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Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: The work presented in this dissertation describes the use of coaxial electrospinning of two miscible polymer solutions in the preparation of core-shell fibres with a semicrystalline core of poly(L-lactic acid) and an amorphous shell of poly(D,L-lactic acid). Additionally it describes using these fibres in the production of single polymer composite yarns and films. These materials can potentially be used in applications that require biodegradable and fibre-reinforced composite materials e.g. suture yarns. Traditional methods, such as TEM, when used to analyse the core-shell fibre structure were not successful with the polymer system used. A method was developed to validate core-shell fibre structure by selective dissolution of the shell material and correlating analyses of the separated components using differential scanning calorimetry (DSC) and optical rotation. The effects of solution concentration and flow rate on resultant core-shell fibre diameters were investigated. Core-solution flow rate was shown to be the most significant variable affecting the core and core-shell fibre diameters. A thermal processing window exists between the glass transition temperature of the amorphous PDLLA shell material and the crystalline melting temperature of the semicrystalline PLLA core material. Heating these core-shell fibres within this processing window resulted in flow and fusion of overlapping shells of these core-shell fibres at their surfaces while the fibrous core components remained intact and reinforced the resulting composite material. This approach was used to produce single polymer composite yarns and films. Thermal treatments on yarns were shown to increase crystallinity of the cores and therefore the modulus and yield strength of the fibres when compared to untreated yarns. / AFRIKAANSE OPSOMMING: Die werk wat in hierdie tesis voorgelê word, beskryf die gebruik van koaksiale elektro-spinnery van twee wedersydsoplosbare polimeeroplossings in die vervaardiging van kern-skilvesels met ‘n gedeeltelik-kristallyne kern van poli-Lmelksuur (PLLA) en ‘n amorfe skil van poli-D,L-melksuur (PDLLA). Verder beskryf dit die gebruik van hierdie vesels in die vervaardiging van enkel-polimeer saamgestelde-materiaalgarings en -films. Hierdie materiale kan moontlik gebruik word in toepassings wat bio-afbreekbare en veselversterkte saamgestelde materiale vereis, soos byvoorbeeld chirurgiese steke. Die polimeervesels wat in hierdie studie gebruik is, kon nie gekaraktiseer word met behulp van transmissie-elektronmikroskopie (TEM), wat gewoonklik gebruik word in die bestudering van kern-skilvesels, nie. ‘n Alternatiewe karakteriseringsmetode is ontwikkel om te bevestig dat die gevormde vesels wel ‘n kern-skilstruktuur het. Hierdie metode het behels dat die skil van die kern-skilvesel selektief opgelos is, waarna beide komponente (d.i. kern en skilmateriale) bestudeer is met behulp van differensiële skanderingskalorimetrie en optiese rotasie. Die invloed van polimeeroplossingskonsentrasie en –vloeitempo op die gevormde kern-skilvesels is daarna ondersoek en die vloeitempo van die kernoplossing is geïdentifiseer as die prosesinsetwaarde wat die mees beduidende invloed het op die deursnee van die vesels. Daar bestaan ‘n temperatuurinterval tussen die glasoorgangstemperatuur van die amorfe PDLLA skilmateriaal en die kristallyne smeltpunt van die gedeeltelikkristallyne PLLA kernmateriaal. Verwerking van die kern-skilvesels by ‘n temperatuur binne hierdie interval het gelei tot vervloeiing en samesmelting van die oorvleuelende skille van die kern-skilvesels, terwyl die veselagtige kernkomponente van die vesels heel gebly het en opgetree het as versterking binne-in die saamgestelde materiaal wat gevorm het. Hierdie benadering is gebruik om enkelpolimeersaamgestelde- materiaalgarings en –films te vervaardig. ‘n Vergelykende studie tussen onbehandelde en hitte-behandelde enkel-polimeer-saamgesteldemateriaalgarings het aangetoon dat die hittebehandeling gelei het tot ‘n verhoging in die kristalliniteit van die veselkerne en daarom ook ‘n verhoging in die modulus en breeksterkte van die garings tot gevolg gehad het.

The main objective of this thesis is to efficiently disperse and align SWNTs in two different polymer matrices to obtain an orthotropic composite whose strength, stiffness and electrical properties depend on the orientation of the SWNTs. The SWNTs are successfully dispersed and aligned in a polyimide matrix and a polymer blend of UDMA/HDDMA. In-situ polymerization under sonication is used to disperse the SWNTs in polyimide matrix and sonication is used to disperse SWNTs in the UDMA/HDDMA matrix. In both cases, an electric field is used to align the SWNTs in the polymer matrices. In the polyimide, the SWNTs are aligned by electrospinning technique, and in (UDMA/HDDMA) the SWNTs are aligned by applying an AC electric field, while the composite is cured.The electrical and mechanical properties of randomly dispersed SWNT polyimide composites and SWNT/UDMA/HDDMA composite are measured. The dielectric constant and storage modulus of SWNT polyimide composite increased with SWNT concentration. Low percolation (0.06 wt%) and an increase of 113% in storage modulus with 0.2 wt% SWNTs, both indicate good dispersion of SWNTs in the polyimide matrix. The dielectric constants, conductivity for the unaligned SWNT/UDMA/HDDMA composite are isotropic. The electrical and mechanical properties of the randomly dispersed SWNT polyimide composite and SWNT/UDMA/HDDMA composite are used as references when analyzing the aligned counter parts. Different characterization methods are used to assess the alignment of the SWNTs in the polyimide and (UDMA/HDDMA) matrices. A variety of characterization techniques, i.e. microscopy, Raman spectroscopy, electrical conductivity, dynamic dielectric spectroscopy and dynamic mechanical analysis, indicate preferential alignment of SWNTs in two types of polymers: Polyimide and (UDMA/HDDMA). Optical microscope images showed alignment of the SWNTs in the UDMA/HDDMA composite. Inspection of the Raman spectra on aligned SWNT polyimide composite fibers and aligned SWNT/UDMA/HDDMA composite indicates a decrease in the intensity of the tangential peak of the SWNT with increase in the polarizer angle. The difference in the perpendicular and parallel Raman peaks indicate preferential alignment of SWNTs in both the polymer matrices. In the aligned polyimide composite, percolation transition is at 0.2 wt% SWNT concentrations when dielectric constant is measured parallel to the aligned SWNTs. But percolation transition is at 0.65 wt% SWNT concentrations when dielectric constant is measured perpendicular to the aligned SWNTs. Electrical measurements on aligned SWNT polyimide and UDMA/HDDMA composite are highly anisotropic. In both cases, the dielectric constant values parallel to the direction of SWNT alignment are higher than the values perpendicular to the direction of SWNT alignment. To analyze the resulting anisotropy in the dielectric constant, Bruggeman's effective medium approach is used. The effective medium theory predicts the effective dielectric constant of a composite with aligned anisotropic inclusions. The effective dielectric constant, perpendicular to the aligned inclusions and parallel to the aligned inclusions is estimated. The dielectric constant values of aligned SWNT polyimide and aligned SWNT/UDMA/HDDMA composites are compared to the experimental results. Both the values from the theory and experiment show anisotropy in dielectric constant. The theory indicated that the dielectric constant parallel to the aligned inclusions is highly influenced by the dielectric constant of the inclusion and the dielectric constant perpendicular to the aligned inclusions is highly influenced by the dielectric constant of the polymer matrix. Results from the different characterizing techniques indicate that SWNTs are successfully aligned in the polyimide matrix and (UDMA/HDDMA) matrix by electrospinning technique and by an AC electric field respectively.

Graphene nanoplatelets (GNPs) were used to reinforce wood polymer composites (WPCs) in order to achieve multifunctionality. Multifunctionality could be achieved through the GNPs because of their excellent mechanical and electrical properties. The research consists of two parts: HDPE/GNP/WF composites and LLDPE/GNP composites. The HDPE part is a continuation of previous work. Here further mechanical characterisation was done (impact testing), impurities in the composites were identified, the manufacturing process that results in damaged wood particles was investigated and the Young's modulus of the composites were modeled. The impact strength was improved due to the addition of GNPs. WF composites exhibited more brittle behaviour and therefore a lower impact strength. The impurities were identified as some form of nanoclay introduced during the extrusion process. The particles were damaged during the extrusion processes. Little can be done about this as different shear configurations and/or screw speeds will result in a poor GNP dispersion and distribution. Modeling of the Young's modulus was the most accurate through applying the laminate analogy and rule of thumbs. The rule of mixtures does not represent the composites which have a preferred orientation. During the previous work done, it was found that the HDPE composite were not electrically conductive and therefore not multifunctional. The work was therefore continued with LLDPE and GNPs. LLDPE has more branches and is less dense, resulting in potential opportunities for the GNPs to form a network through the polymer. This could lead to a better conductivity. Mechanical and electrical characterisation was done of the LLDPE/GNP composites. Here multifunctionality could also not be achieved as the composites were highly electrically resistant. Mechanical testing indicated that the GNPs significantly enhance the LLDPE matrix. Here an increase of up to 170% could be seen in tensile modulus and an increase of 46% in tensile strength. Furthermore the GNPs improved the flexural properties and increase the resistance to viscoplastic deformation during residual strain testing. Overall the GNPs improve the mechanical properties significantly, but at 10wt.% GNP contents, multifunctionality could still not be achieved.

Orientador: Rondinelli Donizetti Herculano / Coorientador: Eduardo Maffud Cilli / Coorientador: Ricardo José de Mendonça / Banca: Ana Maria Minarelli Gaspar / Banca: Ana Marisa Fusca Almeida / Banca: Antonio Carlos Shimano / Banca: Cecilia Amelia de Carvalho Zavaglia / Resumo: Com o aumento dos acidentes automotivos e da expectativa de vida e, consequentemente, o da população de idosos, as fraturas ósseas e a osteoporose estão mais recorrentes, incentivando assim, a busca por novos biomateriais para reparação óssea. Em vista desta problemática, o objetivo desse trabalho consistiu em estudar a influência de diferentes fases de fosfato de cálcio na liberação sustentada utilizando a membrana de latex natural (LN) como carreador para estimular a reparação óssea. Conforme os resultados de MEV/FEG, o sol-gel tratado à 400°C (CPP), 600°C (HA) e 1200°C (α-TCP), apresentaram partículas de 170-650nm, 110-620nm e 10-79nm, respectivamente. A análise de MEV/FEG da superfície das membranas apresentou partículas de CPP inclusas na superfície e no interior das membranas. No entanto, as membranas incorporadas com HA e a α-TCP apresentaram uma inclusão mais superficial. As análises DRX e FT-IR confirmaram a identidade das fases presentes nas membranas. A membrana de LN pura apresentou um valor de rugosidade 71 vezes menor que a amostra de maior rugosidade (LN+ HA). No ensaio de ângulo de contato, as amostras LN pura e LN + CPP apresentaram molhabilidade parcial, enquanto as membranas incorporadas com HA e α-TCP apresentaram molhabilidade completa. Nos ensaios de cinéticas das liberações, as membranas apresentaram uma liberação de 48% para CPP, 95% para HA e 71% para α-TCP durante 330 horas. O ensaio de atividade hemolítica apresentou 1,1% para LN pura, 0% para LN+CP... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The increase in car accidents and life expectancy, and consequently, elderly population, bone fractures and osteoporosis are more frequent, thus encouraging the search for new biomaterials for bone repair. In view of this problem, the objective of this work was to study the influence of different phases of calcium phosphate on sustained release using the natural latex (NL) membrane as carrier to stimulate bone regeneration. According to the FEG/SEM results, the sol-gel treated at 400°C (CPP), 600°C (HA) and 1200°C (α-TCP) had particles of 170-650nm, 110- 620nm and 10-79nm, respectively. FEG/SEM analysis of the membranes surface showed CPP particles included on the surface and inside the membranes. However, the incorporated membranes with HA and α-TCP had a more superficial inclusion. XRD and FT-IR analyzes confirmed the identity of the phases present in the membranes. The pure NL membrane presented a roughness value 71 times lower than the sample of greater roughness (NL + HA). In the contact angle test, the pure NL and NL + CPP samples showed partial wettability, while the incorporated membranes with HA and α-TCP showed complete wettability. In the release kinetics assays, the membranes showed a release of 48% for CPP, 95% for HA and 71% for α-TCP for 330 hours. The hemolytic activity assay presented 1.1% for pure NL, 0% for NL + CPP, 2.2% NL + HA and 1.1% for NL + α-TCP hemolysis. The cytotoxicity assay (MTT) in osteoblasts was inconclusive due enzymes contained in the late... (Complete abstract click electronic access below) / Doutor

This research is aimed at investigating the corrosion durability of polyolefin fiber-reinforced fly ash-based geopolymer structural concrete (hereafter referred to as GPC, in contradistinction to unreinforced geopolymer concrete referred to as simply geopolymer concrete), where cement is completely replaced by fly ash, that is activated by alkalis, sodium hydroxide and sodium silicate. The durability in a marine environment is tested through an electrochemical method for accelerated corrosion. The GPC achieved compressive strengths in excess of 6,000 psi. Fiber reinforced beams contained polyolefin fibers in the amounts of 0.1%, 0.3%, and 0.5% by volume. After being subjected to corrosion damage, the GPC beams were analyzed through a method of crack scoring, steel mass loss, and residual flexural strength testing. Fiber reinforced GPC beams showed greater resistance to corrosion damage with higher residual flexural strength. This makes GPC an attractive material for use in submerged marine structures. / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2013.