Thesis (M.A. (Afrikaans and Dutch))--North-West University, Potchefstroom Campus, 2006.

This work presents the synthesis and the self-assembly of symmetrical amphiphilic ABA and BAB triblock copolymers in dilute, semi-concentrated and highly concentrated aqueous solution. A series of new bifunctional bistrithiocarbonates as RAFT agents was used to synthesise these triblock copolymers, which are characterised by a long hydrophilic middle block and relatively small, but strongly hydrophobic end blocks. As hydrophilic A blocks, poly(N-isopropylacrylamide) (PNIPAM) and poly(methoxy diethylene glycol acrylate) (PMDEGA) were employed, while as hydrophobic B blocks, poly(4-tert-butyl styrene), polystyrene, poly(3,5-dibromo benzyl acrylate), poly(2-ethylhexyl acrylate), and poly(octadecyl acrylate) were explored as building blocks with different hydrophobicities and glass transition temperatures. The five bifunctional trithiocarbonates synthesised belong to two classes: the first are RAFT agents, which position the active group of the growing polymer chain at the outer ends of the polymer (Z-C(=S)-S-R-S-C(=S)-Z, type I). The second class places the active groups in the middle of the growing polymer chain (R-S-C(=S)-Z-C(=S)-S-R, type II). These RAFT agents enable the straightforward synthesis of amphiphilic triblock copolymers in only two steps, allowing to vary the nature of the hydrophobic blocks as well as the length of the hydrophobic and hydrophilic blocks broadly with good molar mass control and narrow polydispersities. Specific side reactions were observed among some RAFT agents including the elimination of ethylenetrithiocarbonate in the early stage of the polymerisation of styrene mediated by certain agents of the type II, while the use of the RAFT agents of type I resulted in retardation of the chain extension of PNIPAM with styrene. These results underline the need of a careful choice of RAFT agents for a given task. The various copolymers self-assemble in dilute and semi-concentrated aqueous solution into small flower-like micelles. No indication for the formation of micellar clusters was found, while only at high concentration, physical hydrogels are formed. The reversible thermoresponsive behaviour of the ABA and BAB type copolymer solutions in water with A made of PNIPAM was examined by turbidimetry and dynamic light scattering (DLS). The cloud point of the copolymers was nearly identical to the cloud point of the homopolymer and varied between 28-32 °C with concentrations from 0.01 to 50 wt%. This is attributed to the formation of micelles where the hydrophobic blocks are shielded from a direct contact with water, so that the hydrophobic interactions of the copolymers are nearly the same as for pure PNIPAM. Dynamic light scattering measurements showed the presence of small micelles at ambient temperature. The aggregate size dramatically increased above the cloud point, indicating a change of aggregate morphology into clusters due to the thermosensitivity of the PNIPAM block. The rheological behaviour of the amphiphilic BAB triblock copolymers demonstrated the formation of hydrogels at high concentrations, typically above 30-35 wt%. The minimum concentration to induce hydrogels decreased with the increasing glass transition temperatures and increasing length of the end blocks. The weak tendency to form hydrogels was attributed to a small share of bridged micelles only, due to the strong segregation regime occurring. In order to learn about the role of the nature of the thermoresponsive block for the aggregation, a new BAB triblock copolymer consisting of short polystyrene end blocks and PMDEGA as stimuli-responsive middle block was prepared and investigated. Contrary to PNIPAM, dilute aqueous solutions of PMDEGA and of its block copolymers showed reversible phase transition temperatures characterised by a strong dependence on the polymer composition. Moreover, the PMDEGA block copolymer allowed the formation of physical hydrogels at lower concentration, i.e. from 20 wt%. This result suggests that PMDEGA has a higher degree of water-swellability than PNIPAM. / Die Arbeit behandelt die Synthese und das Selbstorganisationsverhalten von neuen funktionellen symmetrischen "stimuli-responsiven" Triblockcopolymeren ABA und BAB in wässrigen verdünnten und höher konzentrierten Lösungen. Neue symmetrische, bifunktionelle Bistrithiocarbonate wurden als RAFT-Agentien benutzt, um Triblockcopolymere mit langen hydrophilen (A) Innen- und kurzen hydrophoben (B) Außenblöcken zu synthetisieren. Als hydrophile A Blöcke wurden Poly(N-isopropylacrylamid) PNIPAM und Poly(methoxy diethylene glykol acrylat) PMDEGA benutzt, während als hydrophobe Blöcke B Poly(4-tert-butyl styrol), Polystyrol, Poly(3,5-dibromo benzyl acrylat), Poly(2-ethylhexyl acrylat), und Poly(octadecyl acrylat) als Bausteine mit unterschiedlicher Glasübergangstemperatur untersucht wurden. Die Selbstorganisation von ABA und BAB Copolymeren in Wasser mit A Blöcken aus PNIPAM wurde anhand von Trübungsphotometrie, dynamischer Lichtstreuung (DLS) und Rheologie untersucht. Die amphiphilen Blockcopolymere sind direkt wasserlöslich. Bei Konzentrationen von 0.01 bis 50 wt% zeigen Trübungsmessungen bei den Blockcopolymeren wie bei den Homopolymeren eine Übergangstemperatur bei 28-32 °C. Zurückzuführen ist dies auf die Bildung von Mizellen, bei der die hydrophoben Blöcke von einem direkten Kontakt mit Wasser abgeschirmt werden. DLS zeigt kleine Mizellen bei niedrigen Temperaturen und Aggregate mit großem hydrodynamischem Durchmesser bei Temperaturen oberhalb der Übergangstemperatur. Die rheologische Untersuchung von BAB Polymeren zeigt die Bildung von Hydrogelen bei höheren Konzentrationen (über 30-35 wt%). Die minimal benötigte Konzentration, bei der die von Hydrogelen auftreten, nimmt mit wachsender Glasübergangstemperatur ab, und nimmt mit der Länge der hydrophoben Blöcke B zu. Im Unterschied zu PNIPAM zeigen wässrige Lösungen von PMDEGA und seinen Blockcopolymeren reversible Übergangstemperaturen abhängig von der chemischen Struktur. Außerdem bilden PMDEGA Blockcopolymere Hydrogele bei niedriger Konzentration (ab 20 wt%). Dieses Ergebnis deutet darauf hin, dass PMDEGA stärker Wasser bindet als PNIPAM.

Silicone rubber based on polydimethylsiloxane is used ashigh voltage outdoor insulation, due to its ability to preservethe hydrophobic surface properties during service and evenregain hydrophobicity after exposure to electrical discharges.The underlying processes for the hydrophobic recovery arediffusion of low molar mass siloxanes from the bulk to thesurface and reorientation by conformational changes ofmolecules in the surface region. Only little is known of whichfactors are responsible for the long-term stability of thishydrophobic recovery. It is therefore important to increase theknowledge about the fundamental mechanisms for the loss andrecovery of hydrophobicity of silicone rubbers, exposed toelectrical discharges. Addition-cured polydimethylsiloxanenetworks, with known crosslink densities, were exposed tocorona discharges and air/oxygen-plasma and the loss andrecovery of hydrophobicity was characterised by contact anglemeasurements. The degree of surface oxidation increased withincreasing exposure time with a limiting depth of 100- 150 nm,as assessed by neutron reflectivity measurements. The oxidationrate increased with increasing crosslink density of the polymernetwork, according to X-ray photoelectron spectroscopy. Withinthe oxidised layer, a brittle, silica-like layer was graduallydeveloped with increasing exposure time. The hydrophobicrecovery following the corona or air/oxygen- plasma exposuresoccurred at a slow pace by diffusion of cyclic oligomericdimethylsiloxanes through the micro-porous but uncrackedsilica-like surface layer or at a much higher pace by transportof the oligomers through cracks in the silica-like layer. Theoligomers were present in the bulk, but additional amounts wereformed during exposure to corona discharges. High-temperaturevulcanised silicone rubber specimens were aged in a coastalenvironment under high electrical stress levels (100 V/mm). Thechanges in surface structure and properties were compared tothe data obtained from specimens exposed to coronadischarges/plasma. The dominating degradation mechanism wasthermal depolymerisation, initiated by hot discharges. Thisresulted in the formation of mobile siloxanes, of which the lowmolar mass fraction consisted of cyclic oligomericdimethylsiloxanes. Oxidative crosslinking resulting insilica-like surface layers was not observed during theseconditions. <b>Keywords:</b>silicone rubber, polydimethylsiloxane,hydrophobicity, corona, air-plasma, oxygen-plasma, surfacecharacterisation, degradation products, crosslink density.

Rechargeable batteries play an important role as energycarriers in our modern society, being present in wirelessdevices for everyday use such as cellular phones, video camerasand laptops, and also in hybrid electric cars. The batterytechnology dominating the market today is the lithium-ion(Li-ion) battery. Battery developments, in terms of improvedcapacity, performance and safety, are major tasks for bothindustry and academic research. The performance and safety ofthese batteries are greatly influenced by transport andstability properties of the electrolyte; however, both haveproven difficult to characterise properly. The specific aim of this work was to characterise and modelthe electrolytes used in Li-ion batteries. In particular, themass transport in these electrolytes was studied throughcharacterisation and modelling of electrolyte transport in bulkand in porous electrodes. The characterisation methodology assuch was evaluated and different models were tested to find themost suitable. In addition, other properties such aselectrochemical stability and thermal properties were alsostudied. In the study of electrochemical stability it wasdemonstrated that the electrode material influenced thevoltammetric results significantly. The most versatileelectrode for probing the electrolyte stability proved to beplatinum. The method was concluded to be suitable for comparingelectrolytes and the influences of electrolyte components,additives and impurities, which was also demonstrated for a setof liquid and polymer containing electrolytes. A full set of transport properties for two binary polymerelectrolytes, one binary liquid and the corresponding ternarygel were achieved. The transport was studied both in the bulkand in porous electrodes, using different electrochemicaltechniques as well as Raman spectroscopy. In general, theconductivity, the salt and solvent diffusivity decreasedsignificantly when going from liquid to gel, and to polymerelectrolyte. Additionally, low cationic transport numbers wereachieved for the polymer and gel and significant salt activityfactor variations were found. The results were interpreted interms of molecular interactions. It was concluded that both theionic interactions and the influences from segmental mobilitywere significant for the polymer containing electrolytes. Thecharacterisation methods and the understanding were improved bythe use of a numerical modelling using a model based on theconcentrated electrolyte theory. It was concluded thatelectrochemical impedance spectroscopy and Raman spectroscopywere insufficient for determining a full set of transportproperties. It was demonstrated that the transport is veryinfluential on electrochemical impedance as well as batteryperformance. <b>Keywords:</b>lithium battery, electrolyte, mass transport,stability, modelling, characterisation, electrochemical, Ramanspectroscopy, impedance

A whisker is a common name of single crystalline inorganic fibre of small dimensions, typically 0.5-1 μm in diameter and 20-50 μm in length. Whiskers are mainly used as reinforcement of ceramics. This work describes the synthesis and characterisation of new whisker types. Ti0.33Ta0.33Nb0.33CxN1-x, TiB2, B4C, and LaxCe1-xB6 have been prepared by carbothermal vapour–liquid–solid (CTR-VLS) growth mechanisms in the temperature range 900-1800°C, in argon or nitrogen. Generally, carbon and different suitable oxides were used as whisker precursors. The oxides reacted via a carbothermal reduction process. A halogenide salt was added to form gaseous metal halogenides or oxohalogenides and small amount of a transition metal was added to catalyse the whisker growth. In this mechanism, the whisker constituents are dissolved into the catalyst, in liquid phase, which becomes supersaturated. Then a whisker could nucleate and grow out under continuous feed of constituents. The syntheses of TiC, TiB2, and B4C were followed at ordinary synthesis conditions by means of mass spectrometry (MS), thermogravimetry (TG), differential thermal analysis (DTA) and quenching. The main reaction starting temperatures and reaction time for the different mixtures was revealed, and it was found that the temperature inside the crucible during the reactions was up to 100°C below the furnace set-point, due to endothermic nature of the reactions. Quench experiments showed that whiskers were formed already when reaching the temperature plateau, but the yield increased fast with the holding time and reached a maximum after about 20-30 minutes. Growth models for whisker formation have been proposed. Alumina based composites reinforced by (2-5 vol.%) TiCnano and TiNnano and 25 vol.% of carbide, and boride phases (whiskers and particulates of TiC, TiN, TaC, NbC, (Ti,Ta)C, (Ti,Ta,Nb)C, SiC, TiB2 and B4C) have been prepared by a developed aqueous colloidal processing route followed by hot pressing for 90 min at 1700°C, 28 MPa or SPS sintering for 5 minutes at 1200-1600°C and 75 MPa. Vickers indentation measurements showed that the lowest possible sintering temperature is to prefer from mechanical properties point of view. In the TiNnano composites the fracture mode was typically intergranular, while it was transgranular in the SiCnano composites. The whisker and particulate composites have been compared in terms of e.g. microstructure and mechanical properties. Generally, additions of whiskers yielded higher fracture toughness compared to particulates. Composites of commercially available SiC whiskers showed best mechanical properties with a low spread but all the other whisker phases, especially TiB2, exhibited a great potential as reinforcement materials.

For a long time spectrophotometry has been a powerful method of determining optical material properties. Since the technique measures the parameters of interest, reflectance and transmittance, it is in general easy to use and interpret. Certain materials, such as miniature structures or scattering materials, must be given a more careful analysis to avoid incorrect interpretation. General solutions to measurement challenges for thick scattering samples and anisotropically scattering samples are presented. Thorough knowledge about the components of a spectrophotometer gives a solid base which is necessary when trying to design or modify an instrument for the characterisation of miniature components. Focusing optics and pinhole apertures are two methods investigated for studying samples on a millimeter scale. Focusing optics retain a high intensity but might cause internal reflection. Pinhole apertures are easy to build into a sample holder, but they will reduce light intensity which can give problems with signal to noise ratio. Using a microscope as a focusing lens system permits the measurement of samples of a size down to the order of ten micrometers. However, absolute measurements are difficult due to the strong focusing properties of the microscope. Translucent sheets are of interest for daylighting applications, a growing field in today's energy-conscious society. If sunlight is to be used for indoor illumination it is preferable to make it diffuse. By using Transparent Refractive Index Matched Micro (TRIMM) particles in a transparent polymer sheet, it is possible to obtain high transmittance in combination with tailorability of the scattering profile. Such sheets have been characterised experimentally, as well as by Monte Carlo raytracing simulations. The good agreement between simulation and experiment shows that this type of simulation can be used in the materials design process. A more theoretical study of patterns in multiple Mie scattering has been carried out using the Monte Carlo program developed for characterisation of the TRIMM particle sheets.

In this work an extended literature survey on ceramics and porcelains in particular, has been documented. Samples from two Ugandan deposits of each feldspar and quartz were characterised by means of X-ray diffraction, thermal analysis, chemical analysis and scanning electron microscopy and found to possess requisite properties for making electro porcelain insulators. Five porcelain bodies were formulated and samples were fabricated from materials collected from selected deposits in Uganda using different mixing proportions of clay, feldspar and quartz. The properties of the formulated bodies were studied in relation to workability, firing temperature, dielectric and bending strengths. The strengths (both mechanical and dielectric) were found to decrease as the firing temperature was increased above 1250°C. Additionally, ten formulations with components in the range of 30-60% clay, 20-45% feldspar and 20-25% sand were prepared. Specimens for mechanical and physical characterisation were made using the plastic extrusion method. The samples were characterised in terms of constituent oxide composition, flexural strength, fracture toughness, dielectric strength along with microstructural and phase properties using ICP-AES analyses, 4-point load bending strength test, Vicker’s indentation method, SEM and XRD analyses respectively. XRD studies revealed that the crystalline phases formed were mullite and quartz and their intensity was almost identical for all samples fired at 1250°C but there was a decrease inquartz content as temperature was increased above 1250°C. Samples with 20% sandcontent resulted in higher density, MOR and fracture toughness compared to thosecontaining 25% sand. Mullite content on the other hand did not change at temperatures above 1200°C but there were significant differences in the morphologies of the mullite crystals in the samples. Optimum mechanical and electrical properties were found at maximum vitrification and a microstructure showing small closely packed mullite needles. This occurred at a firing temperature of 1250°C. Three promising porcelain formulations from the above investigations were chosen and five glazes formulated to fit on biscuit fired specimens. The best-fitting glaze was adopted. The formulated specimens were investigated using dilatometry, Steger test, FEG-SEM, XRD, 4-point bending, dielectric strength and fracture toughness tests. A porcelain specimen consisting of 68% SiO2, 19% Al2O3, 4.7% K2O and a glaze of Seger formula RO:0.57Al2O3:4.86SiO2 exhibited MOR of 105MPa with Weibull modulus of 5.6 and a dielectric strength of 18kV/mm upon firing at a heating rate of 6ºC/min to 1250ºC, soaking for 2h at the top temperature and cooling down to 500°C at a rate of 6°C/min, followed by furnace cooling. The microstructure of the high strength specimen exhibited round mullite needles, quartz and glass. Holding samples for 2h at peak temperature resulted in a 22% increase in MOR compared to 1h holding. Glazing further improved strength by 67% for the best sample. Compressive stresses in glaze contributed to the strengthening effect. The dielectric and mechanical strengths obtained make the ormulated sample suitable for application in low voltage electrical insulation. / QC20100609

The field of Information and Communication Technologies is witnessing a development speed unprecedented in history. Moore’s law proves that the processor speed and memory size are roughly doubling each 18 months, which is expected to continue in the next decade. If photonics is going to play a substantial role in the ICT market, it will have to follow the same dynamics. There are mainly two groups of components that need to be integrated. The active components, including light sources, electro-optic modulators, and detectors, are mostly fabricated in III-V semiconductors. The passive components, such as waveguides, resonators, couplers and splitters, need no power supply and can be realized in silicon-related semiconductors. The prospects of silicon photonics are particularly promising, the fabrication is mostly compatible with standard CMOS technology and the on-chip optical interconnects are expected to increase the speed of microprocessors to the next generation. This thesis starts with designs of various silicon-based devices using finite-difference time-domain simulations. Parallel computation is a powerful tool in the modeling of large-scale photonic circuits. High Q cavities and resonant channel drop filters are designed in photonic crystal platform. Different methods to couple light from a single mode fiber to silicon waveguides are studied by coupled-mode theory and verified using parallel simulations. The performance of waveguide grating coupler for vertical radiation is also studied. The fabrication of silicon-based photonic devices involves material deposition, E-beam or optical lithography for pattern defining, and plasma/wet-chemistry etching for pattern transfer. For nanometer-scaled structures, E-beam lithography is the most critical process. Depending on the structures of the devices, both positive resist (ZEP520A) and negative resist (maN2405) are used. The proximity and stitch issues are addressed by careful dose correction and patches exposure. Some examples are given including photonic crystal surface mode filter, micro-ring resonators and gold grating couplers. In particular, high Q (2.6×105), deep notch (40 dB) and resonance-splitting phenomenon are demonstrated for silicon ring resonators. It is challenging to couple light into photonic integrated circuits directly from a single-mode fiber. The butt-coupled light-injecting method usually causes large insertion loss due to small overlap of the mode profiles and large index mismatch. Practically it is not easy to cleave silicon sample with smooth facet where the waveguide exposes. By adding gold gratings to the waveguides, light can be injected and collected vertically from single-mode fiber. The coupling efficiency is much higher. There is no need to cleave the sample. The access waveguides are much shortened and the stitch problem in E-beam lithography is avoided. In summary, this thesis introduces parallel simulations for the design of modern large-scale photonic devices, addresses various issues with Si-based fabrication, and analyses the data from the characterization. Several novel devices using silicon nanowire waveguides and 2D photonic crystal structures have been demonstrated for the first time. / QC 20100923

Some viral metagenomic serum samples contain a huge amount of Anellovirus, which is a genetically diverse family with a few conserved regions making it hard to efficiently characterize. Multiple sequence alignment of the Anelloviruses found in the sample must be constructed to get a clear picture of Anellovirus diversity and to identify stable regions. Using available multiple sequence alignment software directly on these fragments results in an MSA of a very poor quality due to their diversity, misaligned regions and low-quality regions present in the sequence. An efficient MSA must be constructed in order to characterize these Anellovirus present in the samples. Pairwise alignment is used to align one fragment to the database sequences at a time. The fragments are then aligned to the database sequences using the start and end position from the pairwise alignment results. The algorithm will also exclude non-aligned portions of the fragments, as these are very hard to handle properly and are often products of misassembly or chimeric sequenced fragments. Other tools to aid further analysis were developed, such as finding a non-overlapping window that contains the most fragments, find consensus of the alignment and extract any regions from the MSA for further analysis. An MSA was constructed with a high percent of correctly aligned bases compared to an MSA constructed using MSA softwares. The minimal number of genomes found in the sampled sequence was found as well as a distribution of the fragments along the database sequence. Moreover, highly conserved region and the window containing most fragments were extracted from the MSA and phylogenetic trees were constructed for these regions.

This report is the result of a Master Thesis work that has been performed between October 2003 and March 2004. The purpose of the work was to evaluate a part of the signal chain in a product of Micronic Laser Systems AB. The evaluation was performed to obtain the characterisation for the signal chain, such as impedances and crosstalk. The work started with a literature study in order to refresh and increase the knowledge that was needed before the practical work. Then measurements, computer aided simulations and comparisons between these were performed. Measurements were performed using TDR (Time Domain Reflectometry). The results showed the impedance levels along the signal chain. This was interesting since it showed how well the different parts in the system are matched. Unmatched parts result in reflections that disturb the transmitted signal and contribute to crosstalk, which also was measured. Simulations were done using ADS (Advance Design System), a tool from Agilent Technologies Inc. A substantial part of the simulation work was to build models of the real system. These models have been used for simulation. The simulation results were then compared to the measurement results. The results show that the system can be better matched concerning the channel impedance. There are large variations in impedance levels along the signal chain, resulting in signal reflections. Another effect studied is crosstalk between channels. Measurements and simulations showed the presence of crosstalk but it seems to be a minor problem in the current machine.