Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: Polydimethylsiloxane–polyester (PDMS-PES) copolymers produce materials which have enhanced properties and take advantage of the unique properties of the two very dissimilar components. The dissimilar nature of the components results in these types of materials typically having complex morphologies in the solid state as a result of phase segregation. When the polyester component is crystallisable, an even richer variation in morphology can be expected. The chain structure of the copolymer in terms of the distribution of the various segments along the chain and the variation in the composition also has a dramatic impact on the solid state morphology. In this study, two different types of polyesters were used to synthesise five series of PDMS-PES segmented copolymers and one series of PDMS-PES branched copolymer. The two polyester segments selected were polybutyleneadipate (PBA) and polybuthylenecyclohexancarboxylate (PBCH). The copolymers were synthesised via polycondensation in the melt state. Insights on many variations in the PDMS-PES copolymer synthesis are given. The copolymer series synthesized gave systematic series where the influence of the polyester type, chain architecture, bulk composition, block length, crystallinity and processing condition on the bulk and surface morphology could be studied. The remarkable variations in the properties of the copolymer were attributed to the differences in the copolymers morphology in terms of the microphase segregation, crystallization and the free volume properties. These variations were also found to alter the nature of the surface compositions and the related surface properties. Multiphase morphology exhibited in all the PDMS-PES copolymers and the type of morphology observed was dependent on PDMS contents, PDMS segment length and the degree of branching. Three types of morphology were observed: spherical micro-domains of PDMS in a matrix of PES, bicontinuous double diamond type morphology, and spherical micro-domains of PES in a matrix of PDMS. Spherical domains of the PDMS were also observed for low PDMS content copolymers between the crystalline polyester lamellae. The complexity of the PDMS-PBCH copolymer morphology was further investigated, using an extensive set of experimental data that has been drawn together with using positron annihilation lifetime spectroscopy (PALS) and developing and applying a new type of hyphenated technique between fractionation (chromatography) and microscopy (atomic force microscopy) techniques. The outcome has provided a unique perspective regarding the complexity of the PDMS-PBCH copolymer morphology, which is believed to provide basis for a theoretical structure-properties relationship in this fascinating class of thermoplastic material. / AFRIKAANSE OPSOMMING: Polidimetielsiloksaan–poliëster (PDMS–PES) kopolimere lewer verbindings met goeie eienskappe en trek voordeel uit die unieke eienskappe van die twee baie verskillende komponente. Aangesien die aard van hierdie twee verbindings baie verskil het hulle ‘n gekompliseerde morfologie in die vastetoestand as gevolg van faseskeiding. Wanneer die poliëster komponent kristalliseerbaar is kan ‘n nog ryker variasie in morfologie verwag word. Die kettingstruktuur van die kopolimere in terme van die verspreiding van die verskillende segmente al langs die ketting en die variasie in samestelling, het ook ‘n groot invloed op die vastetoestandmorfologie. In hierdie studie is twee verskillende tipes poliëster gebruik om vyf reekse PDMS–PES gesegmenteerde kopolimere en een reeks vertakte PDMS–PES kopolimere te berei. Die twee poliëstersegmente is polibutileenadipaat (PBA) en polibutileensikloheksaankarboksilaat (PBCH). Die kopolimere is berei deur middel van polikondensasie in die smeltfase. Inligting aangaande verskeie faktore in the bereiding van die PDMS–PES kopolimere is ingewin. Die reekse kopolimere wat berei is, het dit moontlik gemaak om die invloed van die tipe poliëster, kettingargitektuur, grootmaatsamestelling, bloklengte, kristalliniteit en reaksiekondisies op die oppervlakte en interne morfologie te bestudeer. Die opmerklike verskille in the eienskappe van die kopolimere word toegeskryf aan die verskille in die kopolimeermorfologie in terme van die mikrofaseskeiding, kristalliniteit en vryevolume eienskappe. Hierdie verskille het ook veranderings in die oppervlakte samestellings en verwante oppervlakte eienskappe teweeggebring. Multifase morfologie, in alle PDMS–PES kopolimere en die tipe morfologie wat waargeneem is, is afhanklik van die PDMS inhoud, die PDMS segmentlengte en die graad van vertakking. Drie tipes morfologie is waargeneem: sferiese mikro-gebiede van PDMS in ‘n PES matriks, ‘n bikontinueerlike dubbele-diamant tipe en sferiese mikro-gebiede van PES in ‘n PDMS matriks. Sferiese gebiede van die PDMS is ook waargeneem in kopolimere met ‘n lae PDMS inhoud tussen die kristallyne poliëster lae. Die kompleksiteit van die PDMS–PBCH kopolimeermorfologie is verder ondersoek deur gebruik te maak van ‘n wye reeks eksperimentele data afkomstig van positronvernietigingsleeftydspektroskopie (PALS), gevolg deur die ontwikkeling en toepassing van ‘n nuwe soort gekoppelde tegniek – tussen fraksionering (chromatografie) en mikroskopie (atoomkragmikroskopie) tegnieke. Die resultate het ‘n unieke perspektief gegee wat betref die kompleksiteit van die PDMS–PBCH kopolimeermorfologie en dien as ‘n basis vir die teoretiese struktuur–eienskapverwantskap van hierdie interessante klas termoplastiese materiale.

Profound sensorineural hearing loss is at the present time a major worldwide health concern, affecting over 5% of the worlds' population. Through cochlear implants (CI), treatment of sensorineural hearing loss now offers the possibility to restore hearing function through electrical stimulation of auditory nerves. Treatment is based on the surgical implantation of a thin, flexible array of microelectrodes into the cochlea. Nevertheless, availability of the treatment is limited due to high costs, and surgical insertion is associated with a high risk of trauma to the fragile soft tissue of the cochlea. At the heart of this thesis lies the proposition that these two problems may be addressed by the development of a novel type of cochlear implant founded on batch-producible, stretchable printed circuit board (PCB) technology. As an alternative to conventional cochlear implant fabrication, this thesis presents a fabrication process based on batch-producible stretchable PCB, featuring liquid alloy microchannels in place of solid metallic wire conductors. A series of proof-of-concept prototypes were designed, fabricated and evaluated. According to results obtained from evaluation of the prototypes, certain steps in the fabrication process were later revisited and improved upon. Preliminary prototype fabrication yielded batches of thin flexible cone-shaped electrode arrays designed for in-vivo evaluation in guinea-pig cochleae. In-vitro evaluation in 3D-printed cochlea models revealed that the prototypes were sufficiently thin and compliant for insertion 23 mm deep into a human cochlea and 4-6 mm into a guinea-pig cochlea, comparable to commercially available counterparts. Characterization of prototype test devices by optical microscopy, optical interferometry and resistance measurements revealed a high inherent variability in the developed fabrication process. In order to ensure consistently adequate quality, further improvement must be done. In particular, results of this work suggest that the deposition of liquid alloy involved in stretchable PCB fabrication should be automated to minimize uncertainty in the deposited liquid alloy thickness and thus enable further miniaturization of the stretchable PCB. Future efforts to successfully produce and integrate electrodes from soft materials, e.g. conductive polymer, liquid alloy or conductive hydrogels are highly recommended to further reduce implant stiffness.

In this study, we were particularly interested in looking at the possibility that cross metathesis of olefins in melt phase could be used to produce polydimethylsiloxane (PDMS) modified polypropylene (PP). The intention of this project was also to study and quantify relationships among the main experimental factors in the reaction: temperature, catalyst concentration and molar ratio of PP to PDMS, through a 2-level factorial statistical design. In order to examine if PP-PDMS copolymers were synthesized in the melt phase, measurement of the chemical, physical and viscoelastic properties of the synthesized copolymers was necessary. Techniques including proton (¹H)-nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), rheometry and scanning electron microscopy (SEM), were all used to characterize the synthesized copolymers. ¹H NMR measurements confirmed the presence of PDMS in the copolymers. They also provided a quantitative measurement of PP to PDMS molar ratio in copolymers by determining the integration of PP PDMS repeating unit signals in NMR spectra. Compared to virgin PP, a lower melting enthalpy of the PP phase in the copolymer was observed from DSC results. This implied that the PDMS component influenced the thermal behavior of the PP crystalline phase in the copolymers. Moreover, TGA measurements indicated that a higher thermal stability was obtained for PP-PDMS copolymers than that for virgin PP wax and this was expected since PDMS is known for its excellent stability at high temperature. Rheological analysis showed that the presence of PDMS in the copolymers gave lower complex viscosities and loss moduli, but higher storage moduli than those for virgin PP. Furthermore, the morphology of copolymers was examined by SEM and elemental analysis at the surface using an energy dispersive X-ray (EDX) analyzer on the SEM. It was found that micrographs of copolymers showed round domains on the surface, which were not observed in virgin PP wax and those round segments were confirmed to contain silicon. Torque values used in a batch mixer for polymerizations and the remaining weight % of copolymers at 350°C were used to conduct statistical analysis, through which models used to describe the relationships between experimental factors and these physical responses were determined.

Materials based on novel Off-Stoichiometry Thiol-Ene polymers, abbreviated OSTE, show promising properties as materials forlow cost and scalable manufacturing of micro- and nanosystems such as lab-on-chip devices. The OSTE materials have tunablemechanical properties, offer possibility for low temperature bonding to many surfaces via tunable surface chemistry, and can beused in soft lithography. Unlike the commonly used elastomer poly(dimethylsiloxane), PDMS, the OSTE materials have lowpermeability for gasses, are resistant to common solvents and can be more permanently surface modified.In this master’s thesis project, the OSTE materials have been evaluated with focus on compatibility with cells, possibility fornanostructuring using soft lithography and the use of OSTE as a flexible support for conducting polymers.Results from cell seeding studies with HEP G2 cells suggest that cells can proliferate on a low thiol off-stoichiometry OSTEmaterial for at least five days. The biocompatibility for this type of OSTE material may be similar to poly(styrene). However, highlevels of free thiol monomers in the material decrease cell viability considerably.By using soft lithography techniques it is possible to fabricate OSTE nanochannels with at least the dimensions of 400 nm x 15nm. Combined with the advantages of using the OSTE materials, such as low temperature bonding and possibility for stablesurface modifications, a candidate construction material for future development of systems for DNA analysis is at hand.OSTE can serve as a flexible support for an adsorbed film of a conducting polymer with the possibility for future applicationssuch as electronic interfaces in microsystems. In this project, a film of PEDOT:PSS with the electrical resistance of ~5 kΩ wascreated by adsorption to an flexible OSTE material. Furthermore, results suggest that it is possible to further optimize theconductivity and water resistance of PEDOT:PSS films on OSTE.

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This dissertation presents the development of novel nano-composite membranes as introduction systems for mass spectrometers. These nano-composite membranes incorporate anodic aluminum oxide (AAO) membranes as templates that can be used by themselves or modified by a variety of chemical deposition processes. Two types of nano-composite membranes are presented. The first nano-composite membrane has carbon deposited within the pores of an AAO membrane. The second nano-composite membrane is made by coating an AAO membrane with a thin polymer film. The following chapters describe the transmission properties these nano-composite membranes and compare them to conventional mass spectrometry introduction systems. The nano- composite membranes were finally coupled to the inlet system of an underwater mass spectrometer revealing their utility in field deployments.

Particle separation is of great interest to many biological and biomedical applications. Flow-based methods have been used to sort particles and cells. However, the main challenge with flow based particle separation systems is the need for a sheath flow for successful operation. Existence of the sheath liquid dilutes the analyte, necessitates precise flow control between sample and sheath flow, requires a complicated design to create sheath flow and separation efficiency depends on the sheath liquid composition. In addition, current gold standard active separation techniques are only capable of separation based on particle size; hence, separation cannot be achieved for same-size particles with different densities. In this dissertation, a sheathless acoustic-based microfluidic platform using surface acoustic wave for not only size-dependent but also density-dependent particle separation has been investigated. In this platform, two different functions were incorporated within a single microfluidic channel with varying the number of pressure node and position. The first function was to align particles on the center of the microfluidic channel without adding any external sheath flow. The second function was to separate particles according to their size or density. Two different size-pairs of polystyrene particles with different diameters (3 µm and 10 µm for general size-resolution, 3 µm and 5 µm for higher size-resolution) were successfully separated. Also, the separation of two 10 µm diameter, different-density particle streams (polystyrene: 1.05 g/cm3, melamine: 1.71 g/cm3) was successfully demonstrated. The effects of the input power, the flow rate, and particle concentration on the separation efficiency were investigated. A range of high separation efficiencies with 94.8-100 % for size-based separation and 87.2 - 98.9 % for density-based separation were accomplished. In this dissertation, an acoustic-based microfluidic platform using dual acoustic streaming for active mixing has also been investigated. The rapid and high efficiency mixing of a fluorescent dye solution and deionized water in a microfluidic channel was demonstrated with single acoustic excitation by one interdigital transducer (IDT) as well as dual excitation by two IDTs. The mixing efficiencies were investigated as a function of applied voltage and flow rates. The results indicate that with the same operation parameters, the mixing efficiency with dual-IDT design increased to 96.7 % from 69.8 % achievable with the traditional single-IDT design. The effect of aperture length of the IDT on mixing efficiency was also investigated. Additionally, the effects of the polydimethylsiloxane (PDMS) channel wall thickness on the insertion loss and the particle migration to the pressure node due to acoustic radiation forces induced by SAW have been investigated. The results indicate that as the PDMS channel wall thickness decreased, the SAW insertion loss is reduced as well as the velocity of the particle migration due to acoustic forces increased significantly. As an example, reducing the side wall thickness of the PDMS channel from 8 mm to 2 mm in the design results in 31.2 % decrease in the insertion loss at the resonant frequency of 13.3 MHz and 186 % increase the particle migration velocity at the resonant frequency of 13.3 MHz with input power of 27 dBm. Lastly, a novel acoustic-based method of manipulating the particles using phase-shift has been proposed and demonstrated. The location of the pressure node was adjusted simply by modulating the relative phase difference (phase-shift) between two IDTs. As a result, polystyrene particles of 5 µm diameter trapped in the pressure node were manipulated laterally across the microfluidic channel. The lateral displacements of the particles from -72.5 µm to 73.1 µm along the x-direction were accomplished by varying the phase-shift with a range of -180° to 180°. The relationship between the particle displacement and the phase-shift of SAW was obtained experimentally and shown to agree with theoretical prediction of the particle position.

Evaluation of solid-phase microextraction as an alternative official method for analysis of polymers migration. The objective this study was to compaire the official methods with solid-phase microextraction (SPME)for the analysis of compounds migrating from cross-linked polyethylene into water. A medium polarity polydimethylsiloxane/divinylbenzene (PDMS/DVB)was proved most efficient for the SPME extraction. However, when applied to water samples in contact with polyethylene, SPME proved to be immensely more sensitive and have a greater extraction range than liquid-liquid extraction (LLE). It was proved the migration of Phenol, 2,4-bis(1,1-dimethylethyl). Concentration of this compound 0,6-0,15mg/l.It was proved the migration of Cyclohexadiene-1,4-dione, 2,6-bis(1,1-dimethylethyl).

In this study, we were particularly interested in looking at the possibility that cross metathesis of olefins in melt phase could be used to produce polydimethylsiloxane (PDMS) modified polypropylene (PP). The intention of this project was also to study and quantify relationships among the main experimental factors in the reaction: temperature, catalyst concentration and molar ratio of PP to PDMS, through a 2-level factorial statistical design. In order to examine if PP-PDMS copolymers were synthesized in the melt phase, measurement of the chemical, physical and viscoelastic properties of the synthesized copolymers was necessary. Techniques including proton (¹H)-nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), rheometry and scanning electron microscopy (SEM), were all used to characterize the synthesized copolymers. ¹H NMR measurements confirmed the presence of PDMS in the copolymers. They also provided a quantitative measurement of PP to PDMS molar ratio in copolymers by determining the integration of PP PDMS repeating unit signals in NMR spectra. Compared to virgin PP, a lower melting enthalpy of the PP phase in the copolymer was observed from DSC results. This implied that the PDMS component influenced the thermal behavior of the PP crystalline phase in the copolymers. Moreover, TGA measurements indicated that a higher thermal stability was obtained for PP-PDMS copolymers than that for virgin PP wax and this was expected since PDMS is known for its excellent stability at high temperature. Rheological analysis showed that the presence of PDMS in the copolymers gave lower complex viscosities and loss moduli, but higher storage moduli than those for virgin PP. Furthermore, the morphology of copolymers was examined by SEM and elemental analysis at the surface using an energy dispersive X-ray (EDX) analyzer on the SEM. It was found that micrographs of copolymers showed round domains on the surface, which were not observed in virgin PP wax and those round segments were confirmed to contain silicon. Torque values used in a batch mixer for polymerizations and the remaining weight % of copolymers at 350°C were used to conduct statistical analysis, through which models used to describe the relationships between experimental factors and these physical responses were determined.

Zugl.: Tübingen, Univ., Diss., 2009