This thesis looks at the study of nanocomposites of Poly(ethylene terephthalate) and organoclays. Two methods of materials blending are investigated for the production of the nanocomposites: solvent blending and melt blending. The main objectives were the investigation of the influence of organoclays and processing conditions on morphological, rheological, mechanical properties, crystal structure and isothermal crystallization kinetics of the nanocomposite and a comparison with unfilled PET. In solvent blending, the use of long sonication time and epoxy led to the formation of a two-dimensional network structure of long, thin particles in a solvent blended PET nanocomposite at low clay loading. The clay network structure seemed not to affect the tensile properties. The long, thin particles were able to be separated and dispersed further by high shear in a twin screw extruder, resulting in a high level of separation and dispersion. The crystallization of the solvent blended nanocomposite was not only influenced by the nanoclay but also by the residual solvent. The extent of clay dispersion did not affect the crystallization of the solvent blended sample. Both solvent blended and melt blended nanocomposites showed that increasing the amount of surfactant improved the degree of nanoclay dispersion in the PET that led to an enhancement in the tensile properties of the nanocomposite compared to the unfilled polymer. The degradation of the organoclay during melt blending did not limit the nanoclay dispersion in the PET. The low thermal stability of the organoclay reduced the strength of the crystalline nanocomposite but it did not affect the strength of the amorphous nanocomposite. In contrast to the solvent blended sample, the extent of clay dispersion influenced the crystallization of the melt blended sample. The poorly dispersed particles were more efficient in nucleating PET crystallization than the well dispersed particles. The crystallization rate of PET increased as the surfactant concentration decreased.

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Thesis (MSc)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: The investigation of the barrier properties of highly filled polymer-clay hybrid latex films is described. Montmorillonite (MMT) clay contents ranging from 10–30 wt.% were effectively incorporated into polystyrene-butyl acrylate (PSBA) random copolymers, via miniemulsion polymerization. The optical properties of the films were evaluated using UV-Vis spectroscopy. Compared to the neat films, the PSBA nanocomposites retained remarkable visual properties. The light transmittance for PSBA films with styrene/n-butyl acrylate (S/BA) comonomer contents of 40:60 and 50:50 (mol.%) only decreased from 70% in the neat films to 50% in the nanocomposite films containing 30 wt.% clay. The best optical properties were observed in the films with S/BA comonomer contents of 30:70 (mol.%), the light transmittance only decreased from 85% (neat film) to 60% in the nanocomposite films containing 30 wt.% clay. The improved optical properties for the PSBA-30:70 films (compared to the PSBA-40:60 and PSBA-50:50 counterparts) were attributed to an increase in the low UV-absorbing butyl acrylate component of the copolymer, which at the same time has a low Tg that probably facilitated dispersion of the rigid MMT platelets in the matrix. In this study, the overall water vapour transport behaviour was governed by the MMT clay presence and less affected by the copolymer composition variation. The lower diffusion coefficients in the polymer clay nanocomposites (PCNs) were a result of the impermeable clay platelets which forced the water vapour molecules to follow longer and more tortuous paths to diffuse through the nanocomposite films. The irregular shape in the PSBA-40:60 and PSBA-30:70 neat latex particles was lost in the hybrid particles and well defined, dumb-bell shaped particles were observed. This was because of the faceting effect of the rigid MMT clay platelets. The MMT clay platelets were predominantly adhered to the surface of the PSBA latex particles because MMT clay particles have a larger size than the effective size of the copolymer particles. The stable overall transport coefficients in the PSBA-30:70-MMT films were attributed to the morphological organization of clay platelets in the matrix. The storage modulus of the materials decreased with an increase in clay content. This was attributed to the dual role played by the organoclay, firstly as nanofiller and reinforcing agent leading to the increase in storage modulus, and secondly as a plasticizer leading to a decrease of storage modulus. / AFRIKAANSE OPSOMMING: Die versperringseienskappe van hoogsgevulde polimeer-klei saamgestelde latekslae is beskryf. „n 10–30 wt % Montmorilloniet (MMT) klei inhoud is inkorporeer in polistireenbutielakrilaat (PSBA) onreëlmatige kopolimere, via miniemulsie polimerisasie. Die optiese eienskappe van die lae is bepaal m.b.v. UV-Vis spektroskopie. In vergelyking met die lae sonder klei (sogenaamde „neat films‟), het die PSBA nanosamestellings interressante visuele eienskappe getoon. Die ligtransmissie van die PSBA lae met „n stireeen/n-butielakrilaat (S/BA) komonomeerinhoud van 40:60 en 50:50 (mol %) het slegs afgeneem vanaf 70% in die „neat films‟ tot 50% in the nanosaamgestelde lae wat 30% klei bevat het. Die beste optiese eienskappe is waargeneem vir die lae wat „n 30:70 (mol %) S/BA komonomeerinhoud bevat het; die transmissie het slegs afgeneem vanaf 85% in die „neat films‟ to 60% in the nanosaamgestelde lae wat 30% klei bevat het. Die verbeterde optiese eienskappe van die PSBA-30:70 films (in vergelyking met die -40:60 and -50:50 films) is toegeskryf aan „n toename in die lae UV-absorberende butielakrilaat komponent van die kopolimeer. Terselfdetyd het laasgenoemde „n lae Tg-waarde, wat dispersie van die onbuigbare MMT kleiplaatjies in die matriks gefasiliteer het. In hierdie studie is die algehele waterdampvervoer deur die teenwoordigheid van die MMT klei beheer; dit is minder geaffekteer deur variasie in die samestelling van die kopolimeer. Die lae diffusiekoëffisiënte in die polimeer-klei nanosamestellings is as gevolg van die ondeurdringbare kleiplaatjies, wat die waterdampmolekules dwing om langs langer en meer gekronkelde paaie te diffundeer deur die nanosaamgestelde lae. Die onreëlmatige vorm wat gesien is in die PSBA-40:60 and PSBA-30:70 latekspartikels (sonder klei) het geleidelik verdwyn in die saamgestelde partikels, en goed-gedefineerde partikels met die vorm van handgewigte is waargeneem (in TEM beelde). Die rede hiervoor is die sogenaamde „faceting‟ effek, wat deur die onbuigbare MMT kleiplaatjies veroorsaak is. Die MMT kleiplaatjies sit hoofsaaklik aan die oppervlaktes van die PSBA latekspartikels. Die rede hiervoor is dat die MMT kleipartikels groter is as die effektiewe grootte van die kopolimeerpartikels. Die stabiele vervoerkoëffisiënte in die PSBA-30:70-MMT films is aan die unieke morfologiese eienskappe toegeskryf. Die bergingsmodulus van die materiale het monotonies afgeneem met „n toename in klei-inhoud. Dit is toegeskryf aan die tweedelige rol wat die organoklei speel – eerstens as 'n nanovuller en versterkingsmiddel, wat „n toename in bergingsmodulus tot gevolg het, en tweedens as „n plastiseerder, wat „n afname in bergingsmodulus tot gevolg het.

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The effect of molecular weight on the dispersion of relatively polar montmorillonite (MMT) in non polar, unmodified high density polyethylene (HDPE) was examined. Polymer layered silicate (PLS) nanocomposites were compounded using three unmodified HDPE matrices of differing molecular weight and an organically modified MMT in concentrations ranging from 2 wt% to 8 wt% via single screw extrusion. The weight average molecular weights of the HDPE matrices used in this study ranged from 87,000 g/mol to 460,000 g/mol. X-ray diffraction (XRD), mechanical testing, dynamic mechanical thermal analysis (DMTA), as well as dynamic and capillary rheometry were performed on the nanocomposites. Nanocomposites generated from the high molecular weight (HMW) HDPE matrix exhibited increased intercalation of the MMT as shown by XRD as well as greater improvements in the Young's modulus compared to nanocomposites generated from both the low (LMW) and middle molecular weight (MMW) matrices. This was attributed to higher shear stress imparted to MMT during compounding from the more viscous matrix facilitating their separation and orientation during injection molding. DMTA showed that the torsional response of the HMW nanocomposites was not as great compared to their LMW and MMW counterparts as observed from a lower percentage enhancement in the storage modulus (Gâ ) and estimated heat distortion temperature (HDT) due to anisotropy in mechanical properties. Dynamic rheology indicated that a percolated network did not exist in any of the nanocomposites as shown by no change in the terminal behavior of Gâ upon addition of clay. / Master of Science

Polymer nanocomposites have been proposed as lightweight replacements for traditional composite materials in various applications. Montmorillonite (MMT) and carbon nanotubes (CNTs) are two nanofillers which have accrued significant interest in the past 20 years due to their superior mechanical and electrical properties, respectively. However, efficient dispersion of the nanofiller and damage to CNTs prevent widespread utilization of these materials in polymer nanocomposites. Novel methods of nanocomposite generation combining the use of supercritical carbon dioxide (scCO2) with melt compounding have been investigated to overcome these issues. The focus of this work is on developing the scCO2 treatment of nanomaterial for thermoplastic nanocomposite generation. First, the supercritical carbon dioxide aided melt blending method was applied to nanoclay nanocomposites of Nylon 6/ and organoclay where the polymer may interact with the nanoclay surface. Second, the effect of scCO2 processing of CNTs was investigated with special consideration to the processing variables. Finally, a study was carried out to analyze the electrical conductivity of polycarbonate nanocomposites generated using CNTs deagglomerated by scCO2 processing. The initial focus of this dissertation is the use of supercritical carbon dioxide (scCO2) as a processing aid in the generation of nylon 6 nanocomposites in which the nylon 6 may interact with the nanoclay surface. Wide-angle X-ray diffraction, transmission electron microscopy, rheology, and tensile tests were carried out to investigate the effect of processing with scCO2 on the final composite morphology and properties. It was observed that mechanical properties of composites prepared with the scCO2 aided melt blending method were similar to or higher than those reported in the literature for samples prepared with twin screw compounding. At 7.6 wt% nanoclay the modulus value reaches 4.75 +/- 0.194 GPa which is one of the highest increases (1.7 GPa) reported for these materials processed at intermediate concentrations. Beyond 7.6 wt% the improvement due to scCO2 processing matched that of direct blending. The next objective of this work is to develop a method for the deagglomeration of commercially available multi-walled carbon nanotubes (MWCNTs) by manipulating processing variables and observing carbon nanotube aspect ratios after deagglomeration. High levels of deagglomeration of Baytubes C 150 P and Nanocyl NC-7000 MWCNT agglomerates were observed, resulting in 30 fold and 50 fold decreases in bulk density, respectively, with median agglomerate sizes < 8 um in diameter. These results were obtained while retaining the aspect ratio of the as-received nanomaterial, irrespective of the MWCNT agglomerate morphology. It was found that the supercritical temperature and pressure of 40 deg C and 7.86 MPa were the optimal temperature and pressure for maximum deagglomeration without damaging the MWCNTs. The final goal of this work is to apply the scCO2 aided melt blending process to generate polycarbonate/ carbon nanotube (CNT) nanocomposites with enhanced electrical conductivity and improved dispersion while maintaining the aspect ratio of the as-received CNTs. Different degrees of scCO2 processed Baytubes C 150 P CNT were benignly deagglomerated with scCO2 resulting in 5 fold (5X), 10X, and 15X decreases in bulk density from the as-received CNTs. The CNT were melt compounded with polycarbonate using single screw melt extrusion and compression molded into plaques. A surface conductivity of 4.8 x 10-8 +/- 2.0 x 10-9 S was observed for samples prepared with the scCO2 aided melt blending at 15X scCO2 processing. Electrical percolation thresholds as low as 0.83 wt% were observed for composites prepared with 15X CNTs using the scCO2 aided melt blending method, while concentrations as high as 1.5% are required without scCO2 processing. The percolation concentration in nanocomposites prepared with 15X scCO2 processing and single screw extrusion is competitive with values reported for similar nanocomposites generated using twin screw melt compounding in the literature. Optical microscopy, transmission electron microscopy, and rheology were used to investigate the dispersion and mechanical network of CNTs in the nanocomposites. The dispersion of CNTs generally improved with scCO2 processing compared to direct melt blending but was found to be significantly worse than that of twin screw melt compounded nanocomposites from the literature. Because the percolation thresholds are similar with substantially different extents of dispersion, the importance of maintaining longer CNTs during nanocomposite generation is emphasized. / Ph. D.

Wood plastic composites (WPCs) were made using matrices of recycled high-density polyethylene (rHDPE) and polypropylene (rPP) with sawdust (Pinus radiata) as filler. Corresponding WPCs were also made using virgin plastics (HDPE and PP) for comparison with the recycled plastic based composites. WPCs were made through melt compounding and hot-press moulding with varying formulations based on the plastic type (HDPE and PP), plastic form (recycled and virgin), wood flour content and addition of coupling agent. The dimensional stability and mechanical properties of WPCs were investigated. Durability performances of these WPCs were studied separately, by exposing to accelerated freeze-thaw (FT) cycles and ultraviolet (UV) radiation. The property degradation and colour changes of the weathered composites were also examined. Dimensional stability and flexural properties of WPCs were further investigated by incorporation of nanoclays in the composite formulation. To understand the changes in WPCs stability and durability performance, microstructure and thermal properties of the composites were examined. Two mathematical models were developed in this work, one model to simulate the moisture movement through the composites in long-term water immersion and the other model to predict the temperature profile in the composites during hot-press moulding. Both rHDPE and rPP matrix based composites exhibited excellent dimensional stability and mechanical properties, which were comparable to those made from virgin plastics. Incorporation of maleated polypropylene (MAPP) coupling agent in composite formulation improved the stability and the mechanical properties. The incorporation of 3 wt. % MAPP coupling agent to WPCs showed an increase in tensile strength by 60% and 35 %, respectively, for the rHDPE based and rPP based composites with 50 wt. % wood flour. Scanning electron microscopy (SEM) images of the fractured surfaces of WPCs confirmed that the MAPP coupling improved the interfacial bonding between the plastic and the wood filler for both series of composites. Long-term water immersion tests showed that the water transport mechanism within the WPCs follows the kinetics of Fickian diffusion. Dimensional stability and flexural properties of the WPC were degraded after 12 accelerated FT cycles as well as 2000 h of UV weathering for both recycled and virgin HDPE and PP based composites. However, the MAPP coupled composites had improved stability and flexural property degradation. The surface of the weathered composites experienced a colour change, which increased with the exposure time. The MAPP coupled composites exhibited less colour change as compared to non-coupled composites. Regarding the effect of the plastic type, the PP based composites experienced higher colour change than those based on HDPE. With weathering exposure, flexural strength and stiffness of the WPCs were decreased, but elongation at break was increased regardless of plastic type and wood flour content. MAPP coupled rPP and rHDPE based UV weathered WPCs lowered the degradation of stiffness by 50% and 75%, respectively compared to non-coupled WPCs. SEM images of the fractured surfaces of FT and UV weathered WPCs confirmed a decrease in the interfacial bonding between the wood flour and matrix. Thermal properties of weathered composites changed with weathering, but the extent of the changes depended on WPCs formulation and matrix type. From the experimental studies on nanoclay-filled rHDPE composites, it is found that stability, flexural properties of WPCs could be improved with an appropriate combination of coupling agent, and nanoclay contents processed by melt blending. Incorporation of 1-5 wt. % nanoclay in the maleated polyethylene (MAPE) coupled wood plastic composite improved the dimensional stability and flexural properties. The thermal properties changed with the addition of nanoclay and MAPE in WPCs. In this work, a hot press-moulding model was proposed based on the one-dimensional transient heat conduction to predict the temperature profile of the WPCs during hot pressing cycle. The results from this work clearly show that rHDPE and rPP can be successfully used to produce stable and strong WPCs, which properties and performances are similar to or comparable to composites made of wood and virgin plastics. Therefore, WPCs based on recycled PP and HDPE matrix could have potential to use as construction materials.

abstract: Dye sensitized solar cells (DSSCs) are currently being explored as a cheaper alternative to the more common silicon (Si) solar cell technology. In addition to the cost advantages, DSSCs show good performance in low light conditions and are not sensitive to varying angles of incident light like traditional Si cells. One of the major challenges facing DSSCs is loss of the liquid electrolyte, through evaporation or leakage, which lowers stability and leads to increased degradation. Current research with solid-state and quasi-solid DSSCs has shown success regarding a reduction of electrolyte loss, but at a cost of lower conversion efficiency output. The research work presented in this paper focuses on the effects of using nanoclay material as a gelator in the electrolyte of the DSSC. The data showed that the quasi-solid cells are more stable than their liquid electrolyte counterparts, and achieved equal or better I-V characteristics. The quasi-solid cells were fabricated with a gel electrolyte that was prepared by adding 7 wt% of Nanoclay, Nanomer&reg; (1.31PS, montmorillonite clay surface modified with 15-35% octadecylamine and 0.5-5 wt% aminopropyltriethoxysilane, Aldrich) to the iodide/triiodide liquid electrolyte, (Iodolyte AN-50, Solaronix). Various gel concentrations were tested in order to find the optimal ratio of nanoclay to liquid. The gel electrolyte made with 7 wt% nanoclay was more viscous, but still thin enough to allow injection with a standard syringe. Batches of cells were fabricated with both liquid and gel electrolyte and were evaluated at STC conditions (25&deg;C, 100 mW/cm2) over time. The gel cells achieved efficiencies as high as 9.18% compared to 9.65% achieved by the liquid cells. After 10 days, the liquid cell decreased to 1.75%, less than 20% of its maximum efficiency. By contrast, the gel cell's efficiency increased for two weeks, and did not decrease to 20% of maximum efficiency until 45 days. After several measurements, the liquid cells showed visible signs of leakage through the sealant, whereas the gel cells did not. This resistance to leakage likely contributed to the improved performance of the quasi-solid cells over time, and is a significant advantage over liquid electrolyte DSSCs. / Dissertation/Thesis / M.S.Tech Engineering 2012

Breast cancer shows a high affinity towards the bone, causing bone-related complications leading to poor clinical prognosis. Approximately 80% of breast cancer patients die within five years after primary cancer has metastasized to the bones. The tumor stage strongly influences the survival rates of patients with breast cancer that has spread to bone at the time of diagnosis. There are currently no effective therapeutics available for bone metastases due to the failure of animal models and the scarcity of human bone metastasized samples, as most patients with advance stages of cancer are already in palliative care. Therefore, it is imperative to develop translational models to elucidate disease mechanisms at the cellular and molecular level. Here, we report the development of tissue-engineered nanoclay-based bone-mimetic three-dimensional (3D) in vitro model for studying later stages of cancer pathogenesis at the metastatic bone site using osteogenically-differentiated human mesenchymal stem cells (MSCs) and human breast cancer cells (MDA-MB-231 and MCF-7). This 3D model provides an ideal microenvironment suitable for cell-cell and cell-matrix interactions while retaining the behavior of breast cancer cells with different metastatic potential along with mimicking mesenchymal to epithelial transition (MET) of breast cancer cells. Sequential cultures of MSCs with MCF-7 gave rise to tumoroids, while sequential cultures of MSCs with MDA-MB-231 formed disorganized clusters of cells with poor cell-cell adhesion. We further evaluated how cancer-derived factors and cytokines affect bone leading to up to metastasis and conferring drug resistance, respectively. Results showed that Wnt/β-catenin and interleukin-6 (IL-6) mediated IL-6/STAT3 pathways are responsible for bone-related complications and conferring drug resistance, respectively. Furthermore, we have utilized the 3D in vitro model to develop methods for non-invasive and rapid prediction of cancer progression using various biophysical techniques such as spectroscopy and nanoindentation. Spectroscopy methods showed significant contributions of proteins, lipids, and nucleic acids, while the nanoindentation method showed F-actin mediated softening of cancer cells during cancer progression at the metastatic bone site, respectively. Collectively, 3D in vitro model provides an ideal platform for studying the molecular mechanism of breast cancer progression at the metastatic bone site, drug development, and discovery of biomarkers for cancer progression.

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