonitrile and 1-phenylethyliodide were used as alkyliodides, acting as degenerative chain transfer agents. First, the effects of these alkyl iodides as chain transfer agents on the molecular mass, molecular mass distribution, glass transition temperature, conversion and particle size for the seeded emulsion polymerisation of styrene were studied. Second, the effects of alkyl iodides as chain transfer agents on the kinetics of radical emulsion polymerisation, especially the average amount of radicals per latex particle, were investigated. Third, the possibility of producing block-copolymers by emulsion polymerisation, using alkyl iodides as chain transfer agents, was investigated. To the best of the author's knowledge, results of work carried out in this study offer the first proof that the "living"/controlled radical polymerisation of styrene, with alkyl iodides as chain transfer agents, can be successfully carried out in emulsion. Addition of different alkyl iodides as chain transfer agents, in different concentrations, led to marked changes in the molecular mass, molecular mass distribution, glass transition temperature, conversion and particle size for the seeded emulsion polymerisation of styrene. The molecular masses of the polystyrene that was produced ranged from 156 to 663 577 while the average molecular mass distribution was below 2. Addition of these alkyl iodides to a seeded styrene polymerisation under zero-one conditions led to an average number of free radicals per latex particle that was greater than 1. A styrene seed latex with functional iodine end-groups was created and was successfully co-polymerised with butyl acrylate to produce a perfect styrene-butyl acrylate block-copolymer. This work has industrial importance as it allows the molecular mass, molecular mass distribution and particle size of polymers to be controlled. These factors are directly related to their micro- and macrostructure of polymers.<br>AFRIKAANSE OPSOMMING: Die vrye-radikaal polimerisasie proses wat die eienskappe van In lewendige polimerisasie sisteem toon, omdat dit moontlik is om 'n polimeer met voorafbepaalde molekulêre massas en 'n baie klein molekulêre massa verspreiding te berei, is bespreek. Dit is ook moontlik om, deur die byvoeging van 'n tweede monomeer, 'n blok ko-polimere te maak. Die doel was om die effekte wat alkieljodiede as ketlingoordragagente op die "seed" homo- en ko-polimerisasie van stireen en butiel akrielaat gehad het te beskryf en te verklaar. Jodoasetonitriel en 1-fenieletieljodied is gebruik as degeneratiewe kettingoordragagente. Eerstens is die uitwerking van hierdie alkieljodiede as kettingoordragagente op die molekulere massa, molekulere massa verspreiding, glas oorgang temperatuur, opbrengs en partikelgrote van die "seed" emulsie polimerisasie van stireen bestudeer. Tweedens is na die uitwerking van alkiekjodiede op die kinetika van In emulsie radikaal polimerisasie gekyk met spesifieke 1<lem op die gemiddelde aantal radikale per emulsie partikel. Derdens is die moontlikheid om blok ko-polimere te berei ondersoek. Na die beste van die outeur se wete is die resultate van hierdie studie die eerste bewys dat die "Iewendige"/gekontroleerde radikaal polimerisasie van stireen met alkieljodiede as ketlingoordragagente suksesvol in emulsie polimerisasie uitgevoer kan word. Die byvoeging van verskillende alkieljodiede, in verskillende konsentrasies, het aanleiding gegee tot opmerklike veranderinge in die molekulere massa, molekulere massa verspreiding, glas oorgang temperatuur, opbrengs en partikelgrote van die "seed" emulsie polimerisasie van stireen. Die molekulere massas van die bereide polistiereen het gewissel tussen 156 en 663 577 en die gemiddelde molekulere massa verspreiding was onder 2. Byvoeging van die alkieljodiede by die "seed" polimerisasie van stireen onder zero-een toestande het In gemiddelde aantal radikale per emulsie partikel van bo 1 gelewer. In Funksionele "seed" emulsie met jodium eindgroepe was geproduseer na 'n suksesvolle ko-polimerisasie met butiel akrielaat en 'n perfekte stireen-butiel akrilaat kopolimeer is verkry. Hierdie werk het industriele belang aangesien dit die beheer van molekulere massa, molekulere massa verspreiding en partikelgrote moontlik maak wat 'n direkte effek het op die mikro- en makro strukture van die polimeer.

Thesis (MSc)--Stellenbosch University, 2013.<br>ENGLISH ABSTRACT: A comparative study of the chemical composition of linear low density polyethylene polymers, synthesised with 1 - hexene as comonomer was conducted. Catalyst trials were conducted on the linear low density 1 - hexene polymer grade material to evaluate alternative catalysts. A comparative analysis was performed in order to investigate if the samples synthesised under catalyst trial conditions showed any significant differences in terms of crystallinity and mechanical properties with the reference sample that was synthesised using the reference catalyst. The results showed that the macro product properties, namely melt flow Index, density, and level of hexene extractables are different for the trial samples in comparison with the reference sample. The differences observed implied that the trial samples were synthesised with differences on a molecular level. The differences in the chemical composition between the reference sample and the comparative samples were fully explored using a wide range of analytical techniques, namely crystallisation analysis by fractionation (CRYSTAF), temperature rising elution fractionation (TREF), differential scanning calorimetry (DSC), Carbon 13 nuclear magnetic resonance (13C NMR), Size exclusion chromatography (SEC), Positron analysis lifetime spectroscopy (PALS) and micro hardness analysis. The results of the characterisation studies indicated the following: - Crystallinity and hardness analysis of the reference sample, catalyst trial sample 1 and catalyst trial sample 2 indicate that the catalyst trial sample 2 having a low cocatalyst concentration is the most crystalline of all the samples. - The reference sample, catalyst trial sample 1 and catalyst trial sample 2 were further fractionated using TREF at fractionation temperature intervals of 10°C. TREF analysis indicates that the bulk of the material is observed to elute between 70°C - 10°C. - 13C NMR analyses of the TREF fractions identified four populations of fractions that could be selectively removed, allowing the bulk of the material to be recombined. As these highly crystalline fractions were removed, there was an observed decrease in the total crystallinity of the bulk recombined material. This trend was further verified by the free volume analysis. - Free volume analysis indicated of the bulk recombined material indicated a general increase in the T3 lifetime and T4 lifetime intervals. Free volume analysis further confirmed a decrease in crystallinity of the bulk recombined material as highly crystalline material was removed. - Micro hardness analysis of the polymers further verified the crystallinity trends observed. As the molecular composition of the polymer changed due to removal of highly crystalline fractions, the total mechanical strength of the material indicated by the hardness value decreased. The study showed that by changing the chemical composition of the polymer by removing highly crystalline fractions, there was an observed change in the mechanical properties of the polymer. It can be concluded that the samples synthesised under catalyst trial conditions show significant differences in terms of crystallinity and mechanical properties in comparison with the sample that was synthesised using the standard reference catalyst.<br>AFRIKAANSE OPSOMMING: ‘n Vergelykende analise studie is onderneem van die chemiese samestellings van lineêre lae digtheid poliëtileen polimere, gesintetiseer met 1-hekseen as ko-monomeer. Alternatiewe kataliste is ge-evavuleer ten opsigte van lineêre lae digtheid 1-hekseen Sasol polimeer graad materiaal. Die vergelykende analise is uitgevoer om die monsters onder katalis proef kondisies te evalueer en te merk of enige beduidende verskille in terme van kristalliniteit en meganiese eienskappe met die verwysings monster voorkom. Die resultate toon dat die makro-produk eienskappe, naamlik smelt vloei indeks, digtheid en vlak van hekseen onttrekking, verskillend is vir die proef monsters in vergelyking met die verwysings monster. Die waargenome verskille impliseer dat die proef monsters op molekulêre vlak verskil. Die verskille in chemiese samestelling tussen die verwysings monster en die vergelykende monsters is ten volle ondersoek deur gebruik te maak van 'n wye verskeidenheid van analitiese tegnieke, naamlik kristallisasie analise fraksionering (CRYSTAF), temperatuur stygende eluering fraksionering (TREF), differensiële skandeer kalorimetrie (DSC), koolstof 13 kernmagnetiese resonansie (13C KMR), gelpermeasie chromatografie (SEC), positron analise leeftyd spektroskopie (PALS) en mikro-hardheid analise. Die resultate van die karakterisering studies het die volgende aangedui:- Kristalliniteit en hardheid analises van die verwysings monster en katalis proef monsters 1 en 2 het getoon dat katalis proef monster 2, wat ‘n lae ko-katalis konsentrasie bevat, die mees kristallyn is. - Die verwysings monster en katalis proef monster 1 en 2 is gefraksioneer met behulp van ‘n TREF met temperatuur tussenposes van 10°C. TREF analise toon dat oormaat materiaal ge-elueer word tussen 70°C en 100°C. - 13C KMR analise van die TREF fraksies het 4 verskillende fraksies geidentifiseer wat selektief verwyder kan word. Dit laat ook toe dat die grootste deel van die materiaal weer geherkombineer kan word. Soos die hoogs kristallyne fraksies verwyder is, is ‘n afname in die totale kristalliniteit van die geherkombineerde materiaal waargeneem. Hierdie tendens is bevestig deur vrye volume analises. - Vrye volume analises van die geherkombineerde materiaal toon ‘n algemene toename in die T3en T4 leeftyd aan. Vrye volume analises toon verder dat ‘n afname in die kristalliniteit van die geherkombineerde materiaal plaasvind soos meer kristallyne fraksies verwyder word. - Verdere mikro-hardheid analises van die polimere bevestig die waargenome kristalliniteit tendense. Soos die molekulêre samestelling van die polimere verander as gevolg van die verwydering van die hoogs kristallyne fraksies, so neem die totale meganiese sterkte van die materiaal af; soos aangedui deur die afname in hardheid waarde. Die studie toon dat die verandering van die chemiese samestelling van die polimeer, deur die verwydering van hoogs kristallyne fraksies, 'n waargenome verandering in die meganiese eienskappe van die polimeer laat plaasvind. Daar kan afgelei word dat die monsters, vervaardig onder die katalis proef voorwaardes, beduidende verskille toon in terme van kristalliniteit en meganiese eienskappe in vergelyking met die monster vervaardig deur die huidige verwysings katalis.

Thesis (PhD)--Stellenbosch University, 2013.<br>ENGLISH ABSTRACT: Heterophasic copolymers (also known as HECO polymers) or often referred to only as impact copolymers or block copolymers comprise a polymer matrix with a dispersed rubbery copolymer phase. The polymer under investigation in this study consists of a polypropylene homopolymer matrix and ethylene-propylene copolymers (EPCs). Due to its diverse range of applications and unique properties, polypropylene is the choice of polymer for a vast array of applications. This has led to the development of an entire class of polypropylene materials known as visbroken or controlled rheology polypropylene. By adding a suitable peroxide to the polymer in the presence of heat, radicals are formed which will attack the polymer chains in a random fashion. The resultant polymers generally have a higher melt flow rate (MFR), a narrower molecular weight distribution than the parent polymer, and good impact-stiffness balance. The main focus of this investigation was to determine if there exist any differences in the molecular structure and physical properties of controlled rheology HECO polymers and if differences do exist, how they influence the physical characteristics of the polymer. Eight HECO polymers with equal ethylene contents were visbroken to varying degrees by making use of two different types of organic peroxide. The effects of the amount of visbreaking on the molecular characteristics and physical properties were subsequently studied by making use various types of fractionation techniques, including preparative temperature rising elution fractionation (PTREF) and crystallisation analysis fractionation (CRYSTAF). Subsequent offline analysis was then done on the fractionated samples that included nuclear magnetic resonance spectroscopy (NMR), differential scanning calorimetry (DSC), high temperature size exclusion chromatography (HT-SEC), Fourier transform infrared spectroscopy (FTIR) and deposition of the SEC fractions via the LC Transform Interface (SEC-FTIR) as well as high temperature high performance liquid chromatography (HT-HPLC), a novel technique for the characterization of olefins according to their chemical composition.<br>AFRIKAANSE OPSOMMING: Heterofase kopolimere, ook bekend as HECO polimere, of dikwels na verwys net as impak kopolimere of blok kopolimere bestaan uit 'n polimeer matriks met 'n verspreide rubberagtige kopolimeer fase. Die polimeer wat in hierdie studie ondersoek was het bestaan uit 'n polipropileen homopolimeer matriks en etileen-propileen kopolimere (EPCs). As gevolg van sy veelseidigheid van toepassings en unieke eienskappe is polipropileen die keuse van polimeer vir 'n wye verskeidenheid van toepassings. Hierdie veelseidigheid het gelei tot die ontwikkeling van 'n hele klas van polipropileen materiaal bekend as gevisbreekte of beheerde reologie polipropileen. Deur die byvoeging van 'n geskikte peroksied tot die polimeer in die teenwoordigheid van hitte, word radikale gevorm wat die polimeerkettings in 'n ewekansige wyse sal aanval. Die gevolglike polimere in die algemeen het 'n hoë smelt vloeitempo (MFR), 'n smaller molekulêre gewig verspreiding as die moeder polimeer, en 'n goeie impak/styfheid balans. Agt HEKO polimere met gelyke etileen inhoude was gevisbreek in wisselende hoeveelhede deur gebruik te maak van twee verskillende tipes organiese peroksiedes. Die gevolge van die hoeveelheid van visbreeking op die molekulêre eienskappe en fisiese eienskappe was vervolgens gebestudeer deur gebruik te maak van verskillende fraksionasie tegnieke, insluitend preparatiewe TREF (P-TREF) en CRYSTAF. Daaropvolgende analiese is gedoen op die gefraktioneerde monsters en sluit in kernmagnetiese resonansie spektroskopie (KMR), differensiële skandeer kalorimetrie (DSC), 'n hoë temperatuur grootte uitsluitings chromatografie (HT-SEC), Fourier transform infrarooi spektroskopie (FTIR) met deponeering van die SEC fraksies via die LC transform koppelvlak (SEC-FTIR) sowel as 'n hoë temperatuur hoë werkverrigting vloeistof chromatografie (HT-HPLC), 'n nuwe tegniek vir die karakterisering van olefiene volgens hul chemiese samestelling.

Thesis (MSc)--University of Stellenbosch, 2007.<br>ENGLISH ABSTRACT: Silicone rubber, particularly poly(dimethylsiloxane) (PDMS), has been increasingly used in the manufacture of outdoor high voltage insulators in the recent years. PDMS offers several advantages that make it suitable for outdoor use, such as low weight, a hydrophobic surface, stability, and excellent performance in heavily polluted environments. PDMS surfaces can, however, become progressively hydrophilic due to surface oxidation caused by corona discharge, UV radiation and acid rain. In this study, PDMS samples of controlled formulations as well as six commercial insulator materials four PDMS based and two ethylene propylene diene monomer (EPDM) based were exposed to various accelerated weathering conditions for various periods of time in order to track changes in the material over time. The ageing regimes developed and used to simulate the potential surface degradation that may occur during in-service usage included needle corona and French corona ageing, thermal ageing, UV-B irradiation (up to 8000 hours) and acid rain (up to 200 days). Both the chemical and physical changes in the materials were monitored using a wide range of analytical techniques, including: static contact angle measurements (SCA), optical microscopy (OM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), gas chromatography (GC), gas chromatography/mass spectroscopy (GC/MS), size-exclusion chromatography (SEC), Fourier-transform infrared photoacoustic spectroscopy (FTIR-PAS) and slow positron beam techniques (PAS). A low molecular weight (LMW) uncrosslinked PDMS model compound was used to further study the chemical effects of corona exposure on PDMS materials. PDMS showed far better performance than EPDM, in terms of resistance to the various ageing regimes and “hydrophobicity recovery”.<br>AFRIKAANSE OPSOMMING: Silikoonrubber, spesifiek polidimetielsiloksaan (PDMS), is gedurende die afgelope paar jaar toenemend gebruik in die vervaardiging van buitelughoogspanningisolators. PDMS het baie voordele vir gebruik in elektriese isolators soos ‘n laer massa, ʼn hidrofobiese oppervlak, stabiliteit en uitstekende werking in hoogsbesoedelde omgewings. Die hidrofobiese oppervlakte kan egter gelydelik hidrofilies word weens oppervlakoksidasie as gevolg van korona-ontlading, UV-bestraling en suurreën. In hierdie studie is PDMS monsters van verskillende samestellings sowel as ses kommersiële isolators (vier PDMS en twee etileenpropileenrubber (EPDM)) blootgestel aan verskillende versnelde weersomstandighede vir verskillende periodes om die veranderinge in die materiale te monitor. Die verskillende materiale is gerangskik volgens hulle werking oor ‘n periode van tyd. Dit het ook ‘n geleentheid gebied om die eienskappe van die verskillende samestellings te bestudeer. Die tegnieke wat ontwikkel is om die moontlike oppervlakdegradasie te simuleer, het naald-korona, “French” korona, UVB-bestraling (tot 8000 uur) en suurreën (tot 200 dae) ingesluit. Beide die chemiese en die fisiese veranderinge in die materiale is gemonitor met behulp van verskeie tegnieke soos statiese kontakhoekbepaling, optiese mikroskopie, skandeerelektronmikroskopie, energieverspreidingsspektroskopie, gaschromatografie, grootte-uitsluitingschromatografie, foto-akoestiese Fouriertransforminfrarooi (PASFTIR) en stadige-positronspektroskopie (PAS). ʼn Lae molekulêre massa PDMS modelverbinding is gebruik om die chemiese effek van korona te bestudeer. Die PDMS materiale het baie beter vertoon teenoor die EPDM materiale in terme van hulle herstel van hidrofobisiteit.

Thesis (PhD)--University of Stellenbosch, 2011.<br>ENGLISH ABSTRACT: The crystallization of polyolefins is an important parameter in determining the properties of such materials. The crystallization phenomenon generally depends on the molecular symmetry (tacticity) and molecular weight of the material. In this study, a series of polypropylenes was prepared using heterogeneous MgCl2-supported Ziegler catalysts with two different external donors, diphenyldimethoxysilane (DPDMS) and methyl-phenyldimethoxysilane (MPDMS), and two different homogeneous metallocene catalysts, racethylene- bis(indenyl) zirconium dichloride, Et(Ind)2ZrCl2 (EI), and rac-ethylene-bis(4,5,6,7- tetrahydro-1-indenyl) zirconium dichloride, Et(H4Ind)2ZrCl2 (EI(4H)). Molecular hydrogen was used as terminating agent. In order to establish a correlation between the molecular weight and the crystallization of these polymers, fractionation of the materials according to crystallizability was performed by means of temperature rising elution fractionation (TREF). This affords the opportunity of blending materials of different molecular weights but similar symmetry. These materials were characterized using various analytical techniques: differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), 13C nuclear magnetic resonance spectroscopy (13C-NMR), high temperature gel permeation chromatography (HT-GPC) and Fourier-transform infrared spectroscopy (FT-IR). DSC was used to study the bulk crystallization of different polypropylene blends, most of which showed only one melting peak. The latter is usually associated with a high degree of cocrystallization. Turbidity analysis of the different polypropylene polymers, obtained using solution crystallization analysis by laser light scattering (SCALLS), provided good crystallization information – similar to that provided by crystallization analysis fractionation (CRYSTAF) and TREF. It was also possible to differentiate between polypropylenes with similar chemical structure but different tacticity and molecular weight. SCALLS results also showed that the blends of different isotactic polypropylene polymers were miscible and cocrystallization had occurred, whereas, the blends of syndiotactic polypropylene and different isotactic polypropylenes were not miscible and some interaction between phases had occurred. Optical microcopy (OM) and scanning electronic microscopy (SEM) were used to study the morphological properties of different isotactic polypropylenes. Results revealed a welldefined and large spherulitic morphology of mixed a1 (disordered) and a2 (ordered) crystal form structures. OM and SEM images also clearly showed an effect of molecular weight and tacticity on the crystal structure of the different polypropylene samples. Finally, various homopolymers and blends were studied to investigate the effect of molecular weight on the mechanical properties of these materials. This was done using microhardness testing and dynamic mechanical analysis.<br>AFRIKAANSE OPSOMMING: Die kristallisasie van poliolefiene is ‘n belangrike faktor wat die eienskappe van hierdie tipe materiale bepaal. In die algemeen hang kristallisasie af van die molekulêre simmetrie (taktisiteit) en molekulêre massa van die materiaal. ‘n Reeks polipropilene is berei deur gebruik te maak van heterogene MgCl2-ondersteunde Ziegler-kataliste met twee verskillende elektron donors, difenieldimetoksisilaan (DPDMS) en metielfenieldimetoksisilaan (MPDMS), en twee verskillende homogene metalloseenkataliste, rac-etileen-bis(indeniel) sirkoniumdichloried, Et(Ind)2ZrCl2 (EI), en rac-etileen-bis(4,5,6,7-tetrahidro-1-indeniel) sirkoniumdichloried, Et(H4Ind)2ZrCl2 (EI(4H)). Molekulêre waterstof is gebruik as termineringssagent. Ten einde ‘n verband te bepaal tussen die molekulêre massa en kristallisasie van hierdie polimere is hulle gefraksioneer op die basis van hulle kristallisseerbaarheid deur gebruik te maak van temperatuurstyging-elueringsfraksionering (TREF). Deur hierdie tegniek verkry ons materiale van verskillende molekulêre massa maar met dieselfde taktisiteit wat ons kan vermeng. Verskeie tegnieke is gebruik om hierdie materiale te karakteriseer: differensiële skandeerkalorometrie (DSC), wyehoek X-straal diffraksie (WAXS), 13C-kernmagnetiese resonansspektroskopie (13C-KMR), hoë-temperatuur gelpermeasiechromotagrafie (HT-GPC) en Fourier-transform-infrarooispektroskopie (FT-IR). DSC is gebruik om die vaste-toestand kristallisasie van verskeie vermengde polipropilene te bestudeer., en net een smeltpunt is in meeste gevalle waargeneem. Laasgenoemde word gewoonlik verbind met ‘n hoë mate van kokristallisasie. Oplossingkristallisasie analise, dmv laserligverstrooiing (SCALLS), is gebruik om die turbiditeit van die verskillende polipropileen kopolimeervermengings te bepaal. Goeie inligting aangaande die kristallisasie in oplossing – soortgelyk aan dié wat dmv die kristallisasie-analise-fraksioneringstegniek (CRYSTAF) en TREF bepaal is, is verkry. Dit was ook moontlik om te onderskei tussen polipropilene met soortgelyke chemiese strukture maar verskillende taktisiteit en molekulêre massas. SCALLS data het ook getoon dat die vermengings van verskeie isotaktiese polipropileen polimere versoenbaar was en dat kokristallisasie plaasgevind het, terwyl vermengings van sindiotaktiese polipropileen en verskeie isotaktiese polipropilene nie versoenbaar was nie en dat ‘n mate van fase-skeiding plaasgevind het. Optiese mikroskopie (OM) en skandeer-elektronmikroskopie (SEM) is gebruik om die morfologiese eienskappe van verskillende isotaktiese polipropilene te bepaal. Goed gedefineerde en groot sferulitiese morfologie van gemengde a1 (onordelike struktuur) en a2 (ordelike struktuur) kristal-strukture is waargeneem. OM en SEM beelde het ook gewys dat molekulêre massa en taktisiteit ‘n effek het op die kristalstruktuur van die verskillende polipropileenmonsters. Laastens is die meganiese eienskappe van ‘n verskeidenheid homopolimere en vermengde materiale bestudeer, deur gebruik te maak van mikro-hardheid metings en dinamiesmeganiese analise (DMA).

Thesis (MSc)--Stellenbosch University, 2012.<br>ENGLISH ABSTRACT: In the modern, fast moving society of today, there is a strong focus in research placed on the elimination of lengthy invasive medical procedures. Target specific, and chemo selective treatments are of great interest. Various advantages of this include patient comfort and over and above all cost reduction of invasive procedures. This project focused on the development of an injectable gel system with the use of biocompatible polymers. A system is regarded as injectable if the functional polymers are in solution before administration, but gels when added together. In order to design this system, one has to make use of polymers with complimentary functional groups. Telechelic amino-functionalized PVP with narrow molecular weight distribution was synthesized via RAFT-mediated polymerization. The polymer was thoroughly characterized and cross-linked with Poly(styrene-alt-maleic anhydride) to form a three dimensional polymeric network capable of absorbing and retaining large amounts of water and or biological fluid. Unfortunately the cross-linking needed to be performed in non-aqueous solution due to hydrolysis of maleic anhydride as a competing reaction in water. The gel was used in two model studies. The first model study focused on the attachment of a synthetic polypeptide onto the gel. The second model study evaluated the cytotoxicity effects of these gels when placed in direct contact with rodent cardiac myoblast and myocyte cells. These studies rendered promising results for future biological applications.<br>AFRIKAANSE OPSOMMING: In die moderne, vinnig bewegende samelewing van vandag, word daar in navorsing, 'n sterk fokus geplaas op die uitskakeling van lang indringende mediese prosedures. Doel spesifieke, en chemo selektiewe behandelings is van groot belang. Verskeie voordele van hierdie is die toename in gemak van die pasiënt en die verlaging van kostes verbonde aan hierdie indringende prosedures. Hierdie projek het gefokus op die ontwikkeling van 'n inspuitbare gel stelsel deur gebruik te maak van biologiese aanvaarbare polimere. ‘n Stelsel word beskou as inspuitbaar, indien die funksionele polimere in oplossing is voor toediening, maar wel kan gel wanneer bymekaar gevoeg word. Om hierdie tipe stelsel te kan ontwerp moet daar gebruik gemaak word van polimere met beskikbare funksionele groepe. Telecheliese amino-funksionele Poly(N-vinielpirollideen) met 'n smal molekulêre gewig verspreiding is gesintetiseer deur middel van RAFT-bemiddelde polimerisasie. Die polimeer is deeglik gekarakteriseer en daarna gekruis-koppel met P(STY-alt-MAnh) om 'n driedimensionele polimeriese netwerk te vorm. Hierdie netwerk is dan ook in staat om groot hoeveelhede water en/of biologiese vloeistof te absorbeer en te behou. Ongelukkig was hierdie reaksie uitgevoer in ʼn nie-waterige oplossing as gevolg van die hidrolise van Maleïne anhydride as 'n mededingende reaksie in water. Die gel is in twee model studies gebruik. Die eerste model-studie het gefokus op die beslaglegging van 'n sintetiese polipeptied op die gel. Die tweede model studie het die sitotoksiese uitwerking van hierdie gels in direkte kontak met knaagdier hart myoblast en lymfocyten selle geëvalueer. Hierdie studies het dan ook belowende resultate vir toekomstige biologiese toepassings gelewer.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2009.<br>In papermaking, the addition of filler can be detrimental to the properties of the resulting paper hence the use of additives that enhance paper properties are of paramount importance. Syndiotacticity rich poly(vinyl alcohol) (PVA) microfibrils were prepared for use as filler retention aids. They were prepared via in situ fibrillation during the saponification of high molecular weight poly(vinyl pivalate). The resulting fibers had high thermal stability and crystalline melting temperature. They were not fully soluble in water even at 100 oC. In order to make them less water resistant the syndiotacticity of the PVA microfibrils was varied by copolymerizing vinyl pivalate with vinyl acetate and saponifying the resultant copolymer. It was observed that changes in syndiotacticity had a significant effect on the crystallinity, morphology and thermal properties of the resultant PVA. The surfaces of the fibers were modified by first crosslinking using glyoxal (a dialdehyde), and then attaching cationic and anionic groups by grafting and by carboxymethylation. Crosslinking prior to modification was beneficial in minimizing the solubility of the fibers in the aqueous media in which they were modified. Heterogeneous modification techniques were employed so that fiber properties could be preserved. Carboxymethylation was carried out using the two step Williamson’s ether synthesis. The first step involves the formation of a highly reactive alkoxide by the reaction of PVA with a strong base and the second its etherification using a functional alkyl halide. Poly(methacryloyloxy ethyl trimethyl ammonium chloride) and poly(acrylic acid) were grafted from the PVA microfibrils using the KPS/Na2S2O3 redox initiation system. Grafting was confirmed by FTIR and NMR spectroscopy. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were carried out on both modified and unmodified PVA microfibrils. The results showed that crosslinking resulted in an enhancement of the thermal properties of the microfibrils. A decline in the onset temperature for thermal degradation and crystalline melting temperature were observed, and were attributed to the modification of the PVA microfibrils.

Thesis (MSc)--Stellenbosch University, 2000.<br>ENGLISH ABSTRACT: Various companies produce waxes, which are used extensively in various applications, either as produced or as chemically or physically modified value-added products. They are used in the traditional candle industry and applications including hot melt adhesives, inks, plastics, polishes and emulsions for rust prevention or fruit coating. Insight into the properties of these waxes is required to assist the applications chemist in understanding the role of the wax component in a specific formulation. Analytical techniques such as differential scanning calorimetry (DSC), thermogravimetry (TG), rheometry, gel permeation chromatography (GPC), high temperature gas chromatography (HTGC) and infra-red spectroscopy (IR) were used to characterise Fischer Tropsch, polyethylene, natural and petroleum waxes. Property profiles were formulated by integrating the results from the various techniques. The results of traditional wax analyses (e.g. congealing point, melting point, penetration, density and viscosity) were also correlated to relevant analytical results obtained from the instrumental techniques. Structure-property relationships have been proposed.<br>AFRIKAANSE OPSOMMING: Verskeie maatskappye vervaardig wasse, wat in menige toepassings gebruik word - of direk, of as chemies- of fisies- veranderde produkte van hoër waarde. Benewens die tradisionele kersbedryf, word die wasse in toepassings soos warmsmeltkleefmiddels, ink, plastiek, roeswerende- en vrugtebedekkings- emulsies en politoere gebruik. Wetenskaplikes betrokke by die formuleering van wasse vir verskillende toepassings sal baat vind by beter inligting van waseienskappe en die rol van waskomponente in formulasies. Tegnieke, bv. differensialeskandeerkalorimetrie (DSC), termogravimetrie (TG), reologie, gelpermeasiechromotografie (GPC), hoëtemperatuurgaschromatografie (HTGC) en infrarooispektroskopie (IR), is gebruik om Fischer Tropsch-, polietileen-, petroleum- en natuurlike wasse te karakteriseer. Profiele van waseienskappe is geformuleer deur die integrasie van die data verkry van die verskillende analitiese tegnieke. Die resultate van tradisionële wasanalises (bv. stolpunt, smeltpunt, penetrasie, digtheid, viskositieit en olie-inhoud) word ook in verband gebring met die resultate van die instrumentele analises. Verbande tussen struktuur en waseienskappe word ook voorgestel.

Thesis (MSc)--Stellenbosch University, 2001.<br>ENGLISH ABSTRACT: In this study, the feasibility of the non-conjugated 1,5-hexadiene as monomer in metallocene catalised cyclopolymerizations was considered. Homopolymers and copolymers with ethylene, propylene, 1-pentene, 1-hexene and 2-methyl-1,5- hexadiene as comonomers were synthesised in the presence of Cp2ZrCh and rac-Et(lnd)2Zrh. The microstructure (stereoregularity and cyclisation) and number-average molecular weight were determined from NMR analysis. Crystalline oligomers with functional (eg -OH) and vinylidene end groups were obtained.<br>AFRIKAANSE OPSOMMING: Die studie behels die ondersoek rakende die gebruik van ongekonjugeerde 1,5- heksadieen as monomeer in metalloseengekataliseerde polimerisasies. Homopolimere, sowel as kopolimere van etlieen, propileen, 1-penteen, 1- hekseen en 2-metiel-1,5-heksadieen, is in die teenwoordigheid van Cp2ZrChen rac-Et(lnd)2ZrCI2 gepolimeriseer. Die mikrostruktuur (stereochemie en siklisering) en die getal-gemiddelde molekulêre gewig van die gesintetiseerde polimere is met behulp van KMR spektroskopie ondersoek. Die studie het getoon dat kristallyne oligomere met funksionele (bv -OH) en vinilideen endgroepe gesintetiseer is.

Thesis (MSc)-- Stellenbosch University, 2012.<br>ENGLISH ABSTRACT: Over the past two decades, field flow fractionation (FFF), as a polymer characterization technique, has become cutting edge technology. The demand for molar mass and size characterisation of complex polymer systems has increased, especially in cases where classical calibration techniques such as size exclusion chromatography (SEC) has shown several shortcomings. FFF is a technique resembling chromatography. It has several significant advantages over SEC, especially for the characterisation of ultrahigh molar mass (UHMM), branched and gel-containing polymers. In this study, polybutadienes, which often contain the abovementioned species, were analysed by SEC and asymmetric flow field flow fractionation (AF4). Both separation techniques were coupled to refractive index and multi-angle laser light scattering detection. Similarly, polyrotaxanes, which are polymers with complex and unique molecular architectures, were also investigated. Results showed that AF4 can explicitly be used as a superior tool over SEC. In the case of UHMM polybutadienes, much higher molar masses could be detected by AF4, due to the absence of shear degradation which is often encountered in SEC. Gel-containing species could be detected by AF4 as no filtering is required prior to injection. Abnormal retention behaviour, a phenomenon often encountered in UHMM branched polymers, was observed in SEC analysis of the polyrotaxanes materials. AF4 provided sufficient separation from low to high molar masses, without out any irregularities.<br>AFRIKAANSE OPSOMMING: Gedurende die afgelope twee dekades het veldvloeifraksionering (FFF) as ‘n polimeerkarakteriseringstegniek groot veld gewen. Die aanvraag na molekulêre massa en groottekarakterisering van komplekse polimeersisteme het toegeneem, veral in die gevalle waar klassieke kalibrasietegnieke soos grootte-uitsluitingschromatografie (SEC) etlike tekortkominge getoon het. FFF is ‘n tegniek soortgelyk aan chromatografie, en het voorheen bewys dat dit oor ‘n redelike aantal voordele bo SEC beskik, veral in die geval van ultrahoë molekulêre massa- (UHMM-), vertakte- en jelbevattende spesies. In die huidige studie is polibutadieenpolimere, wat dikwels bogenoemde spesies bevat, geanaliseer met behulp van SEC en onsimmetriese vloei-veldvloeifraksionering (AF4). Beide skeidingstegnieke is gekoppel aan ‘n brekingsindeks en multihoek-laserligverstrooiingsdetektors. Op dieselfde wyse is polirotaksane (polyrotaxanes) met komplekse molekulêre argitektuur bestudeer. Daar is bewys dat AF4 uitsluitlik gebruik kan word as ‘n meer geskikte tegniek bo SEC. Baie hoër molekulêre massas kon deur middel van AF4 vir UHMM polibutadieenpolimere raakgesien word as gevolg van die verminderde afbrekende degradasie wat dikwels voorkom met SEC. Jel-bevattende spesies is suksesvol geïdentifiseer met behulp van AF4 waartydens geen filtrering vir analise nodig was nie. Abnormale retensie was sigbaar tydens SEC analise van monsters van polirotaksane, wat dikwels voorkom in vertakte polimere. In teenstelling het AF4 bewys dat ‘n bevredigende skeiding van klein na groot molekulêre massas, sonder enige tekortkominge, moontlik is.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2006.<br>Rectangular components were produced by both standard injection moulding and by a process called Lomolding. Both moulding grade polypropylene homopolymer and glass-filled polypropylene were used. The effect of processing parameters on material properties, as measured by tensile and impact strength, and warpage were determined for both injection moulding and lomolding, for both unfilled and glass-filled polypropylene materials. Sampling of the components allowed for critical evaluation of processing parameters’ effect on material properties at points close to and distant from the injection point, as well as in the direction of materials flow and transverse to material flow. Glass-filled components were also evaluated in terms of glass fibre length and fibre distribution (post-injection). Overall conclusions could be drawn with respect to the 2 different processes and the materials used. It was seen, inter alia, that the specimen orientation had no effect on the mechanical properties when using unfilled polypropylene, but that the orientation of the glass fibres in the testing direction resulted in an increase in the tensile strength and the impact strength for the injection moulded samples. Similar results were seen for lomolded samples, except that the fibre orientation effects were different. In the same vein, other notable differences could be observed for samples produced by lomolding and injection molding. Fibre length and distributions obtained by polymer burn-off experiments served to help explain differences in properties of glass-filled products produced by the two processes.

Thesis (PhD)--Stellenbosch University, 2014.<br>ENGLISH ABSTRACT: Complex polymer systems have multiple distributions with regard to molecular parameters such as molar mass, functionality, chemical composition, molecular architecture and microstructure. These distributions affect the properties of the polymers making it necessary to develop separation methods to be able to correlate structure to property. A single onedimensional chromatographic method is usually not sufficient to separate these complex polymers with respect to all the distributions. Hence, multidimensional liquid chromatography is necessary for the complete analysis of complex polymers using two or more chromatographic techniques before detection. In this work, two novel liquid chromatographic methods were developed to separate complex polymers according to microstructure. Comprehensive two-dimensional liquid chromatography (LC x LC) was carried out to observe the correlation between microstructure and molar mass. The separation according to microstructure was coupled to NMR (LC-NMR) to observe, identify and quantify the different microstructural components during chromatographic elution. The first chromatographic method separated hydrogenated and deuterated polystyrene homopolymers with respect to the isotope effect. For the LC x LC experiments, liquid chromatography at critical conditions (LCCC) was employed as the first dimension separating according to the isotope effect and size exclusion chromatography (SEC) as the second dimension separating according to molar mass. The LC x LC results of the blends showed that there was an improvement in isotopic separation with an increase in molar mass. The LCNMR coupling using both 1H and 2H NMR detection allowed for the identification of low molar mass blend components which were not sufficiently separated by liquid chromatography. The second chromatographic method separated stereoregular poly(methyl methacrylate)s (PMMAs) with respect to tacticity. The LC x LC experiments of stereoregular PMMAs utilised solvent gradient liquid chromatography as the first dimension to separate according to tacticity and size exclusion chromatography (SEC) as the second dimension to separate according to molar mass. The LC x LC results showed a change in the triad composition with elution of the stereoregular PMMAs with a slight influence of molar mass. The LC-NMR coupling allowed the observation of the triad composition during chromatographic elution.<br>AFRIKAANSE OPSOMMING: Komplekse polimeriese sisteme het meervoudige verspreidings ten opsigte van molekulêre parameters, soos byvoorbeeld, molêre massa, funksionaliteit, chemiese samestelling, molekulêre argitektuur en mikrostruktuur. Hierdie verspreidings beïnvloed die eienskappe van die polimere en dus is dit nodig om skeidingsmetodes te ontwikkel ten einde polimeerstruktuur met polimeereienskappe te kan korreleer. ‘n Enkele een-dimensionele chromatografiese metode is gewoonlik nie voldoende om hierdie komplekse polimere te skei met betrekking tot al die verspreidings nie. Multidimensionele vloeistofchromatografie, met die insluiting van twee of meer chromatografiese tegnieke, is dus nodig om polimere te skei voor waarneming kan plaasvind. Twee nuwe chromatografiese metodes is ontwikkel om komplekse polimere volgens mikrostruktuur te skei. Twee-dimensionele vloeistofchromatografie (LC x LC) is uitgevoer ten einde die korrelasie tussen mikrostruktuur en molêre massa te ondersoek. Daarna is die skeiding wat op mikrostruktuur gebasseer is, gekoppel aan KMR (LC-KMR) om die verskillende mikrostrukturele komponente gedurende chromatografiese eluering waar te neem, te identifiseer en te kwantifiseer. Die eerste chromatografiese metode het die gehidrogeneerde en gedeutereerde polistireen geskei met betrekking tot die isotoopeffek. Hier het die LC x LC skeiding bestaan uit vloeistofchromatografie onder kritiese kondisies (LCCC) as die eerste dimensie, wat skeiding bewerkstellig het gebasseer op die isotoopeffek, en grootte-uitsluitingschromatografie (SEC) as die tweede dimensie, wat skeiding bewerkstellig het gebasseer op die molêre massa. Die LC x LC resultate van die vermengings het ‘n verbetering in isotopiese skeiding met ‘n toename in molêre massa getoon. Deur gebruik te maak van die LC-KMR koppeling, waar beide 1H en 2H KMR waarneming gebruik is, was dit moontlik om die lae-molêre-massakomponente van vermengings wat nie volledig d.m.v. LC geskei kon word nie, te identifiseer. Die tweede chromatografiese metode het stereoreëlmatige polimetielmetakrilate (PMMAs) m.b.t. taktisiteit geskei. Die LC x LC skeiding van stereoreëlmatige PMMAs het bestaan uit oplosmiddel -gradiënt-LC as eerste dimensie om volgens taktisiteit te skei, en SEC as tweede dimensie om volgens molêre massa te skei. Die LC x LC resultate het ‘n molêre massa afhanklikheid van stereoreëlmatige PMMAs op taktisiteit getoon. Die LC-KMR koppeling het dit moontlik gemaak om die triade-samestelling gedurende chromatografiese eluering waar te neem.

Thesis (PhD)--University of Stellenbosch, 2006.<br>ENGLISH ABSTRACT: Metalloxycarbene complexes [(CO)5M1=O(R)M2(Cl)L2] (M1 = Cr , W; M2 = Zr, Hf; L = Cp, Cp*) were synthesized from the reaction between anionic Fischer-type carbene complex salts [(CO)5M1=C(O)R][NEt4] and metallocene chlorides. The molecular and crystal structures of [(CO)5W=C(Me)OZr(Cp)2Cl], [(CO)5Cr=C(Me)OZr(Cp)2Cl] and [(CO)5W=C(Ph)OHf(Cl)Cp2] determined by X-ray methods, show a short Ccarbene-O and relatively long O-Zr and O-Hf separations. Metalloxycarbene complexes in the presence of MAO are active catalysts for homo- and copolymerization of -olefins and produce polymers with heterogeneous properties. 1-Pentene oligomers, homopolymers of ethylene and ethylene/1-pentene copolymers were successfully synthesized using metalloxycarbenes/MAO and the results obtained were critically compared with those synthesized with metallocene/MAO catalysts. The GC and GPC show that 1-pentene oligomers produced with both metalloxycarbenes and metallocenes catalysts range from simple dimers to more complicated high molecular weight (2 600 g/mol) products. The properties of polyethylene and ethylene/1-pentene copolymers were evaluated by, among others, GPC, SEC-FTIR, preparative molecular weight fractionation and HPer DSC. Generally the polymers obtained using metalloxycarbene/MAO catalysts have broad and bimodal molecular weight distributions. The copolymers have higher concentration of 1- pentene in the lower molecular weight fraction than those produced with metallocene/MAO as shown by SEC-FTIR. Consequently, HPer DSC shows a decrease of melting and crystallization temperature towards the low molecular weight fractions.<br>AFRIKAANSE OPSOMMING: Metaaloksikarbeenkomplekse [(CO)5M1=C(R)OM2(Cl)L2] (M1 = Cr , W; M2 = Zr, Hf; L = Cp, Cp*] is gesintetiseer in die reaksie tussen anioniese Fischer-tipe karbeenkomplekssoute, [(CO)5M1=C(O)R][NEt4], en metalloseen dichloriedes. Die molekulêre- en kristalstrukture van [(CO)5W=C(Me)OZr(Cp)2Cl], [(CO)5Cr=C(Me)OZr(Cp)2Cl] en [(CO)5W=C(Ph)OHf(Cl)Cp2] bepaal deur X-straalkristallografiese metodes, toon die aanwesigheid van kort Ckarbeen-O- en relatief lang O-Zr- en O-Hf-bindings. Metaaloksikarbeenkomplekse, in die aanwesigheid van MAO, is aktiewe katalisatore vir die homo- en ko-polimerisering van α-olefiene en is verantwoordelik vir die vorming van polimere met heterogene eienskappe. 1-Penteen oligomere, homopolimere van etileen en etileen/1-penteen ko-polimere is suksesvol gesintetiseer met metaaloksikarbeenkomplekse/MAO en die resultate sodoende verkry, is krities vergelyk met produkte gesintetiseer vanuit metalloseen/MAO prekatalisatore. Die GC en GPC resultate toon dat die 1-penteen oligomere, geproduseer met beide metaaloksikarbeenkomplekse en metallosene, kan wissel van eenvoudige dimere tot meer komplekse, hoë molekulêre massa (2 600g/mol) produkte. Die polietileen en etileen/1- penteen ko-polimere is gekarakteriseer deur onder andere gevorderde, GPC, SEC-FTIR, preparatiewe molekulêre massa fraksionering en HPer DSC. In die algemeen het die polimere verkry met metaaloksikarbeen/MAO katalisatore, breë en bimodale molekulêre massaverspreidings. Die ko-polimere bevat hoër konsentrasies van 1-penteen in die lae molekulêre massa fraksie in vergelyking met dié gevorm vanuit metalloseen/MAO–gekataliseerde mengsels, soos aangedui deur SEC-FTIR-analise. HperDSC wys 'n verlaging in smelt- en kristallisasietemperature in die laer molekulêre massa fraksies.

Thesis (MSc)--Stellenbosch University, 2003.<br>ENGLISH ABSTRACT: Controlled free radical polymerisation techniques offer several practical and theoretical advantages compared to many other polymerisation techniques. Living polymerisation techniques such as anionic polymerisations require the total exclusion of impurities such as oxygen and moisture. Controlled free radical polymerisations, however, do not require such stringent methods of practice. This is very advantageous for industrial purposes. Atom Transfer Radical Polymerisation (ATRP) is a form of a controlled/living free radical polymerisation technique by which one is able to synthesize controlled architectural structures and predetermine the molecular weights of macromolecules. The monomers that were investigated for this research project include methyl methacrylate (MMA), 4-vinylpyridine (4VP) and lauryl methacrylate (LMA). The latter two monomers (4VP and LMA) are not commonly used in ATRP-mediated reactions. The synthesis of block copolymers ofMMA and LMA were attempted. The homopolymerisation of 4VP did not give the control expected when polymerising by means of ATRP. This prompted an investigation into possible side reactions that could take place with 4VP in this specific ATRP system. This included possible quatemization of 4VP with the alkyl halide initiator species.<br>AFRIKAANSE OPSOMMING: Beheerde vrye-radikaalpolimerisasietegnieke bied verskeie praktiese en teoretiese voordele bo verskeie ander vrye-radikaalpolimerisasietegnieke. Lewende polimerisasietegnieke soos anioniese polimerisasie, vereis die totale uitsluiting van onsuiwerhede soos suurstof en water. Beheerde vrye-radikaalpolimerisasies vereis egter nie sulke streng reaksiekondisies nie. Hierdie is baie voordelig vir industriële doeleindes. Atoomoordragradikaalpolimerisasie (ATRP) is 'n tipe beheerde/lewende vryeradikaalpolimerisasietegniek wat dit moontlik maak om die samestelling en struktuur van makromolekules asook die molekulêre massa presies te beheer. In hierdie studie is die monomere metielmetakrilaat (MMA), 4-vinielpiridien (4VP) en laurielmetakrilaat (LMA) bestudeer. Laasgenoemde twee monomere (4VP en LMA) word beskou as ongewone monomere om in ATRP-sisteme te gebruik. Daar is gepoog om blok kopolimere van MMA en LMA te sintetiseer. Die homopolimerisasie van 4VP het minder beheer gelewer as wat by beheerde vrye-radikaal sisteme soos hierdie verwag word. Na aanleiding van hierdie resultate is 'n ondersoek geloods om die moontlike newereaksies van 4VP in hierdie spesifieke ATRP-sisteem te ondersoek. Daar is gepoog om te bewys dat die alkielchloriedinisieerder verdwyn deur kwatemisasie met 4VP.

Thesis (MSc)--Stellenbosch University, 2004.<br>ENGLISH ABSTRACT: This study describes the design, building and optimization of a fully functional preparative TREF (Prep-TREF) apparatus. This apparatus allows for the fractionation of semicrystalline polyolefins according to the crystallizability of the molecules. Various factors, such as the sample cooling rate and the effect of on-support and off-support crystallization, are investigated. The preparative TREF is used to fractionate a commercial low-density polyethylene (LOPE), two commercially available plastomers (polyethylene-l-octene copolymers), as well as blends of the LOPE and the respective plastomers. It is shown that in each case the samples fractionated by crystallizability. The fractions recovered from the Prep-TREF were characterized by CRYSTAF, OSC and NMR analysis. It is shown how the results of this preparative fractionation allow for a better understanding of the molecular heterogeneity in the LOPE and plastomers. New ways of presenting the data from the preparative fractionation, in terms of 3- dimensional plots, are also investigated. These plots offer a novel way of presenting the molecular heterogeneity in the samples in terms of the molecular crystallizability. These plots highlight features that are difficult to detect in the conventional two-dimensional plots. In conclusion, the influences of various blending ratios of LOPE and plastomer on the morphological and physical properties of the blends, such as haze, clarity, and tear-and impact strength are determined.<br>AFRIKAANSE OPSOMMING: Die doel van hierdie studie was die ontwikkeling en optimisering van 'n ten volle funksionerende TREF. Hierdie tegniek word gebruik om polimeermengsels te fraksioneer deur gebruik te maak van die kristaliseerbaarheid van polimere. Verskeie faktore soos die afkoel spoed en die effect van met en sonder 'n ondersteuning(seesand) vir kristaliseering was ondersoek. Hierna is navorsing gedoen om 'n beter begrip ten opsigte van die meganiese, fisiese en optiese eienskappe van lae-digtheid poliëtileen (LDPE) te ontwikkel. Hierdie LDPE is met die affiniteitsreeks plastomere van die maatskappy, Dow Chemicals, gemeng om tendense in die gefraksioneerde polimere te indentifiseer. Een van Sasol se kommersiële LDPE produkte en twee van Dow Chemicals se plastomere is individueel gefraksioneer. Die mengsel van die twee ongefraksioneerde LDPE en plastomere is nog nooit voorheen op 'n molekulêre basis ondersoek nie. Dit is in hierdie studie gedoen deur van TREF gebruik te maak. Nuwe maniere is ontwikkel om data op 'n nuwe manier voor te stel deur middel van 3 Dimensionele grafieke te skep om resultate voor te stel wat andersins baie moelilik was om voor te stel in een dimensie agv die hoeveelheid data wat geinterpreteer word. Ten slotte is die invloed van die verskillende mengverhoudings van LDPE en plastomere op die morfologiese en fisiese eienskappe soos deursigtigheid, helderheid, skeur- en impaksterkte, ook ondersoek.

Thesis (MSc)--Stellenbosch University, 2001.<br>ENGLISH ABSTRACT: A novel approach to conducting controlled free radical polymerization in aqueous systems using Reversible Addition-Fragmentation Chain Transfer (RAFT) has been studied. When conducting RAFT in aqueous systems, reaction conditions must be chosen such that monomer transport across the aqueous-phase is either eliminated or facilitated. This is to prevent the formation of the red layer associated with RAFT in emulsions. The formation of the red layer is ascribed to the inability of waterinsoluble, dithiobenzoate-endcapped oligomers to be sufficiently transported across the aqueous phase. The novel approach in this study focussed on eliminating monomer transport and comprises two fundamental steps: the synthesis of dithiobenzoate-encapped oligomers in bulk followed by miniemulsification of these oligomers to yield a polymerizable miniemulsion. Dithioesters that act as chain transfer agents in the RAFT -process were synthesized in situ, thereby eliminating laborious and time-consuming organic purification procedures of dithioesters. In situ formation of the RAFT-agents involved conducting the reaction between di(thiobenzoyl) disulfide and conventional azo-initiators of differing structures in the presence of monomer. The structure of the chosen azo-initiator played a role in the efficiency of the RAFT process when the reaction was conducted in the presence of monomer to control the free radical polymerization process. Synthesis of the oligomers was performed by heating di(thiobenzoyl) disulfide and a selected azo-initiator, in the presence of monomer for a specific reaction duration in bulk. After the reaction was stopped, these oligomers were then miniemulsified by adding water, surfactant and cosurfactant, followed by the application of shear to form the resulting mini emulsion. The free radical polymerization of the dithiobenzoate-endcapped oligomers in the miniemulsion proceeded in a controlled manner with molecular weight increasing in a linear fashion with increasing conversion, while polydispersities remained low. The familiar red layer formation associated with RAFT polymerization in conventional emulsions was not observed under these conditions. The effects of changing the cosurfactant (hydrophobe) as well as changing the degree of polymerization of the emulsified oligomers were also investigated and described.<br>AFRIKAANSE OPSOMMING: Hierdie studie is geloods om 'n nuwe benadering tot die beheerde vry-radikaal polimerisasie in water gebaseerde sisteme te ondersoek. Daar is spesifiek gekyk na die uitvoer van die RAFT (Reversible Addition-Fragmentation Chain Transfer) proses in emulsies. Wanneer RAFT in emulsies toegepas word, moet die toestande waaronder die reaksie uitgevoer word, versigtig opgestel word. Die toestande moet so gekies word dat die vervoer van monomere deur die waterfase óf geëlimineer word óf gefasiliteer word. Dit word gedoen om die faseskeiding in die vorm van 'n rooi laag, wat so kenmerkend van RAFT -polimerisasie in emulsies is, te voorkom. Hierdie faseskeiding vind plaas omdat die vervoer van ditiobensoaat endgroep-bevattende oligomere deur die waterfase tydens interval II, moeilik is a.g.v. hulle oplosbaarheid in water. Die nuwe benadering wat hier bestudeer is, het twee basiese stappe. Eerstens word die ditiobensoaat endgroep-bevattende oligomere in bulk gesintetiseer. Dit word gevolg deur die emulsifisering van die oligomere. Hierna vind verdere polimerisasie van die oligomere plaas deur die dormante oligomere te heraktiveer. Die ditio-esters wat as kettingoordrag agente optree in die RAFT proses, word in situ gesintetiseer. Hierdie modifikasie sny tydrowende organiese suiweringsmetodes uit. Die in situ RAFT agente word gesintetiseer deur di(tiobensoïel) disulfied met verskillende konvensionele azo-inisieerders te laat reageer. Die struktuur van die spesifieke azoinisieerder het wel 'n rol gespeel in die effektiwiteit van die RAFT proses om molekulêre massa te beheer as bg. reaksie in die teenwoordigheid van monomere uitgevoer is. Die sintese van die oligomere is gedoen deur di(tiobensoïel) en 'n azo-inisieerder te verhit in die teenwoordigheid van monomere. Die reaksie is gedoen in bulk en die graad van polimerisasie van die oligomere is beheer deur die reaksie te stop by verskillende tydstippe. Nadat die bulk reaksie gestop is, is hierdie oligomere ge-emulsifiseer deur die oligomere te meng met 'n seep, hidrofoob en water. Hierdie mengsel word dan onderwerp aan 'n vermengingskrag om 'n polimeriseerbare mini-emulsie te vorm. Die voortsetting van die polimerisasie van die oligomere in die mini-emulsie het op 'n beheerde wyse verloop, m.a.w. molekulêre massa wat linieêr toeneem met stygende omsetting. Polidispersiteit indekse van die polimere het deurentyd laag gebly in die stabielste sisteme. Onder hierdie toestande was daar geen kenmerkende rooi laagvorming te bespeur nie. Die effekte wat die verandering van die hidrofoob, asook die verandering van die graad van polimerisasie van die oligomere op die sisteem gehad het, is onder andere ook ondersoek en beskryf.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2006.<br>This study concerns the polymerization of propylene both in the presence and absence of molecular hydrogen. The percentage of hydrogen used as a terminating agent in the polymerization reactions was varied from 0.1 wt% to 15.0 wt% in order to compare a variety of polymers with different percentages of hydrogen incorporated. Two ansa metallocene catalysts were used: (A) rac-[ethylene bis(indenyl)] zirconium dichloride (rac-Et(Ind)2ZrCl2) and (B) dimethylsilyl-bis(2-methyl benzoindenyl) zirconium dichloride (rac-Me2Si(2-MeBenz[e]Ind)2ZrCl2). Methylaluminoxane (MAO) was used as cocatalyst for both of the two catalysts. Characterization of the polymers included using nuclear magnetic resonance spectroscopy (NMR) for information concerning the microstructure of the polymers, high temperature gel permeation chromatography (HT-GPC) for molecular weight and molecular weight distributions and differential scanning calorimetry (DSC) to investigate the melting point and crystallization behaviour of the polymers. The polypropylenes prepared with the dimethylsilyl-bis(2-methyl benzoindenyl) zirconium dichloride catalyst system were compared to the polypropylenes synthesized with ethylene-bis(indenyl) zirconium dichloride. In particular, the effects of hydrogen on the microstructure, molecular weight, molecular weight distribution, melting point and crystallization behaviour were investigated.

Thesis (MSc)--Stellenbosch University, 2012.<br>ENGLISH ABSTRACT: The presence of mineral oils in dry foodstuff was found to originate from the packaging materials, namely, paperboard manufactured from recovered fibres, and these oils subsequently migrate to the foodstuff via the vapour phase. The presence of mineral oils in food is of concern as it originates from the use of paper products not originally intended for food contact applications, i.e., before the paper is subjected to a suitable recycling process. These mineral oils consist of technical grade compounds which may contain aromatic compounds and other components with unknown toxicological effects. Although the related authorities are currently considering the safe and legal limits of these contaminants in foodstuffs, as well as establishing a standardised test method for monitoring mineral oils in food and packaging materials, paperboard manufacturers wish to ensure that their products are safe for food contact applications. Since recycling is unavoidable, particularly from an ecological and economical point of view, one of the proposed solutions the industry is focussing on is the use of a functional barrier towards mineral oils – be it an inner bag as a direct food-contact surface, or a barrier coating directly applied on the inner side of the paperboard. In this study, a permeation test method was established, and developed, to evaluate the transmission rate of a volatile organic compound, acting as a mineral oil simulant, through model paper and plastic packaging materials. This was correlated to the transmission rate of actual mineral oil through the packaging materials, and therefore used as a highly accelerated tool to characterise packaging materials in relation to their barrier properties. The test method, referred to as the “heptane vapour transmission rate,” was subsequently used to derive the required transport parameters’ characteristics of each of the tested materials, which enabled an evaluation of the potential shelf-life of the packaged product. This research demonstrated that barrier-coated paperboards have the ability to behave in the same way as, and often even better than, commercial plastic films, towards the migration of mineral oil. Detailed information on the interaction between the packaging materials and mineral oil simulant, n-heptane, was acquired from gravimetric sorption. Insight was obtained into a material’s ability to function as a mineral oil barrier. It was established that the quick and easy permeation method was sufficient for evaluating packaging materials as potential mineral oil barriers, and resulted in the determination of transport parameters that were higher than that obtained by sorption. The obtained transport parameters could therefore be considered a worst case scenario when predicting the package content shelf-life.<br>AFRIKAANSE OPSOMMING: Daar is voorheen bevind dat die teenwoordigheid van mineraalolies in droë voedsel afkomstig is van die verpakkingsmateriaal, naamlik karton, wat vervaardig is van herwonne papierprodukte, en daarna migreer die olies na die voedsel deur die gasfase. Die teenwoordigheid van hierdie mineraalolies in kos wek groot kommer aangesien dit afkomstig is van papierprodukte wat nie oorspronklik bedoel is vir voedselkontak voor die herwinningsproses nie. Die olies bestaan uit industriële graad mineraalolies wat moontlik aromatiese verbindings asook ander komponente bevat waarvan die toksiekologiese effekte onbekend is. Terwyl die betrokke owerhede tans besig is om die veilige en wettige grense van hierdie kontaminante in voedsel te oorweeg, asook die vestigting van 'n gestandaardiseerde toetsmetode vir die kontrole van mineraalolies in die voedsel-verpakkingsmateriaal-kombinasie, wil karton- en papiervervaardigers graag verseker dat hul produkte veilig is vir voedselkontak. Siende dat herwinning onvermydelik is vanuit 'n ekologiese en ekonomiese oogpunt, is een van die voorgestelde oplossings in die bedryf om te fokus op die gebruik van 'n funksionele keerfilm ten opsigte van mineraalolies, wat ‘n sakkie binne-in die karton, wat dien as die direkte kos-kontakoppervlak, of 'n keerlaag, wat direk aangewend word op die binnekant van die karton, kan behels. Hierdie studie ondersoek die daarstel en deursypelingsontwikkeling van 'n toetsmetode om die oordragtempo van 'n vlugtige organiese verbinding, wat optree as 'n mineraalolie simulant, deur middel van model papier- en plastiekverpakkingsmateriale, te evalueer. Dit stem ooreen met die oordragtempo van werklike mineraalolies deur die verpakkingsmateriaal en kan dus gebruik word as 'n hoogs versnelde instrument om verpakkingsmateriale te karakteriseer met betrekking tot hul keereienskappe. Die toetsmetode, die sogenaamde "heptaangasoordragtempo," is vervolgens gebruik om die vereiste oordragparameters af te lei wat kenmerkend is van elk van die geëvalueerde verpakkingsmateriale en wat sodoende gebruik kon word om die potensiële raklewe van die verpakte produk te bepaal. Hierdie navorsing het getoon dat kartonprodukte met ‘n keerlaag die vermoë het om dieselfde op te tree as kommersiële plastiekfilms en dikwels selfs beter, ten opsigte van die migrasie van mineraalolies. Gedetailleerde inligting oor die interaksie tussen die verpakkingsmateriale en mineraalolie simulant, n-heptaan, is verkry vanaf gravimetriese sorpsie. Dit gee insig in 'n materiaal se vermoë om te funksioneer as 'n mineraalolie-keermiddel. Daar is vasgestel dat die vinnige en maklike deurwerking metode voldoende is vir die evaluering van verpakkingsmateriale as potensiële mineraalolie-keermiddels, en verleen oordragparameters wat hoër is as dié verkry deur sorpsie. Hierdie oordragparameters kan dus as 'n ergste scenario vir die voorspelling van die raklewe van ‘n verpakte produk beskou word.

Dissertation (Ph.D.)--Stellenbosch University, 2002.<br>ENGLISH ABSTRACT: The deposition of platinum catalyst on cation-exchange membranes was achieved by a counter diffusion deposition method known as the Takenaka- Torikai method. The morphology of the platinum catalyst on the membranes were controlled by varying the conditions of the platinum deposition process, such as, temperature, type of reducing agent and concentration of the platinic acid solution. The effect of the sonication of platinic acid solution and the pre-treatment of membranes on the morphology of a platinum catalyst was also investigated. Platinum loading on cation-exchange membranes was determined by UV spectrophotometric and gravimetric analyses. Suitable conditions for the quantitative determination of the platinum loading on membranes by UV spectrophotometric analysis was established through the development of a protocol. Membranes were characterised using different techniques such as, Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM), Infrared spectrometry (IR), Dielectric analysis (DEA) and Brunauer Emmett Teller adsorption (BET). The roughness profile of a platinum catalyst embedded on a membrane was explored by various statistical methods. The statistical analysis of various data sets for a surface of a platinum-containing membrane was investigated using the Hurst exponent. The effect of surface modification of membranes on the deposition process, as well as the morphology of the platinum catalyst, was investigated. Membranes were modified with ethylene diamine (EDA) and cetyltrimethylammonium bromide surfactant. Modification of membranes with cetyltrimethylammonium bromide surfactant resulted in a unique textured platinum catalyst. The electrochemical "switching" phenomenon was investigated for EDAmodified membranes and EDA-modified membranes embedded with platinum catalyst. The "switching" phenomenon was observed in i-V cyclic curves, which were obtained by galvanodynamie measurements. The application of electro catalytic membrane systems in the anodic oxidation of water was investigated by electrochemical techniques such as galvanostatic and cyclic voltammetric measurements.<br>AFRIKAANSE OPSOMMING: Die deponering van 'n platinum katalis op katioon-uitruil membrane is suksesvol gedoen d.m.v. die Takenaka-Torikai metode. Die morfologie van die platinum katalis op die membrane is gekontrolleer deur variasie van die kondisies van die platinum deponeringsproses, bv. temperatuur, tipe reduseermiddel gebruik en konsentrasie van die platiensuuroplossing, asook die ultrasonifikasie van die platiensuuroplossing en voorafbehandeling van die membrane. UV spektrofotometriese asook gravimetriese analitiese metodes is gebruik om die platinumlading op katioon-uitruil membrane te bepaal. Geskikte kondisies vir die kwantitatiewe bepaling van die platinumlading op membrane d.m.v. UV spektrofotometriese analise is ontwikkel deur die skep van 'n protokol. Membrane is gekarakteriseer d.m.v. die volgende tegnieke: Atoomkrag Mikroskopie, Skanderingselektron Mikroskopie, Infrarooi Spektrometrie, di-elektriese analise en Brunauer Emmett Teller adsorpsie. Die skurtheidsprofiel van 'n platinum katalis op 'n membraan is ondersoek deur gebruik te maak van verskeie statistiese metodes. Statistiese analises van verskeie data stelsels van 'n platinum-bevattende membraan is ondersoek deur gebruik te maak van die Hurst eksponent. \ Die effek van oppervlakmodifikasie op membrane sowel as die deponeringsproses en morfologie van die platinum katalis is ondersoek deur die modifikasie van membrane met etileen diamien (EDA) en setieltrimetielammonium bromied as versepingsmiddel Die elektrochemiese omswaai van EDA-gemodifiseerde membrane sowel as gemodifiseerde platinum bevattende membrane is ondersoek d.m.v. galvanodinamiese metings. Die gebruik van elektro-katalitiese membraansisteme in die anodiese oksidasie van water is ondersoek deur gebruik te maak van elektrochemiese tegnieke, bv. galvanostatiese en sikliese voltammetriese metings.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2010.<br>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.<br>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 (PhD)--Stellenbosch University, 2003.<br>ENGLISH ABSTRACT: Alkali-soluble rheology modifiers are commercially synthesised via conventional freeradical polymerisation processes. This results in the end product having certain limitations; there is poor control over the molar mass, molar mass distribution and chain architecture of the polymer chains. These limitations can be overcome by using a controlled/living free radical polymerisation process, for example the RAFT process. This alternate method of synthesis was used here to prepare model alkali-soluble rheology modifiers. The structure/property relationships of model alkali-soluble rheology modifiers synthesised via the RAFT process were studied. Model alkali-soluble rheology modifiers of different molar masses and chain architectures (block, co- and ter-polymers) were successfully synthesised by the RAFT polymerisation of methyl methacrylate, methacrylic acid and various hydrophobic macromonomers. The different types of alkali-soluble rheology modifiers were synthesised in solution and in miniemulsion. Each of the two systems had certain advantages and disadvantages. The conversion limit of reactions in solution was about 60 % and reaction times were much slower than those of the miniemulsion reactions. Higher final conversions were recorded for miniemulsion reactions, reactions were faster and no solvent removal was required. Unfortunately it was not possible to synthesise all the different types of associative rheology modifiers investigated here in a miniemulsion system. The latex solutions thickened with conventional rheology modifiers (co-polymers) show very contrasting behaviour (rheology profile and dynamic properties) to that of the latex solutions thickened with the associative rheology modifiers (ter-polymers). The AB block copolymers gave the latex solutions rheology results between those obtained with conventional rheology modifiers and those with the associative rheology modifiers. Varying the number of ethylene oxide spacer units in the hydrophobic macromonomers of the associative rheology modifiers had a significant influence on the rheology properties of the latex and alkali solutions. As the number of ethylene oxide spacer units was increased from 20 to 100 there was a significant increase in the zero-shear viscosity of the latex solutions thickened with the associative rheology modifiers. Contrasting results were obtained for the polymer solutions (no latex present), where the use of the associative rheology modifiers containing the highest number (EO = 100) of ethylene oxide spacer units resulted in solutions with the lowest viscosity, but the rheology modifiers containing the 50 ethylene oxide spacer units gave the highest steady shear viscosity.<br>AFRIKAANSE OPSOMMING: Alkali-oplosbare reologie-modifiseerders word kommersieël gesintetiseer d.m.v. konvensionele vrye-radikaal polimerisasieprosesse. Hierdie prosesse lewer gewoonlik 'n eindproduk met sekere tekortkominge, a.g.v. swak beheer oor molekulêre massa, molekulêre massa-verspreiding, en polimeerkettingstruktuur (Eng. chain architecture). Hierdie tekortkominge kan oorbrug word deur gebruik te maak van 'n beheerde/lewende vrye-radikaal polimerisasieproses, soos byvoorbeeld die RAFT-proses (Eng. RAFT: reversible addition-fragmentation chain transfer polymerisation). Hierdie alternatiewe metode is in die studie gebruik om model alkali-oplosbare reologiemodifiseerders te sintetiseer. Die struktuur-eienskapverhoudings van die model alkali-oplosbare reologie modifiseerders wat d.m.v. die RAFT-proses gesintetiseer is, is bestudeer. Model alkali-oplosbare reologiemodifiseerders van verskillende molekulêre massas en kettingstrukture (blok, ko- en ter-polimere) is suksesvol gesintetiseer d.m.v. RAFT-polimerisasie van metielakrilaat, metakrielsuur en hidrofobiese makromonomere. Die verskillende alkali-oplosbare reologiemodifiseerders is in organiese oplosmiddel sowel as in mini-emulsie gesintetiseer. Elkeen van die sisteme het sekere voordele en nadele getoon. In die reaksies wat in organiese oplosmiddels gedoen is, is slegs 60 % van die monomere ingebou in die polimeerkettings en die tydsduur van hierdie reaksie was heelwat langer as by die wat uitgevoer is in mini-emulsie. Meer as 60 % van die monomere is omgeskakel na polimeer tydens die reaksies wat in mini-emulsie uitgevoer is, die reaksietempo was vinniger en dit was nie nodig om die organiese oplosmiddel te verwyder nie. Ongelukkig was dit nie moontlik om al die verskillende tipes assosiatiewe-reologiemodifiseerders (Eng: associative rheology modifiers) in miniemulsie te sintetiseer nie. Die lateks wat met konvensionele reologiemodifiseerders (ko-polimere) verdik is, het kontrasterende eienskappe (reologie-profiel en dinamiese eienskappe) getoon teenoor die van die lateks-oplossings wat met assosiatiewe-reologiemodifiseerders (ter-polimere) verdik is. Die AB-tipe blok ko-polimere gee reologieresultate vir die lateks-oplossings wat lê tussen die wat bepaal is vir konvensionele reologieodifiseerders en assosiatiewe reologiemodifiseerders. Variasie in die aantal etileenoksiedeenhede in die hidrofobiese makromonomere van die assosiatiewe reologiemodifiseerders het 'n betekenisvolle invloed op die reologie-eienskappe van die lateks, sowel as die alkali-oplossings gehad. Namate die aantal etileenoksiedeenhede van 20 tot 100 vermeerder is, het 'n betekenisvolle verhoging in die "zero-shear " viskositeit van die lateks oplossings wat met die assosiatiewe reologiemodifiseerders verdik is voorgekom. Teenstrydige resultate is verkry vir die polimeeroplossings met geen lateks teenwoordig nie: die assosiatiewe reologiemodifiseerders met die hoogste aantal etieleenoksiedeenhede (EO = 100) het die laagste viskositeitsresultate opgelewer en die reologiemodifiseerders met slegs 50 etieleenoksiedeenhede het die hoogste viskositeitsresultate gelewer.

Thesis (MSc)--University of Stellenbosch, 2005.<br>ENGLISH ABSTRACT: Chemical and molecular tagging agents have illustrated their diversity in a number of different applications. One of the most significant applications includes the use of chemical tagging agents for product registration in industry. Industrial enterprises producing good products need to ensure product authenticity to prevent duplication through piracy and unscrupulous industrialists. Fluorescent probes are chemical compounds that satisfy most of the technical and commercial aspects that are required to be excellent tagging agents. They are generally quick to synthesize, do not affect the product integrity, display little or no impact on the uses of the product or the environment and they can be identified by relatively simple detection procedures. The aim of the present study was to synthesize fluorescent polymers as tagging agents for the paint industry. 7-Hydroxy-2H-chromen-2-one (A1) and 7-hydroxy-4-methyl-2H-chromen-2-one (B1), commercially available fluorescent hydroxyl compounds, were selected as the starting materials. An esterification reaction resulted in the production of 2-oxo-2H-chromen-7-yl acrylate (A2) and 4-methyl-2-oxo-2H-chromen-7-yl acrylate (B2), which are acrylic-type monomers that were required for polymerisation. Studies showed that fluorescence was maintained during the esterification. Copolymers poly(MMA-co-A2), poly(MMA-co-B2), poly(BA-co-A2) and poly(BA-co-B2), synthesized via homogeneous free radical initiated copolymerisation, revealed how copolymer compositions were affected by the feed compositions and the pattern of monomer incorporation over time. This was investigated by following individual monomer consumption rates by 1H-NMR spectroscopy. Fluorescence studies revealed that the fluorescence behaviour of A2 and B2 was maintained during the copolymerisation. Latex particles, with fluorescent behaviour, were synthesized via in situ miniemulsion polymerisation. High molecular weight copolymers with monodisperse particle sizes (nm range) were obtained. A bench-top UV lamp and UV-reflectance studies confirmed the fact that fluorescent latex particles can be identified and quantified respectively, when dispersed in paints that are either free of titanium dioxide or paints that contain titanium dioxide.<br>AFRIKAANSE OPSOMMING: Die diversiteit van chemiese en molekulêre merkers in ‘n verskeidenheid van toepassings is al telkemale geïllustreer. Een van die mees belangrike toepassings in die industrie is die gebruik van chemiese merkers vir produkregistrasie. Industrieë wat goeie produkte verskaf moet die egtheid van hul produkte kan verseker deur duplikasie via nadruk (Eng: piracy) deur ander te voorkom. Fluoresserende merkers is chemiese stowwe wat aan die meeste van die tegniese en kommersiële vereistes voldoen om as uitstekende merkers te dien. Die sintese van die merkers is gewoonlik nie tydrowend nie, beïnvloed nie die integriteit van die produk nie, het min of geen impak op die gebruike van die produk of die omgewing en kan deur relatief eenvoudige prosedures bepaal word. Die doel van hierdie studie was die sintese van fluoresserendepolimere om as merkers in die verfindustrie te dien. 7-Hidroksie-2H-chromen-2-oon (A1) en 7-hidroksie-4-metiel-2H-chromen-2-oon (B1), fluoresserende hidroksielverbindings wat kommersieël beskikbaar is, is gekies as uitgangstowwe vir die bereiding van die merkers in hierdie studie. ‘n Esterifikasie-reaksie het gelei tot die produksie van 2-okso-2H-chromen-7-ielakrilaat (A2) en 4-metiel-2-okso- 2H-chromen-7-ielakrilaat (B2). Hierdie produkte is tipiese akrilaat-tipe monomere wat benodig word vir polimerisasie. Ondersoeke het getoon dat fluoressensie behoue tydens esterifikasie gebly het. Die kopolimere poli(MMA-ko-A2), poli(MMA-ko-B2), poli(BA-ko-A2) en poli(BA-ko-B2) is deur homogene vry-radikaal-geïnisieerde kopolimerisasie gesintetiseer. Daar is vasgestel hoe die kopolimeersamestelling geaffekteer is deur die samestelling van die reagense (Eng: feed composition) en die patroon van monomeer inkorporasie met tyd. Dit was ondersoek deur die tempo van verbruik van die individuele monomere d.m.v. 1H-KMR spektroskopie te bepaal. Daar is verder vasgestel dat die fluoressensie van A2 en B2 gedurende kopolimerisasie behoue gebly het. Latekspartikels, met fluoressensie gedrag, is via in-situ mini-emulsie-polimerisasie gesintetiseer. Hoë molekulêre massa kopolimere met monodisperse partikelgroottes (in die order van nanometers) is verkry. Deur van ‘n UV-lamp en UV-refleksie studies gebruik te maak is daar bepaal dat fluoresserende latekspartikels in polimere, in verf - wat of titaniumdioksied bevat of geen titaniumdioksied bevat nie -, beide geïdentifiseer and gekwantifiseer kan word.

Dissertation (Ph.D.)--Stellenbosch University, 2001.<br>ENGLISH ABSTRACT: Self-emulsifiable and self-assembling nano-particle phosphated and siloxane-modified polyurethane dispersions, for use in metal coatings, were synthesised from a new phosphate monomer, a carboxylate monomer, a polysiloxane macroglycol and a . cycloaliphatic diisocyanate, and characterised. Crosslinked nano-particles of acrylic-modified, self-assembling, phosphated polyurethane dispersions with better water swell resistance were obtained using the phosphated nanoparticles as the 'seed' to polymerise monofunctional and multifunctional acrylic monomers in the dispersed phase. This was done by reacting 2-hydroxyethyl methacrylate end-capped polyurethane with monofunctional and multifunctional acrylate monomers in the dispersed phase. Phase inversion of the polyurethane resin from an organic solvent into dispersion was accompanied by three stages, as studied by viscosity and conductivity measurements. In an attempt to modify existing synthesis procedures of the traditional polyurethane acrylic dispersions for which organic solvents are used, polymerisable acrylic monomers were used as diluents during the urethane-forming reaction. This resulted in overcoming the limitations of the existing process. Particle-size analysis indicated that the above dispersions had smaller particle sizes, narrower distributions and better hydrophobicity than any reported to date. Aqueous vinylterminated phosphated polyurethane dispersions were studied for their viscosity behaviour under shear and showed Newtonian behaviour. The polyurethane dispersions were evaluated for their hydrolytic stability with respect to the location of the ionic groups on the segments. Greater hydrolytic stability was obtained when the ionic groups were on the urethane hard segment. The polyurethane dispersionsresponded well to UV curing, a curing technique that has not received much attention to date. The surface and interface analyses of the self-assembling coatings obtained from the phosphated and siloxane-modified polyurethane dispersions showed increased silicon enrichment at the coating/air interface and phosphorus enrichment at the metal/coating interface. Results of dynamic contact angle studies proved the poor wettability of the coatings, as shown by the increase in contact angle by probe liquids. Dynamic thermogravimetry studies of the phosphate-containing polyurethanes showed a decrease in activation energy with increasing phosphate content. This is a good indication that phosphate-containing polyurethanes could be used as fire retarding coatings that comply with fire limit regulations.<br>AFRIKAANSE OPSOMMING: Self-emulgeerbare en selfsamestellende, nanopartikel, fosfaat- en siloksaanbevattende poliuretaandispersies, vir gebruik as deklae vir metale, is gesintetiseer en gekarakteriseer. Die uitgangstowwe vir die ~ bereiding was 'n splinternuwe fosfaatmonomeer, 'n karboksilaatmonomeer, 'n polisiloksaanglikol en 'n siklo-alifatiese diisosianaat. Deur die polimerisasie van die monofunksionele en multifunksionele akriel-monomere in die dispergeerde fase in te ent met die fosfaat-bevattende nanopartikels, is kruisgebinde nanopartikels van akrielgemodifiseerde, selfsamestellende, fosfaatbevattende poliuretaandispersies met goeie waterswelweerstand berei. Dit is bewerkstellig deur poliuretaan, met reaktiewe hidroksietiel-endgroepe, te reageer met monofunksionele akrilaatmonomere in die gedispergeerde fase. Fase-omkering van die poli-uretaanhars uit die organiese oplosmiddel, tot in dispersie, het in drie stappe plaasgevind. Dit is bepaal deur viskositeit en konduktiwiteit. Bestaande metodes van sintese Vir tradisionele poli-uretaanakrieldispersies, waarvoor organiese oplosmiddels gebruik is, is gewysig om die beperkinge van die bestaande metodes te oorkom. Suskes is behaal met die gebruik van polimeriseerbare akrielmonomere as verdunningsmiddels in die uretaanvormingsreaksie. Partikelgrootte-analises het getoon dat die verkreë dispersies kleiner partikelgroottes, nouer verspreidings en beter hidrofobisiteit gehad het as enige wat tot dusver beskryf is. Die viskositeit van die wateroplosbare, vinielgetermineerde, fosfaatbevattende poliuretanandispersies is onder afskuiwing bepaal en het Newtoniese gedrag getoon. Die hidrolitiese stabiliteit van die poli-uretane, met betrekking tot die posisie van die ioniese groepe in die segmente, is bepaaL ..Die polimere met die ioniese groepe in die harde segment van die poli-uretaan het hoër hidrolitiese stabiliteit vertoon. Kruisbinding (verharding) deur middel van UV, wat tot dusver min aandag geniet het, was baie suksesvol. Analises van die oppervlakte en die tussenvlak van die selfsamestellende deklaag, wat van die fosfaat- en siloksaanbevattende dispersies berei is, het verhoogde siloksaanverryking by die deklaag/lug tussenvlak en verhoogde fosfaatverryking by die metaal/deklaag tussenvlak getoon. Resultate van dinamiese kontakhoekstudies het bewys dat die deklae swak benat is, dws daar was 'n toename in die kontakhoek deur peilvloeistowwe. Termogravimetriese studies het getoon dat daar 'n afname was in die aktiveringsenergie van die fosfaatbevattende poli-uretane met 'n toenemende fosfaatinhoud. Hierdie feit dui daarop dat hierdie poli-uretane moontlik as brandvertragende deklae gebruik kan word.

Thesis (PhD)--Stellenbosch University, 2012.<br>ENGLISH ABSTRACT: The use of co-sonication (ad-miniemulsion) polymerisation for the preparation of highly filled polymer/clay hybrid latexes is described. Laponite (Lap) content levels in the range of 10–50 wt% were effectively encapsulated in both polystyrene (PS) and polystyrene-co-butyl acrylate nanoparticles (PSBA). The latex and film morphological features of these highly filled hybrid materials were evaluated using both transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). PS/Lap latexes exhibited mixed particle morphologies from armoured particles at low clay content (10 wt%) to encapsulated particles at high clay content (50 wt%). However, PSBA/Lap hybrid latexes exhibited predominantly crumpled particle morphologies through the clay content studied. The resultant polymer/clay nanocomposites (PCNs) of PS/Lap and PSBA/Lap exhibited either partially or fully exfoliated structures. It was found that generally these PCNs exhibited superior properties than the neat polymers except for thermal stability properties. As much as 5000% storage modulus improvement was observed for both PS/Lap and PSBA/Lap relative to the neat polymers. The Tg of PSBA/Lap showed a 14 ºC shift towards higher temperature. Rheology tests showed that the resultant PCNs exhibited solid-like viscoelastic behaviour. The encapsulation of montmorilonite clay (MMT) using the ad-miniemulsion procedure was found to be ineffective. The MMT platelets remained adhered onto the polymer particles surfaces. Ineffective encapsulation of MMT platelets was attributed to their dimensions which were either large or equal to those of the polymer particles. Despite the ineffective encapsulation, the MMT platelets were completely exfoliated within the final PCNs as shown by both SAXS and TEM. Overall, the ad-miniemulsion was found to be an effective method for the preparation of highly filled water based polymer/clay hybrid latexes. However, the clay encapsulation in polymer particles and the extent of clay exfoliation were found to be dependent on clay dimensions relative to the polymer particles, monomer/clay compatibility and clay modifier reactivity. It was found that clay dimensions and use of clay modifier that improve monomer/clay compatibility enhances encapsulation. On the other hand, the modifier reactivity influenced the extent of clay exfoliation in the final PCN, irrespective of clay encapsulation in the polymer particles. These findings were based on comparative studies conducted on the use of Lap versus MMT and non-reactive modifier versus reactive modifier during ad-miniemulsion polymerisation.<br>AFRIKAANSE OPSOMMING: Die gebruik van mede-sonikasie (ad-miniemulsie) polimerisasie vir die voorbereiding van die hoogsgevulde polimeer/klei hibriedlatekse word beskryf. Laponiet (Lap) vlakke in hoeveelhede van 10-50 gew% is effektief ge-inkapsuleer in beide polistireen (PS) en polistireen-ko-butielakrilaat nanopartikels (PSBA). Die morfologiese eienskappe van die latekse en films van hierdie hoogsgevulde hibried materiale is geëvalueer deur beide transmissie-elektronmikroskopie (TEM) en klein-hoek X-straal-verstrooiing (SAXS). PS/Lap latekse het gemengde partikel morfologieë getoon, bv. vanaf gepantserde partikels by lae kleihoeveelhede (10 gew%) tot ge-inkapsuleerde partikels by hoë kleihoeveelhede (50 gew%). Daarteenoor het PSBA/Lap hibriedlatekse „n oorwegend verkreukelde partikelmorfologie getoon vir die reeks kleihoeveelhede wat bestudeer is. Die gevolglike polimeer/klei nanokomposiete (PKNs) van PS/Lap en PSBA/Lap het, óf gedeeltelike, óof ten volle geëksfolieerde strukture getoon. Oor die algemeen is bevind dat hierdie PKNs beter eienskappe as die suiwer polimere getoon het, behalwe vir die termiese stabiliteit eienskappe. Verbeteringe van soveel as 5000% in die stoormodulus is waargeneem vir beide PS/Lap en PSBA/Lap met betrekking tot die suiwer polimere. Die Tg van PSBA/Lap het „n 14°C verskuiwing na „n hoër temperatuur getoon. Reologiese toetse het getoon dat die gevolglike PKNs vastestofagtige visko-elastiese gedrag getoon het. Die inkapsulering van montmorilonietklei (MMT), deur middel van die ad-miniemulsieproses, was ondoeltreffend. Die MMT plaatjies het agtergebly op die oppervlaktes van die polimeerpartikel. Oneffektiewe inkapsulering van MMT plaatjies is toegeskryf aan hul grootte, wat óf groter, óf gelyk was aan dié van die polimeerpartikels. Ten spyte van die oneffektiewe inkapsulering was al die MMT plaatjies in die finale PKNs geëksfolieer soos deur beide SAXS en TEM aangedui. Oor die algemeen is bevind dat ad-miniemulsie „n effektiewe metode is vir die voorbereiding van hoogsgevulde waterbasis polimeer/klei hibriedlatekse. Daar is egter bevind dat klei inkapsulering in polimeerpartikels asook die omvang van klei eksfoliëring, afhanklik is van die klei afmetings in verhouding tot die polimeerpartikels, monomeer/klei verenigbaarheid en die reaktiwiteit van die kleiwysiger. Daar is bevind dat die klei afmetings en die gebruik van „n kleiwysiger wat die monomeer/klei verenigbaarheid verbeter, inkapsulering bevorder. Aan die ander kant het die reaktiwiteit van die kleiwysiger die omvang van klei eksfoliëring in die finale PKNs beïnvloed, ongeag van klei inkapsulering in die polimeerpartikels. Hierdie bevindings is gebaseer op vergelykende studies van die gebruik van Lap teenoor MMT en nie-reaktiewe wysiger teenoor reaktiewe wysiger gedurende ad-miniemulsiepolimerisasie.

Thesis (PhD)--Stellenbosch University, 2012.<br>ENGLISH ABSTRACT: New methods are described for the synthesis of polymer/graphite nanocomposites using the miniemulsion polymerization process. Natural graphite was functionalized by oxidation to produce graphite oxide (GO) nanosheets. Poly(styrene-co-butyl acrylate) (poly(St-co-BA)) nanocomposite latices containing GO nanosheets were successfully synthesized using miniemulsion as a one-step nano-incorporation technique. The approach followed included expanding the GO nanosheets in situ during the miniemulsification step and then polymerizing the monomers in the presence of these expanded nanosheets. Styrene (St) and butyl acrylate (BA) were mixed with GO and then emulsified in the presence of a surfactant and a hydrophobe to afford pre-miniemulsion latex particles. The stable pre-miniemulsions were then polymerized to yield poly(St-co-BA)/GO nanocomposite latices. The polymerization proceeded with relatively high monomer conversion and produced stable nanocomposite latex particles. The nanocomposites exhibited mainly an intercalated morphology, irrespective of the percentage of GO filler loading. The synthesis of exfoliated polymer nanocomposites made with modified GO is described. GO was modified with a surfmer (reactive surfactant), 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS), which widened the gap between the GO nanosheets and facilitated monomer intercalation between its nanogalleries. The AMPS-modified GO was used for the synthesis of poly(St-co-BA)/GO nanocomposite latices using a similar miniemulsion procedure. The obtained nanocomposites had exfoliated morphologies and the GO nanosheets were largely exfoliated (about 2–5 nm thick) in the resultant films obtained from the synthesized nanocomposite latices. The synthesized nanocomposites had enhanced thermal and mechanical properties compared to pure polymer as a result of the presence of AMPSmodified GO. Furthermore, the nanocomposites made with AMPS-modified GO had better thermal and mechanical properties than the unmodified GO. The mechanical properties of the nanocomposites depended on the AMPS-modified GO loading in the nanocomposites. The synthesis of polystyrene/GO (PS-GO) nanocomposites using the reversible additionfragmentation chain transfer (RAFT) mediated polymerization method is also described. The GO was synthesized and immobilized with a RAFT agent to afford RAFT-functionalized GO nanosheets. The RAFT-immobilized GO was used for the synthesis of PS nanocomposites in a controlled manner using miniemulsion polymerization. The molar mass and dispersity of the PS in the nanocomposites depended on the amount of RAFT-grafted GO in the system, in accordance with the features of the RAFT-mediated polymerization. X-ray diffraction and transmission electron microscopy analyses revealed that the nanocomposites had exfoliated morphology, even at relatively high GO content. The thermal stability and mechanical properties of the PS-GO nanocomposites were better than those of the neat PS polymer. Furthermore, the mechanical properties were dependent on the modified-GO content (i.e., the amount of RAFT-grafted GO). The hydrophobicity and barrier properties of the resulting films prepared from the synthesized poly(St-co-BA)/GO nanocomposite latices to water and water vapor were also investigated. The hydrophobicity of the synthesized nanocomposite films was determined using contact angle measurements. The water permeability was determined by measuring the moisture vapor transmission rate of the films. The GO in the nanocomposites was reduced to its original form (i.e., graphite), and the barrier properties of the obtained nanocomposite films were determined and compared to films containing the unmodified GO (as-prepared GO). Results showed that reduction of GO had a significant impact on the water affinity of the resultant films prepared from the synthesized nanocomposite latices. The presence of reduced-GO (RGO) instead of unmodified GO in the miniemulsion formulation significantly improved the hydrophobicity and barrier properties of the final films to water. However, the barrier properties of the nanocomposites were unaffected by the amount of RGO in the nanocomposites.<br>AFRIKAANSE OPSOMMING: Nuwe metodes is beskryf vir die sintese van polimeer/grafiet nanosamestellings deur gebruik te maak van die miniemulsie polimerisasieproses. Natuurlike grafiet is gefunksionaliseer dmv oksidasie om grafietoksied (GO) nanovelle te vorm. Polistireen-ko-butielakrilaat (poli[St-ko- BA]) nanosamestellinglatekse wat GO nanovelle bevat is suksesvol gesintetiseer deur gebruik te maak van miniemulsie polimerisasie as ‘n een-stap nano-insluitingstegniek. Die benadering wat gevolg is het die uitbreiding van die GO nanovelle, in situ, gedurende die miniemulsifiseringstap behels, gevolg deur die polimerisasie van die monomere in die teenwoordigheid van hierdie uitgebreide nanovelle. Stireen (St) en butielakrilaat (BA) is met GO gemeng en daarna emulgeer in die teenwoordigheid van ‘n seepmiddel (surfactant) en ‘n hidrofoob om pre-miniemulsielateksdeeltjies te lewer. Die stabiele pre-miniemulsies is gepolimeriseer om poli(St-ko-BA)/GO nanosamestellinglatekse te vorm. Die polimerisasie het met redelike hoë monomeeromskakeling verloop en het stabiele nanosamestellinglateksdeeltjies gelewer. Hierdie nanosamestellings het hoofsaaklik geïnterkaleerde morfologie, onafhanklik van die persentasie GO vullers, getoon. Die sintese van afgeskilferde polimeernanosamestellings berei met gewysigde GO is beskryf. GO is gewysig met ‘n ‘surfmer’ (reaktiewe seepmiddel), 2-akrielamido-2-metiel-1- propaansulfoonsuur (AMPS), wat die gapings tussen die GO nanovelle vergroot het en die monomeer interkalering tusssen sy nanogange fasiliteer. Die AMPS-gewysigde GO is gebruik vir die sintese van poli(St-ko-BA)/GO nanosamestellinglatekse deur gebruik te maak van ‘n soortgelyke miniemulsie prosedure. Die nanosamestelling sό verkry het ‘n afgeskilferde morfologie getoon en die GO nanovelle was grootendeels afgeskilfer (ongeveer 2–5 nm dik) in die films wat berei is van die gesintetiseerde nanosamestellinglatekse. Laasgenoemde het verhoogde termiese en meganiese eienskappe gehad in vergelyking met die suiwer polimeer, as gevolg van die teenwoordigheid van die AMPS-gewysigde-GO. Die meganiese eienskappe van die nanosamestellings hang af van persentasie AMPS-gewysigde GO vullers in die nanosamestellings. Die sintese van PSt/GO nanosamestellings dmv die omkeerbare-addisie-fragmentasieoordrag- (OAFO-, Eng. RAFT-) bemiddelde polimerisasie metode is ook beskryf. Die GO is berei en geïmmobiliseer met ‘n RAFT verbinding om GO nanovelle met RAFT funksionaliteit te lewer. Die RAFT-geïmmobiliseerde GO is gebruik vir die sintese van PSt nanosamestellings in ‘n gekontrolleerde manier mbv miniemulsie polimerisasie. Die molêre massa en dispersie van die PSt in die nanosamestellings hang af van die hoeveelheid RAFTgeënte GO in die sisteem, in ooreenstmming met die kenmerke van RAFT-bemiddelde polimerisasie. X-straaldiffraksie en transmissie-elektronmikroskopie analises het bewys dat die nanosamestellings, selfs by relatiewe hoë GO inhoud, ‘n afgeskilferde morfologie gehad het. Die termiese stabiliteit en meganiese eienskappe van die PSt-GO nanosamestellings was beter as dié van die suiwer PSt polimeer. Verder was die meganiese eienskappe afhanklik van die gewysigde-GO-inhoud (dws, die hoeveelheid RAFT-geënte-GO). Die hidrofobisiteit en spereienskappe van die films berei vanaf die gesintetiseerde poli(St-ko- BA)/GO nanosamestellinglatekse teenoor water en waterdamp is ook ondersoek. Die hidrofobisiteit is ondersoek deur gebruik te maak van kontakhoekmeting. Die waterdeurlaatbaarheid is bepaal deur die waterdampoordragtempo van die films te bepaal. Die GO in die nanosamestellings is gereduseer tot sy eenvoudigste vorm (grafiet) en die spereienskappe van die nanosamestellingfilms is bepaal en vergelyk met die films wat die ongewysigde GO bevat het. Resultate het getoon dat reduksie van GO ‘n groot invloed gehad het op die wateraffiniteit van die films wat berei is vanaf die gesintetiseerde nanosamestellinglatekse. Die teenwoordigheid van die gereduseerde-GO (RGO) in plaas van die onveranderde GO in die miniemulsie formulasie het die hidrofobisiteit en spereienskappe van die finale films, teenoor water, baie verbeter. Die spereienskappe van die nanosamestellings is egter nie beïnvloed deur die hoeveelheid RGO in die nanosamestellings nie.

Thesis (PhD)--Stellenbosch University, 2011.<br>ENGLISH ABSTRACT: Fully exfoliated polystyrene-clay nanocomposites were prepared via free radical polymerization in dispersion polymerization, in a mixture of ethanol and water. Sodium montomorillonite clay (MMT) was pre-modified using 3-(trimethoxysilyl) propyl methacrylate (MPTMS) before being used in a dispersion polymerization process. The particles obtained were not completely stable and TEM images showed that most of the clay platelets were distributed in the dispersing phase. A second objective included, the preparation of low molecular weight of polystyrene (PS) and amphiphilic block copolymers of poly(styrene-b-2-hydroxyethyl acrylate) (PS-b-PHEA)using reverse iodine transfer polymerization (RITP) living/controlled free radical polymerization.The reaction kinetic profile of the RITP process for styrene and 2-Hydroxyethyl acrylate (HEA) was also studied. The formation of the block copolymer PS-b-PHEA was confirmed by GPC and gradient HPLC. The resulting PS-I and (PS-b-PHEA)-I were chemically modified by dimethylethylamine and triethylamine respectively, ended with PS and PS-b-PHEA has quaternary ammonium end-chain functionality (PS-cationic and (PS-b-PHEA)-cationic). The obtained functional polymers (PS-cationic) and (PS-b-PHEA)-cationic) were then grafted onto MMT via a simple ion-exchange process to offer MMT with polymer chains on the surface (PS-MMT) and (PS-b-PHEA)-MMT). Furthermore, the ability of the interaction ofPS-b-PHEA with MMT by adsorption via several functional groups was also investigated. The third objectiveincluded the use of this new class of pre-modified clay PS-MMT in the preparation of PCNs as stabilizers, the clay particles were encapsulated into PS latexes with a partially exfoliated structure at 100% CEC, upon stoppage of the polymerization process, and the final dispersion found to be stable for up to 5 wt% of clay filler loading. The thermal and thermo-mechanical properties of PS-nanocomposites were found to be dependent on both nanocomposites morphology, and clay loading. (PS-b-PHEA)-MMT was also used as stabilizers in the preparation of PS via dispersion polymerization. PS colloidal particles obtained were found to be armoured by (PS-b-PHEA)-MMT layers, with particles sizes in the micro-size range, with fair stability were obtained for clay loadings up to 5%. Analysis of the structure and thermo-mechanical properties of the resulting PCNs revealed the efficiency of the clay surface pre-modification in stabilizing the system throughout the heterophasic polymerization process.The melt flow properties of final PCNs were found to be strongly dependent on the clay loading, with shift observed from liquid-like viscoelastic to solid-like viscoelastic behaviour as the clay content increased due to percolation of the clay network within the PS matrix taking place upon film formation above Tg.<br>AFRIKAANSE OPSOMMING: Die eerste doelwit was die voorbereiding van ten volle geëksfolieerde polistireen-klei nanosamestellings deur vrye radikaal polimerisasie in dispersie-polimerisasie, in 'n mengsel van etanol en water. Natrium montmorilloniet klei (MMT) is gemodifiseer deur gebruik te maak van 3-(trimetoksiesiliel) propiel metakrilaat (MPTMS), voordat dit gebruik is in die dispersie-polimerisasie. Die bekomde partikels was nie heeltemal stabiel nie. Transmissie elektronmikroskopie (TEM) resultate het getoon dat die meeste van die klei plaatjies in die dispersie-fase versprei is. Die tweede doelwit was die voorbereiding van polistireen (PS) met 'n lae molekulêre massa, gevolg deur die vorming van amfifiliese blok kopolimere van poli(stireen-b-2-hidroksie-etiel akrilaat) (PS-b-PHEA) met behulp van omgekeerde jodium oordrag polimerisasie (RITP) lewendige/gekontroleerde vrye radikaal polimerisasie. Die reaksie kinetiese profiel van die RITP proses was bestudeer met betrekking tot stireen en 2-hidroksie-etiel akrilaat (HEA). Die vorming van die blok kopolimeer PS-b-PHEA is bevestig deur GPC en gradiënt HPLC. Die gevolglike PS-I en (PS-b-PHEA)-I was chemies gewysig deur onderskeidelik dimetieletielamien en trietielamien, waardeur PS en PS-b-PHEA een kwaternêre ammonium ketting-endfunksionaliteit bekom het (PS-kationies en (PS-b- PHEA)-kationies). Laasgenoemde twee funksionele polimere was toe gekoppel aan MMT deur 'n eenvoudige ioon-ruilingsproses wat MMT met polimeerkettings op die oppervlak (PS-MMT) en (PS-b-PHEA)-MMT) tot gevolg het. Die interaksie van PS-b-PHEA met MMT deur middel van adsorpsie van verskeie funksionele groepe is ook ondersoek. Die derde doel was gerig op die gebruik van hierdie nuwe klas gemodifiseerde klei PS-MMT as stabiliseerders vir die voorbereiding van polimeer-klei-nanosamestellings (PCNs). Die 100% CEC gemodifiseerde klei deeltjies is ge-inkapsuleer in die PS emulsies met 'n gedeeltelik geëksfolieërde struktuur, na afloop van die polimerisasie proses. Die finale dispersie was stabiel tot en met 'n klei inhoud van 5 wt%. Daar is gevind dat die termiese en termo-meganiese eienskappevan die PS-nanosamestellings afhanklik is van beide die morfologie en die klei inhoud. (PS-b-PHEA)-MMT was ook gebruik as stabiliseerder in die voorbereiding van PS deur dispersie polimerisasie. Daar is gevind dat die PS kolloïdale partikels wat verkry is, versterk was deur (PS-b-PHEA)-MMT lae. Partikel groottes was in die mikro-grootte gebied, en voldoende stabiliteit is verkry vir 'n klei inhoud van tot 5%. Analise van die struktuur en die termo-meganiese eienskappe van die bekomde PCNs het getoon dat die vooraf modifisering van die klei oppervlak doeltreffend was in die stabilisering van die sisteem gedurende die heterofase polimerisasie proses. Daar is ook gevind dat die smelt vloei eienskappe van die finale PCNs sterk afhang van die klei inhoud; 'n verskuiwing vanaf vloeistof-agtige viskoelastiese tot vaste-agtige viskoelastiese gedrag is waargeneem soos die klei-inhoud verhoog. Hierdie verskynsel was te danke aan perkolasie van die klei netwerk binne die PS matriks wat plaasvind tydens film vorming by 'n hoër temperatuur as die glasoorgangstemperatuur (Tg).

The intrinsic relationships between polymer structure, composition and fire behavior have been explored to develop new fire-safe polymeric materials. Different experimental techniques, especially three milligram-scale methods—pyrolysis-combustion flow calorimetry (PCFC), simultaneous thermal analysis (STA) and pyrolysis GC/MS—have been combined to fully characterize the thermal decomposition and flammability of polymers and polymer composites. Thermal stability, mass loss rate, char yield and properties of decomposition volatiles were found to be the most important parameters in determining polymer flammability. Most polymers decompose by either an unzipping or a random chain scission mechanism with an endothermic decomposition of 100–900 J/g. Aromatic or heteroaromatic rings, conjugated double or triple bonds and heteroatoms such as halogens, N, O, S, P and Si are the basic structural units for fire-resistant polymers. The flammability of polymers can also be successfully estimated by combining pyrolysis GC/MS results or chemical structures with TGA results. The thermal decomposition and flammability of two groups of inherently fire-resistant polymers—poly(hydroxyamide) (PHA) and its derivatives, and bisphenol C (BPC II) polyarylates—have been systematically studied. PHA and most of its derivatives have extremely low heat release rates and very high char yields upon combustion. PHA and its halogen derivatives can completely cyclize into quasi-polybenzoxazole (PBO) structures at low temperatures. However, the methoxy and phosphate derivatives show a very different behavior during decomposition and combustion. Molecular modeling shows that the formation of an enol intermediate is the rate-determining step in the thermal cyclization of PHA. BPC II-polyarylate is another extremely flame-resistant polymer. It can be used as an efficient flame-retardant agent in copolymers and blends. From PCFC results, the total heat of combustion of these copolymers or blends changes linearly with composition, but the change of maximum heat release rates also depends on the chemical structure of the components. The flammability of various polymers and polymer composites measured by PCFC, cone calorimeter ASTM E1354 and Ohio State University (OSU) calorimeter ASTM E906 were also compared. For pure polymers, there is a relatively good correlation between different methods. However, for polymer composites with inert fillers or flame-retardant additives, OSU and cone calorimetries are more suitable evaluation methods.

This thesis investigates the physics of various polymeric systems via the tool of computer simulation. The problems addressed include the tunable conformations of dendritic polyelectrolytes, the complexation of oppositely charged linear polyelectrolytes to charged dendrimers, the molecular mechanisms of polymer crystallization, and the retractive response of polymers perturbed from their equilibrium conformations. The algorithms employed include both equilibrium Metropolis Monte Carlo and Brownian dynamics methods. The computational investigations are augmented by scaling and variational theory treatments. The results of these studies complement experimental ventures in the respective fields and provide new insight into the limitations of existing theoretical descriptions.* *This dissertation is a compound document (contains both a paper copy and a CD as part of the dissertation).

Interfacial cracks in bimaterial and sandwich specimens in 4-point flexure were analyzed using the finite element method. The energy release rate(G) and the loading phase angle($\Psi$)were calculated in a variety of bimaterial and sandwich specimens. In the sandwich specimens, different crack configurations were analyzed. For sandwich specimens with fully formed cracks on both interface #s 1 and 2, the analysis predicted crack arrest on interface #1 and growth on interface #2. This phenomenon was observed in previous studies with glass/epoxy/glass sandwich specimens. The analysis also showed that the G value for the crack on interface #2 can be calculated by multiplying the G value for a crack on interface #1 by an appropriate correction factor. This correction factor depends on whether the precrack penetrated the epoxy layer or was arrested at interface #1. The loading phase angle for the crack on interface #2 was found to be greater when the precrack penetrated the intermediate layer than when it was arrested at interface #1. Subcritical crack growth and fracture energy(G$\sb{\rm c})$ measurements were made on glass/PMMA and glass/epoxy/PMMA specimens under high humidity. Threshold values for subcritical crack growth and G,values were lowest for the glass/PMMA interface and highest for the epoxy/PMMA interface with the precrack penetrating the epoxy layer. The Van der Waals bonds between glass and PMMA appear to be weaker than those between epoxy and PMMA. For a crack at the epoxy/PMMA interface in the glass/epoxy/PMMA sandwich specimen, threshold values for subcritical crack growth and G$\sb{\rm c}$ values were lower when the precrack was arrestedon interface #1 than when it penetrated the epoxy layer. The lower phase angle ($\Psi = 5\sp\circ)$ for the crack on interface #2 with the precrack arrested at interface #1 results in a large opening mode stress state on interface #2 which facilitates subcritical crack growth at lower threshold values and also lower G$\sb{\rm c}$ values as compared to the case when the precrack penetrates the epoxy layer and grows along interface #2($\Psi = 66\sp\circ).$

The research presented in this dissertation focuses on the design and synthesis of novel hybrid conjugated polymer materials using two different approaches: (1) inorganic/organic hybrid semiconductors through the incorporation of carboranes into the polymer structure and (2) the modification of surfaces with conjugated polymers via grafting approaches. Hybrid conjugated polymeric materials, which are materials or systems in which conjugated polymers are chemically integrated with non-traditional structures or surfaces, have the potential to harness useful properties from both components of the material to help overcome hurdles in their practical realization in polymer-based devices. This work is centered around the synthetic challenges of creating new hybrid conjugated systems and their potential for advancing the field of polymer-based electronics through both greater understanding of the behavior of hybrid systems, and access to improved performance and new applications. Chapter 1 highlights the potential applications and advantages for these hybrid systems, and provides some historical perspective, along with relevant background materials, to illustrate the rationale behind this work. Chapter 2 explores the synthesis of poly(fluorene)s with pendant carborane cages. The Ni(0) dehalogenative polymerization of a dibromofluorene with pendant carborane cages tethered to the bridging 9-position produced hybrid polymers produced polymers which combined the useful emissive characteristics of poly(fluorene) with the thermal and chemical stability of carborane cages. The materials were found to display increased glass transition temperatures and showed improved emission color stability after annealing at high temperatures relative to the non-hybrid polymer. The design and synthesis of a poly(fluorene)-based hybrid material with carborane cages in the backbone, rather than as pendant groups, begins in chapter 3. Poly(fluorene) with p-carborane in the backbone is synthesized and characterized, and the material is found to be a high MW, soluble blue emitter which shows a higher glass transition temperature and greater stability than a non-hybrid polymer. UV absorbance and fluorescence spectroscopy indicated some electronic interaction between the conjugated polymer and the cages, but they did not appear to be fully conjugated in the traditional sense. Chapter 4 describes the design, synthesis, and characterization of poly(fluorene) with o-carborane in the backbone. Profound changes in the behavior of the polymer, from its polymerization behavior to its emission characteristics, were observed and their origins are discussed. Experiments to explore the nature of the cage/polymer interactions were performed and possible applications which take advantage of the unique nature of the o-carborane hybrid polymer are explored and discussed. Hybrid conjugated polymer materials via grafting approaches to surfaces and surface modification are discussed starting in chapter 5. The synthesis of a dibromofluorene-based silane coupling agent for the surface functionalization of oxide surfaces is presented, and the surface directed Ni(0) dehalogenative polymerization of poly(dihexylfluorene) is explored. Chapter 6 focuses on the exploration of conjugated polymer/cellulose hybrid materials. Surface medication of cellulose materials with monomer-like anchor points is discussed. Grafting of the modified cellulose with conjugated polymers was explored and the grafting of three different repeat structures based on fluorene-, fluorenevinylene-, and fluoreneethynylene motifs were optimized to provide a general route to cellulose/conjugated polymer hybrid materials. Characterization and possible applications of such hybrid materials are discussed. Finally, chapter 7 is devoted to the simultaneous surface patterning and functionalization of poly(2-hydroxyethylmethacrylate) thin films using a silane infusion-based wrinkling technique. While not a conjugated polymer system, the spontaneous patterning and functionalization methods explored in this chapter produce hybrid organic/inorganic polymer thin films which have applications that range from optics, to adhesion, to polymer-based electronics, and the research compliments the other chapters. The spontaneous generation of complex patterns, of a small scale approaching 100nm feature size, over a large area with simultaneous control over surface chemistry is explored. Examples of complex, hierarchically patterned films which integrate lithographic processes such as nanoimprint lithography and electron beam lithography with spontaneous patterning via wrinkling are presented.

In this dissertation we report new theoretical results—both analytical and numerical—concerning a variety of polymeric systems. Applying path-integral and differentiable manifolds techniques, we have obtained original results concerning the statistics of a Gaussian polymer embedded on a sphere, a cylinder, a cone and a torus. Generally, we found that the curvature of the surfaces induces a geometrical localization area. Next we employ field theoretical (instanton calculus) and differential equations techniques (Darboux method) to obtain approximate and exact new results regarding the average size and the Green function of a Gaussian, one-dimensional polymer chain subjected to a multi-stable potential (the tunnel effect in polymer physics). Extending the multiple scattering formalism, we have investigated the steady-state dynamics of suspensions of spheres and Gaussian polymer chains without excluded volume interactions. We have calculated the self-diffusion and friction coefficients for probe objects (sphere and polymer chain) and the shear viscosity of the suspensions. At certain values of the concentration of the ambient medium, motion of probe objects freezes. Deviation from the Stokes-Einstein behavior is observed and interpreted. Next, we have calculated the diffusion coefficient and the change in the viscosity of a dilute solution of freely translating and rotating diblock, Gaussian copolymers. Regimes that lead to increasing the efficiency of separation processes have been identified. The parallel between Navier-Stokes and Lamé equations was exploited to extend the effective medium formalism to the computation of the effective shear and Young moduli and the Poisson ratio of a composite material containing rigid, monodispersed, penetrable spheres. Our approach deals efficiently with the high concentration regime of inclusions.

This dissertation describes research performed using siloxane polymers. This includes the reactions of siloxane polymers with inorganic oxide surfaces to form covalently attached monolayers, and the electrical properties of crosslinked silicone composite films fabricated by compounding with nickel particles. In addition to these topics, the use of contact line pinning as a practical and controllable method for the deposition of materials on superhydrophobic and chemically patterned surfaces is also described. The first chapter provides a general review of siloxane polymer chemistry, focusing in particular on the relationship between molecular structure and physical properties. The use and fabrication of silicone composite materials is also discussed, including typical methods for crosslinking siloxane polymers and the effects of filler materials. Finally, contact angle hysteresis and contact line pinning phenomena are presented. Following this introduction, four separate but interrelated projects are presented. First, the surface modification of titania via hydridomethylsiloxanes is discussed. This work represents an extension of the reaction of hydridosilanes and provides an environmentally clean method for the hydrophobization of titania. Linear and cyclic hydridomethylsiloxanes, as well as hydridomethylsiloxane-co-dimethylsiloxane polymers, are used as reagents and the resulting surfaces are discussed. Unpredicted results from this method lead to the consideration of poly(dimethylsiloxane) as a previously unconsidered reagent presented in the next project. The second project discusses the covalent attachment of siloxane polymers, particularly poly(dimethylsiloxane), to a range of inorganic oxide surfaces, including titania, nickel oxide, alumina, and silica. This reaction is presented as a thermally activated equilibrium process, and offers insight into certain aging processes found in silicone materials. Particular focus is made on the development of a highly reproducible method for the fabrication of low contact angle hysteresis surfaces. Furthermore, this reaction is shown to be general for the siloxane bond through the reaction of functional and cyclic siloxanes. The third project describes the preparation of electrically conductive silicone coatings, containing nickel and titania particles. The effect of nickel concentration and geometry on the electrical properties of these coatings is examined and the effects on the percolation threshold are presented. In addition to this, the addition of titania nanoparticles to diminish electrical conductance is also investigated. The fourth project discusses the contact line pinning of liquids on hydrophobic surfaces. In this chapter, the use of ionic liquids exhibiting no vapor pressure is used to experimentally determine the de-wetting process of liquids from pillared, superhydrophobic surfaces through micro-capillary bridge rupture. Furthermore, this technique is used as a preparative technique for the fabrication of individual salt crystals supported on pillared surfaces.

Geometrically hindered motions of a single large solute (particle or polymer) can be imaged in real time via optical microscopy. The dynamics of fluorescent colloidal particles near surfaces and in porous membranes were monitored using confocal microscopy. A method of analysis to estimate diffusivity of particles in the axial direction by observing their intensity fluctuations was developed. The intensity fluctuations correspond to the Brownian motion of the particles in the axial direction. The method was successful in capturing the hindered diffusion of particles close to surfaces and in pores. This study provides a novel route to monitor the dynamics of particles, including biomacromolecules, near surfaces, through porous substrates and biological tissues. Ionic liquid (IL) as a medium for room temperature preservation of biomacromolecules has been proposed and, to investigate the possibility, physicochemical and enzymatic properties of proteins in the neat hydrophilic IL, ethylmethyl imidazolium ethyl sulfate [EMIM][EtSO4] were studied. Spectroscopic techniques were employed to probe the secondary and tertiary structure of proteins whereas light scattering and viscometry were used to estimate the hydrodynamic size. The secondary structure of the protein was retained in the ionic liquid but the tertiary structure was found to change. Alterations in protein conformation/activity were investigated after transfer of the dissolved protein from the IL to buffer. Further, suitability of ionic liquid gels as protein encapsulation and preservation media was assessed.