Thesis (PhD)--Stellenbosch University, 2003. / ENGLISH ABSTRACT: The synthesis of structured nanoparticles, in particular core/shells, IS of great technological and economical importance to modem materials science. One of the advantages of structured particles is that they can be synthesized with either a solid core (albeit soft or hard) or a liquid core (of varying viscosity). This adds to the versatility of structured particles and their relevance to a majority of industrial and commercial endapplications. The synthesis of core/shell particles with liquid cores was investigated for the effective impact modification of glassy amorphous polymers. Polybutyl acrylate was chosen as the shell due to its rubbery nature. Hexadecane functioned as the core oil and facilitated osmotic stability by being a suitable hydrophobe for the miniemulsion synthesis. Polymer synthesis was preceded by the prediction of particle morphology by using thermodynamic prediction models. Core/shell particles with liquid cores were synthesized via miniemulsion polymerization. This resulted in the direct introduction of core-oil and monomer into the miniemulsion droplets. Polymerization was achieved in situ, resulting in the formation of particles with the desired morphology. For additional strength, stability and matrix mixing capabilities, methyl methacrylate (MMA) was grafted onto the initial core/shell particles. The obtained morphology was in contradiction with the predicted morphology, thus pointing to strong kinetic influences during the polymerization process. These influences could be attributed to surface anchoring of polymer chains due to the initiator (KPS) used, the establishment of the polymerization locus as well as the increase in viscosity at the polymerization locus. To test these influences a surface-inactive initiating species (AIBN) and an interfacial redox initiating species (cumyl hydroperoxide/Fe/") were used. Use of the former resulted in the formation of solid polymer particles due to homogeneous polymerization throughout the droplet, thus leading to an inverse core/shell morphology as a result of thermodynamic considerations. The redox initiator promoted kinetic influences as a result of fast polymerization kinetics at the droplet/water interface. This, as well as the increase in viscosity, facilitated the production of core/shell particles. To obtain core/shell particles with the desired size, the influence of surfactant concentration was investigated. Capillary hydrodynamic fractionation (CHDF) was used to determine the particle size of the initial core/shell particles as well as the size of the MMA-grafted core/shell particles. The area stabilized per surfactant molecule was calculated stoichiometrically and compared to "classical" miniemulsion results, i.e. data generated from the synthesis of polymeric latexes in the presence of a hydrophobe, but at a much lower hydrophobe:monomer ratio than was used here. The influence of methanol as well as the possibility of scaling-up the process was also investigated. The study was further expanded to the investigation of living miniemulsion polymerization techniques to control the molecular architecture of synthesized core/shell latexes. The influence of different RAFT agents, initiators and monomers were investigated on the core/shell formation properties of the investigated systems. The combined effects of establishing the polymerization locus as well as increased polymerization kinetics, thus increasing the viscosity at the polymerization locus, lead to the successful formation of liquid- filled core/shell particles. To conclude, the ability of the synthesized core/shell particles to induce impact modification in glassy amorphous polymers was investigated. Results showed that incorporation of these particles could effectively modify the intrinsic properties of the investigated polymers, resulting in a brittle-to-ductile transition. Improved impact results of the investigated glassy matrix were obtained. Keywords: core/shell, liquid-filled, RAFT, miniemulsion, impact modification / AFRIKAANSE OPSOMMING: Die sintese van gestruktureerde nano-partikels, meer spesifiek kern/skil partikels, is van onskatbare tegnologiese en ekonomiese belang vir moderne materiaalkunde. Een van die voordele van hierdie tipe partikels is dat sintese kan geskied met 'n soliede kern (hard of sag) of vloeistofkern (met wisselende viskositeit). Dit dra by tot die veelsydigheid van gestruktureerde partikels en dus tot grootskaalse aanwending in industriële en kommersiële toepassings. Die sintese van kern/skiI partikels met vloeistofkerne is ondersoek met die oog op effektiewe slagsterkte modifikasie van glasagtige amorfe polimere. Polibutielakrilaat is gekies as skil-polimeer op grond van sy rubberige voorkoms. Heksadekaan moes funksioneer as die kern-olie, maar het ook bykomende osmotiese stabiliteit verleen tydens die miniemulsie-polimerisasie proses. Dit is as gevolg van die gepaste hidrofobiese eienskappe van heksadekaan. Polimeer sintese is voorafgegaan deur die voorspelling van partikel morfologie met behulp van termodinamies gebaseerde voorspellingsmodelle. Kern/skil partikels is gesintetiseer deur middel van 'n miniemulsie-polimerisasie reaksie wat die direkte inkorporering van kern-olie en monomeer in die miniemulsiedruppel teweeg bring. Polimerisasie vind in situ (lat. vir in die oorspronklike plek, m.a.w. binne-in die druppel) plaas en lei tot die vorming van partikels met die gewenste morfologie. Metielmetakrilaat is ge-ent op die oorspronklike kern/skil partikels om addisionele sterkte, stabiliteit en vermenging met die matriks polimeer te bewerkstellig. Die verkrygde morfologie is teenstrydig met die voorspelde morfologie, wat dus die teenwoordigheid van sterk kinetiese invloede aandui. Hierdie invloede kan toegeskryf word aan die oppervlak-aktiewe afsetter (KPS, kaliumpersulfaat) wat gebruik is, die daarstelling van die polimerisasie lokus asook die toename in viskositeit by die lokus van polimerisasie. Om hierdie invloede te toets is 'n oppervlak-onaktiewe afsetter (AIBN, asobisisobutironitriel) en intervlak redoks-afsetter (kumielhidroperoksied/Pe'") gebruik. Gebruik van eersgenoemde het die vorming van soliede partikels teweeg gebring. Dit is as gevolg van homogene polimerisasie in die druppel en dus die ontstaan van omgekeerde kern/skiI partikels weens termodinamiese oorwegings. Die redoks-afsetter het egter die kinetiese oorwegings bevoordeel as gevolg van vinnige polimerisasiekinetika by die druppel/water intervlak. Dit, tesame met die toename in viskositeit, maak die produksie van kern/skil partikels moontlik. Vir die verkryging van kern/skiI partikels met die gewenste partikelgrootte is die invloed van die seep konsentrasie ondersoek. CHDF (eng. capillary hydrodynamic fractionation) is gebruik om die partikelgrootte van die oorspronklike kern/skiI partikels, sowel as dié ge-ent met metielmetakrilaat, te bepaal. Die area gestabiliseer per seepmolekule is bereken d.m.v. stoichiometrie en vergelyk met "klassieke" miniemuisie data, d.i. data verkry deur die sintese van latekse in die teenwoordigheid van 'n hidrofoob, maar teen 'n baie laer hidrofoob:monomeer-verhouding as wat hier gebruik is. Die invloed van metanol, asook die moontlikheid om die reaksie op te skaal, is ondersoek. Die studie is verder uitgebrei om die invloed van lewende miniemulsie-polimerisasie tegnieke in te sluit, om sodoende beheer uit te oefen oor die molekulêre argitektuur van die gesintetiseerde latekse. Die invloed van verskeie RAFT (eng. reversible additionfragmentation chain transfer) agente, afsetters en monomere op die kern/skiI vormingsmoontlikhede van die bestudeerde stelsels, is ondersoek. Die gesamentlike effek van die daarstelling van die polimerisasie lokus en dus die verhoging van die viskositeit by die lokus, lei tot die suksesvolle vorming van vloeistof-gevulde kern/skiI partikels. Laastens is die invloed van die gesintetiseerde kern/skil partikels op die slagsterkte van glasagtige amorfe polimere ondersoek. Resultate dui daarop dat die insluiting van hierdie partikels kan lei tot die effektiewe verandering van die intrinsieke eienskappe van die bestudeerde polimere, en dus 'n oorgang van bros na rekbaar kan veroorsaak. 'n Verbetering in die slagsterkte resultate van die bestudeerde glasagtigte matriks is ook waargeneem.

The effects of melt state compounding and addition order of ethylene-butyl acrylate-maleic anhydride (E-BA-MAH), ethylene-glycidyl methacrylate (E-GMA), ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA) terpolymer and/or three types of organoclays (Cloisite&reg / 15A, 25A and 30B) on morphology, thermal, mechanical and dynamic mechanical properties of polyamide-6 are investigated. XRD patterns show that the interlayer spacing for Cloisite&reg / 15A remained unchanged / however it increased for the organoclays Cloisite&reg / 25A and Cloisite&reg / 30B in both polyamide-6/organoclay binary nanocomposites and in polyamide-6/organoclay/impact modifier ternary systems. TEM analyses indicate that exfoliated-intercalated nanocomposites are formed. Sizes of elastomeric domains in nanocomposites are larger than the domains in their corresponding blends. The MFI results show that incorporation of elastomer reduces the MFI, due to the formation of graft copolymer. Both storage and loss moduli and complex viscosity of polyamide-6 increase with organoclay addition. In DMA measurements, in rubbery region, all nanocomposites show higher storage modulus than the unfilled counterparts. In general, the organoclays increase tensile and flexural strength, Young&amp / #8217 / s and flexural modulus and elongation at break, but decrease the impact strength, on the contrary, the addition of elastomer has the opposite effect. Generally, Cloisite&reg / 15A containing ternary nanocomposites have higher tensile, flexural and impact strength and Young&amp / #8217 / s and flexural modulus than the ternary nanocomposites prepared with Cloisite&reg / 25A and Cloisite&reg / 30B. In general, nanocomposites processed by adding all the ingredients simultaneously give higher tensile and flexural strength and modulus than the nanocomposites produced by other mixing sequences.

This study was conducted to investigate the effects of component concentrations and addition order of the components, on the final properties of ternary nanocomposites composed of poly(ethylene terephthalate), organoclay, and an ethylene/methyl acrylate/glycidyl methacrylate (E-MA-GMA) terpolymer acting as an impact modifier for PET. In this context, first, the optimum amount of the impact modifier was determined by melt compounding binary PET-terpolymer blends in a corotating twin-screw extruder. The amount of the impact modifier (5 wt. %) resulting in the highest Young&rsquo / s modulus and reasonable elongation at break was selected owing to its balanced mechanical properties. Thereafter, by using 5 wt. % terpolymer content, the effects of organically modified clay concentration and addition order of the components on ternary nanocomposites were systematically investigated. Mechanical testing revealed that different addition orders of the materials significantly affected mechanical properties. Among the investigated addition orders, the best sequence of component addition (PI-C) was the one in which poly(ethylene terephthalate) was first compounded with E-MA-GMA. Later, this mixture was compounded with the organoclay in the subsequent run. Young&#039 / s modulus of not extruded pure PET increased by 67% in samples with 5 wt. % E-MA-GMA plus 5 wt. % clay loading. The highest percent elongation at break was obtained as 300%, for the addition order of PI-C, with 1 wt. % clay content, which is nearly 50 fold higher than that obtained for pure PET. In X-ray diffraction analysis, extensive layer separation associated with delamination of the original clay structure occurred in PI-C and CI-P sequences with both 1 and 3 wt. % clay contents. X-ray diffraction patterns showed that, at these conditions exfoliated structures resulted as indicated by the disappearence of any peaks due to the diffraction within the consecutive clay layers.

Polymeric composites are any of the combinations or compositions that comprise two or more materials as separate phases, at least one of which is a polymer. By mixing a polymer with another material, such as glass, carbon, or another polymer, it is often possible to improve the desired properties of the polymer. In this study, ternary composites were prepared by using recycled poly(ethylene terephthalate), PET as the matrix material, short glass fiber (SGF) as the reinforcing filler and thermoplastic elastomer as the impact modifier. Bottle grade recycled PET was mixed in a twin screw extruder with a thermoplastic elastomer which is a terpolymer of ethylene/methyl acrylate/glycidyl methacrylate (E-MA-GMA), and E type short glass fiber is fed to the extruder from a side feeder. During this study, recycled PET was mixed with from 10 to 50 wt. % elastomer, and SGF was added to the system in the range from 10 to 40 % by weight. Processing parameters were kept constant during extrusion. The composites were then compression molded for characterization experiments. The produced composites were characterized in terms of their mechanical and thermal properties and morphologies. Melt behavior and fiber length distribution of the composites were also determined for selected composites. In ternary systems with 10 % elastomer, highest tensile strength values were observed. High tensile and flexural moduli values were obtained for the composites containing 20 % elastomer. Results of impact tests designated that impact strength increased significantly after 30 % elastomer content. Thermal analyses of the composites were done by using a DSC (Differential Scanning Calorimeter). Degree of crystallinity of ternary system decreased with increasing elastomer content, but melting points of the composites were not affected significantly. SEM micrographs showed that the adhesion between the matrix and fiber increased considerably with elastomer addition.

Abstract Impact cratering is a fundamental geomorphic process on planetary surfaces. More than 60% of known hypervelocity impact craters on Earth are either partially or completely buried beneath post-impact sediments and one-third have been discovered with geophysical methods. In this thesis, geophysical surveys (gravity, magnetics, seismic, bathymetric mapping) were conducted at the deeply buried (>400 m) Holleford impact crater (~2.35 km) and two probable impact structures (Charity Shoal, Skeleton Lake) in southern Ontario, Canada. 3-D potential field models were constructed to determine the subsurface geology and buried crater morphology, and to evaluate evidence for possible impact versus endogenic origins. Holleford Crater is a deeply buried, Late Proterozoic-Early Cambrian (ca. 550 ±100 Ma) simple impact crater (~2.4 km) in southeastern Ontario, Canada. Land-based magnetic and gravity surveys and modelling were conducted in this study, recorded a ~ -3 mGal Bouguer anomaly and small (~30 nT) magnetic anomaly over the crater basin. 3-D gravity modelling revealed a deeply buried simple impact basin in Mesoproterozoic basement with an estimated rim-to-rim diameter (D) of 1.8-2 km, a residual rim height of ~20-30 m and true depth (dt) >400 m. The southeast crater rim is dissected by a 150 m deep, 400 m wide erosional channel produced by fluvial rim dissection. The outflow is infilled by >50 m of Late Cambrian clastic sediments, indicating a probable Late Proterozoic to Early Paleozoic impact event. Charity Shoal is a 1.2-km-diameter, 20 m deep, circular bedrock shoal in eastern Lake Ontario. Marine seismic profiling and total field magnetic surveys (140-line km) were conducted over a 9-km2 area and combined with available multi-beam bathymetric data to evaluate the subsurface geology and structure origin. Seismic surveys revealed ~30 m of Quaternary sediments overlying Middle Ordovician (Trenton Group) carbonates in the central basin and evidence for folding and faulting of the structure rim. Magnetic surveys recorded an annular magnetic high (> 600 nT) and a central magnetic low (~500-600 nT) coincident with a ~-1.7 mGal Bouguer gravity anomaly. The continuity of Middle Ordovician bedrock below the structure rules out a post-Paleozoic intrusion and a pre-Paleozoic intrusion is ruled out with the gravity anomaly. A deeply-buried (> 450 m) impact crater is the only scenario consistent with geophysical evidence. The crater has a rim-to-rim diameter of ~1.2 km, and rim height of ~15-20 m. A 100-m wide breach in the southwestern rim records a possible outflow channel. Skeleton Lake is a suspected (~4.0 km) Paleozoic-age impact structure in Muskoka, Ontario. The lakebed morphology, subsurface structure and possible impact origin were investigated with high-resolution geophysical surveys (magnetics, bathymetry; ~140 line-km) and 3-D magnetic modelling. Bathymetric data reveal a deep (>65 m) central basin with arcuate (Paleozoic?) bedrock ridges that rise >30 m above the southwestern lakebed. Magnetic surveys recorded a >700 nT magnetic low, which truncates northwest-southeast regional magnetic trends. Low-amplitude, northwest-trending magnetic lineaments delineate basement shear zones below the basin centre. Through-going magnetic lineaments and lack of thermal alteration (e.g., dikes, fenitization) in Mesoproterozoic rocks indicate a volcanic origin is unlikely. A 1.2 km diameter volcanic plug with an Early Cambrian remanence (D = 82.2°, I = 82.7°) can reproduce some aspects of the magnetic anomaly but is at odds with the Bouguer gravity anomaly (~ -3 mGal). Forward modelling of a crater-form basin with induction and remanence magnetization yielded an estimated structure depth of ~1200 m. The basement surface model shows a complex basement topography with no apparent rim structure and elevated ‘pinnacles’ that may represent eroded remnants of a central uplift or a highly-dissected basement topography. The structure apparent diameter (> 4.2 km) and complex basement topography suggest a heavily-modified transitional crater, similar with the Gow (Saskatchewan, Canada) and Kärdla (Estonia) impact structures. This thesis demonstrates the subsurface exploration of confirmed and suspected impact structures, integrating seismic, potential field (magnetics, gravity) and digital elevation data within a 3-D geophysical modelling workflow. The approach provides important new insights into the surface and subsurface geology, morphology, and post-emplacement modification of the Holleford impact crater, and new geophysical constraints for evaluating two suspected impact structures. Geophysical data confirm that Charity Shoal and Skeleton Lake are deep-seated, crater-form depressions in Mesoproterozoic basement rocks. The weight of geophysical and geological evidence points to impact cratering processes as opposed to an endogenic (volcanic) origin for both structures. / Thesis / Doctor of Science (PhD)