Yes / Interpolymer complexes of homopolymer macromolecules are often described as ‘laddered’ or ‘ribbon’ type structures. The proposition of the existence of these ladder structures seems to us not reasonable and here we examine this hypothesis. To address this we have used polymers enabled for Förster Energy Transfer (FRET). Chromophores bound to a macromolecular backbone can transfer energy across short distances via FRET. The close binding of poly(acrylamide) and poly(acrylic acid) interpolymer complex formation at low pH forms a structure compact enough for significant energy transfer to occur between different chains containing naphthalene and anthracene labels. In the context of the proposition that ladder polymers can form it was surprising that the distance between labels on the same polymer back-bone was equivalent regardless of whether the polymer was complexed or not. The data indicated that the bicomponent structure may be more compact than previously supposed: I.e. the complexes are not ladders composed of extended chains. This evidence suggests formation not of ordered ‘ladder’ systems but colloidal ‘co-globules’. / This work was carried out in part thanks to an EPSRC CASE funded PhD studentship at the University of Sheffield, sponsored by SNF (UK) Ltd.

Shape memory alloys (SMAs) are unique metallic alloys which can undergo large deformations while reverting back to their undeformed shape through either the application of heat (shape memory effect) or the removal of the load (superelastic effect). A multi-scale and multi-disciplinary approach is taken to explore the use of large diameter NiTi SMAs for applications in earthquake engineering. First, a materials characterization study is performed by studying precipitate formation, grain size and orientation, thermal transformation behavior, and strength. Cyclic tensile tests on coupon specimens and full-scale large diameter bars are then used to correlate the microstructural properties to the macroscopic behavior. Further experimental studies using NiTi wire are performed in order to optimize their properties for seismic applications. The ability of mechanical training to stabilize NiTi cyclic properties, the ability of pre-straining to increase damping levels, and the influence of different types of earthquake loadings are considered. Phenomenological mechanical models are then developed based on these results. An analytical study is then used to evaluate the performance of structural systems incorporating SMAs. One type of system evaluated includes an SMA bracing system used to modify the response of a structure during a seismic event. Overall, the results of this study have shown the ability to optimize the properties of NiTi SMAs for seismic applications through material processing. The analytical results show potential for the use of SMAs in seismic applications and provide areas for continued research.

Magnetorheologische Elastomere sind eine Klasse von Smart Materials, welche elastische mit magnetischen Materialeigenschaften verbindet. Die Einbettung von magnetischen Mikropartikeln in eine Elastomermatrix führt zu einem komplexen, bisher nicht vollständig verstandenen Materialverhalten. Die Beeinflussbarkeit der mechanischen Eigenschaften mittels von außen applizierten Magnetfeldern stellt die herausragende und namensgebende Eigenschaft dieser Materialien dar. Das Verständnis der mikroskopischen Anordnung und der magnetisch induzierten Bewegung der eingebetteten Partikel bildet den zentralen Schlüssel zur Ergründung der komplexen makroskopischen Materialeigenschaften. Um sich diesem Ziel zu nähern, wurden unterschiedlichste breitgefächerte Messmethoden auf mikroskopische und makroskopische Aspekte eines einzigen Probenmaterials angewendet. So entstand eine umfassende und skalenübergreifende Charakterisierung eines magnetorheologischen Elastomers. Kern der Experimente bildete die Analyse der Anordnung und der magnetisch induzierten Bewegung der eingebetteten magnetischen Mikropartikel mittels Röntgen-Mikrotomographie. Die tomographisch erhobenen Bilddaten ermöglichten sowohl eine Auswertung der Partikelstruktur auf Basis der Partikelgesamtheit, als auch auf Einzelpartikelbasis mit Hilfe eines Particle-Tracking. So konnten neue Erkenntnisse über den magnetisch induzierten Kettenbildungsprozess der Partikel gewonnen und skalenübergreifende Zusammenhänge zwischen mikroskopischen Partikelbewegungen und makroskopischen mechanischen Materialverhalten aufgezeigt werden.:Danksagung v Inhaltsverzeichnis vii Symbolverzeichnis ix Abkürzungsverzeichnis xii 1 Einleitung 1 2 Grundlagen 8 2.1 Magnetorheologische Elastomere 8 2.1.1 Elastomermatrix 8 2.1.2 Magnetische Partikel 10 2.1.3 Magnetische Eigenschaften 11 2.1.4 Partikelstruktur und mechanische Eigenschaften 19 2.2 Mikrostrukturanalyse 22 2.2.1 Röntgentomographie 23 2.2.2 Digitale Bildverarbeitung 32 2.2.3 Statistik von Partikelverteilungen 37 3 Materialien und Methoden 39 3.1 Probenmaterial 39 3.1.1 Wahl geeigneter Materialien 39 3.1.2 Probensynthese 42 3.2 Messmethoden 44 3.2.1 Messkampagnen 45 3.2.2 Mechanische Charakterisierung 49 3.2.3 Mikrostrukturanalyse 52 3.2.4 Auswertung der Bilddaten 58 3.2.5 Vibrating Sample Magnetometrie 72 3.2.6 Begleitende Messmethoden 73 4 Ergebnisse 78 4.1 Makroskopische mechanische Eigenschaften 78 4.1.1 Elastomer 78 4.1.2 Komposit 79 viii Inhaltsverzeichnis 4.2 Partikelstruktur im Ausgangszustand 83 4.2.1 Datenlage 83 4.2.2 Geometrische Charakterisierung der Partikel 86 4.2.3 Räumliche Verteilung der Partikel 89 4.3 Partikelstruktur im Magnetfeldeinfluss 90 4.3.1 Ausrichtungsverhalten der Partikel im Magnetfeld 91 4.3.2 Einbindung der Partikel in die Matrix 93 4.3.3 Statistische Verteilung der Partikelwinkel 96 4.3.4 Partikelbewegung als Reaktion auf das lokale Feld 101 4.3.5 Partikelbewegung als Reaktion auf sukzessive Magnetisierung 114 4.3.6 Paarkorrelationsfunktionen der Partikelstruktur 123 4.4 Magnetische Eigenschaften 130 5 Zusammenfassende Diskussion 135 5.1 Gewonnene Erkenntnisse 135 5.2 Gegenseitige Beeinflussung von Partikelstruktur, magnetischen und mechanischen Eigenschaften 137 5.3 Grenzen der Messgenauigkeit und Fehlerbetrachtung 137 6 Abschließende Worte und Ausblick 140 Literaturverzeichnis I Abbildungsverzeichnis XIII Tabellenverzeichnis XVII

The objective of this work is to understand the structure-property relationships in a pseudoelastic composition of polycrystalline NiTiPt (Ti-42.7 at% Ni-7.5 at% Pt). Structural characterization of the alloy includes grain size determination and texture analysis while the thermo-mechanical properties are explored using tensile testing. Variation in heat treatment is used as a vehicle to modify microstructure. The results are compared to experiments on Ni-rich NiTi alloy wires (Ti-51.0 at% Ni), which are in commercial use in various biomedical applications. With regards to microstructure, both alloys exhibit a <111> fiber texture along the wire drawing axis, however the NiTiPt alloy's grain size is smaller than that of the Ni-rich NiTi wires, while the latter materials contain second phase precipitates. Given the nanometer scale grain size in NiTiPt and the dispersed, nanometer scale precipitate size in NiTi, the overall strength and ductility of the alloys are essentially identical when given appropriate heat treatments. Property differences include a much smaller stress hysteresis and smaller temperature dependence of the transformation stress for NiTiPt alloys compared to NiTi alloys. Potential benefits and implications for use in vascular stent applications are discussed.

For passive (classical) materials, stress and strain are used to extract the material behavior from the sample behavior in a tensile test. In analogy, the actuation behavior of active (smart) materials can be normalized. In the present research, we show the normalization using the example of hydrogels that react with a volume change (swelling and deswelling) when exposed to stimulus-changes like temperature, chemical concentrations, pH or light intensity changes. The normalized behavior can then be implemented with the Temperature-Expansion-Model which is based on the analogy of active behavior with thermal expansion. This allows the simulation of arbitrary active structures and the extraction of the sensitivity measure to a stimulus.

It is common knowledge that water is one of the basic needs for human beings. However, the consumption of contaminated water can lead to waterborne diseases and fatalities. It is, therefore imperative to constantly monitor the quality of potable water. There are numerous technologies used for water quality monitoring. These technologies are relatively effective however these tests are expensive and complex to use, which then require experienced technicians to operate them. Other tests are not rapid, making consumers of water susceptible to waterborne diseases. In this study, dye-doped, surface functionalized silica nanoparticles (SiNPs) and surface-functionalized magnetic nanocomposites (MNCs) were proposed as materials that can be applied in order to reduce the time taken to get results as well as to make the processes less complex and portable. The aim of this study was to synthesize and characterize surface functionalized dye-doped SiNPs and surface functionalized MNCs for detection and preconcentration of in water. Additionally, proof of concept had to be shown using the synthesized materials. SiNPs were the materials of choice due to their easily functionalized surfaces and their strong optical properties. SiNPs are photostable and they do not leach in solution due to the inert nature of the silica matrix in aqueous media. MNCs were chosen as materials of choice for preconcentration of E. coli in water because they are easy to synthesize and they can be applied in various biological applications due to their functional groups. SiNPs were synthesized using the water-in-oil microemulsion. The SiNPs were further functionalized with amine and carboxyl groups and avidin. Thereafter, they were bioconjugated with biotinylated anti-E. coli antibodies. The pure and surface functionalized SiNPs were characterized using ATR-FTIR spectroscopy, FE-SEM, HR-TEM, Zeta Sizer, UV-vis spectroscopy and spectrofluorometry. The application of the dye—doped surface functionalized SiNPs in E. coli detection was characterized using the fluorescence plate reader. The SiNPs were spherical and uniform in size. They increased in size as they were being functionalized, ranging from 21.20 nm to 75.06 nm. The SiNPs were successfully functionalized with amine and carboxyl groups as well as with avidin and antibodies. Two methods were investigated for carboxyl group attachment (direct and indirect attachment) and the direct attachment method yielded the best results with a surface charge of -31.9 mV compared to -23.3 mV of the indirect method. The dye loading was found to be 1% after particle synthesis. The optical properties of the Ru(Bpy) dye were enhanced 3 fold when they were encapsulated in the Si matrix. The SiNPs were binding to the E. coli cells and enabled detection. MNCs were synthesized through in-situ polymerization. The MNCs were characterized using ATR-FTIR spectroscopy, SEM, TEM and XRD. The MNCs were successfully functionalized with carboxyl groups. The increase in size of the nanocomposites as seen in SEM images proved that the Fe3O4 was successfully encapsulated in the polymer matrix. The MNCs were proven to be magnetic by a simple magnetism test whereby they were separated in an aqueous solution using an external magnetic field. The antibody-labelled MNCs were binding to the E. coli cells as shown in TEM images. E. coli cells were removed from water at varying concentrations of 1x106 CFU/mL to 1x109 CFU/mL at 10 mL volumes. This study has demonstrated that dye-doped SiNPs amplify the signal of E. coli cells using fluorescence. The study has also demonstrated that the MNCs can be applied in sample preconcentration and enrichment for E. coli detection. However, further studies should investigate and optimize the combination of the two techniques in a point of use device for water quality testing of 100 mL-samples as per the requirement of the SANS 241 standard. / Civil and Chemical Engineering / M. Tech. (Chemical Engineering)

The present thesis work deals with the development of a novel manufacturing protocol for the realization of excimer laser micro-patterned freestanding hydrogel layers (50 to 300 ??m thickness) based on thermo-responsive poly-(N-isopropyl)acrylamide (PNIPAAm) which can operate as temperature-triggered actuators for cells-on-chip applications. PNIPAAm based thin films were synthesized in house and manufactured by an injection/compression moulding based technique in order to obtain flat hydrogels attached to rigid polyvinyl chloride (PVC) substrates to facilitate laser focusing. Laser machining parameters were empirically optimized to fabricate arrays of through-holes with entrance diameter ranging from 30 ??m to 150 ??m and having different exit diameter (from 10 to 20 ??m) on the PNIPAAm employing a stencil aluminum mask. After laser processing, the microstructured layers were detached from the PVC using a chemical treatment and then left to swoll in pure water. The KrF excimer laser machined through-holes could be reversibly modulated in terms of size as a consequence of the polymer volumetric phase transition induced by a temperature change above the critical value of 32 ??C. Thermo-responsiveness characterization was carried out on the detached water swollen freestanding layers using a thermostat bath, by changing the temperature from 18 ??C to 39 ??C and each sample could undergo multiple cycles. As a result of the polymer water loss, the shrinkage of the layer caused the holes to shrink homogeneously, thus reducing their original size of about the 50% in the polymer collapsed state. To prove the functionality of these stimuli-responsive smart surfaces in the frame of cells-on-chip systems, they were integrated in a multilayer microfluidic device to operate as self-regulating cell sorting actuators for single cell assays applications. Using mechanical fastening as the packaging strategy, the hydrated hydrogel was sealed between two micro-milled poly-methyl methacrylate (PMMA) components, which provided the fluid accesses and ducts to the cell suspension to be flown over the thermoresponsive actuator (top layer) and the well to collect the sorted sample (bottom layer). The device is also equipped with a thin transparent heater to control the microfluidic chip temperature. When the system is assembled, the temperature-triggered actuation mechanism was exploited to trap a cellular sample in the shrunken exit hole on the top of the hydrogel layer by applying a negative pressure across the film via the bottom PMMA component when the system is kept at 37 ??C. Subsequently, the sorting of the trapped cell took place through the micro-capillary when the polymer natural relaxation at room temperature towards its initial state occurred; the operational principle of the device was proved using MG63 cells as a model cell line by monitoring the sorting through the size-modulating structures using optical microscopy.

published_or_final_version / Mechanical Engineering / Doctoral / Doctor of Philosophy

It is more than a decade that Ionic Polymer-Metal Composites (IPMCs) have been known as an exciting class of smart materials and attracted growing worldwide attention. IPMCs are soft and flexible, and can generate large and reversible strains in response to electrical stimulus. Thus, they have potential applications in industrial and biomedical fields, as actuators. Before these applications can be realized , however, the performance of IPMCs must be understood and improved through improvement of component characteristics and of preparation methods. In general, the aim of this thesis is to gain a fundamental understanding of the chemical and structural factors that affect the electromechanical performance of IPMCs. To this end, a multi-technique investigation is applied to correlate the electrochemical and electromechanical behavior of IPMCs, during operation, with their chemistry, microstructure and nanostructure. Researchers have suggested several plausible mechanical and mathematical models to reveal that ion transport occurs within IPMCs and that it is an important factor in their actuation performance. However, there is still a need for further experimental studies to help refine our understanding of the actuation mechanism of these materials. In this work, the powerful, non-invasive and non-destructive technique of Magnetic Resonance Imaging (MRI) is employed to study the internal structure and water content distribution in Nafion membranes and also IPMCs. Moreover, MRI is also applied to image electrically-induced diffusion of ions with their associated water molecules in real time, in operating IPMC actuators. This forms the major part of this project and, to the best of our knowledge, it is the first recorded electrochemical experiment of this kind. The size and dimensions of IPMCs can affect their actuation performance. Thus, in this work, model IPMC actuators are prepared based on the available commercial Nafion membrane and fabricated cast Nafion membrane and their electromechanical behaviors are compared. The effect of parameters such as electrode composition and Nafion thickness on actuation behavior is also studied by measuring displacement and force generation of the IPMC actuators during actuation cycles. Simultaneous current and electrochemical measurements are made to correlate electrochemical processes with actuation behavior directly. Scanning electron microscopy (SEM) is also used to study the internal and surface structure of IPMCs.

A Research Report Submitted to the Faculty of Commerce, Law and Management, Witwatersrand University School of Economics and Business Sciences, In partial fulfilment of the requirements of a Master Degree in Marketing, May 2017 / The consumer market of Smart wearable technology has shown a massive growth, therefore convincing that Smart wearable technology will be the next great thing, with market analysts forecasting its market to be worth over $30 billion by 2020. However this belief is mainly driven by major new technology manufacturers to produce Smart wearable devices that commoditise cellphones, tablets, and portable computers to influence consumer purchase intention. Consumers purchase intention is crucial for every business survival, therefore cannot be overemphasised. With the increasing number of Smart wearable technology brands on the electronics market, South African consumers have to make a choice on which brands to purchase. This study examines the factors influencing the purchase intention of Smart wearable technology in South Africa, with a special focus on product quality, design, price, and consumer attitude. From the academic side, the study makes a significant contribution by exploring the impact of product price and consumer attitude on consumer purchase intention. As a result, manufacturers in the wearable technology industry may apply this study information to develop proper strategies that will help influence more people to purchase wearable devices and ensure Smart wearable technology market growth. The study data were collected through the aid of a self-administered hardcopy questionnaire, which was circulated by the researcher in the University of the Witwatersrand Johannesburg. The research findings show that both consumer attitude and product price have a significant positive effect on the intention to purchase Smart wearable devices. Nevertheless, to be more precise, the effect of consumer’s attitude on purchase intention goes through the positive effect of a product design on consumer’s attitude. Both product quality and price are found to extend the effect of positivity of consumer’s attitude toward the product or brand, and the price tag of the product. These scenarios are fully supported in hypotheses one, two, and three. Although both quality and design positively influence product price, Product design is found to have an enlarging effect on product price. Generally, it can be stated that the design of a product successfully influence the price set for product. / XL2018