Ce travail a eu pour objectif la création de matériaux composites à base de nanocharges de carbonate de calcium. L'étude des phénomènes interfaciaux qui régissent ces systèmes, ainsi que leurs impacts sur les propriétés fonctionnelles du matériau et plus particulièrement des propriétés de transport, ont été réalisées. Pour ce faire, nous avons considéré deux matrices polymères de nature chimique différente : le polylactide et le polyfluore de vinylidène. Les nanocomposites ont été élaborés par deux voies de mise en œuvre : la voie fondu et la voix solvant. Une analyse fine des relations structure/morphologie/propriétés des composites a été réalisée. Nous avons mis en évidence, quelle que soit la matrice polymère choisie, l'importance du traitement de surface des charges afin d'améliorer leurs états de dispersion dans le matériau et d'augmenter la qualité de l'interface charge/polymère. Ces paramètres ont été corrélés aux propriétés de transport de ces matériaux composites. / The aim of this PhD work is to elaborate composites based on calcium carbonate nanoparticles. Polylactide and polyvinylidene fluoride were used as polymer matrix and nanocomposite were elaborated either by melting process and either by casting method. The interfacial behaviour between polymer and calcium carbonate were studied and we especially focused on their impact on the composite gas barrier properties. The importance of filler surface treatment had been highlighted on the filler dispersion state improvment and filler/polymer interface reinforcement. Both parameters were important in the improvement of composite gas barrier properties.

The study of impurity diffusion in semiconductor hosts is an important field that has both fundamental appeal and practical applications. Ion implantation is a good technique to introduce impurities deep into the semiconductor substrates at relatively low temperature and is not limited by the solubility of the dopants in the host. However ion implantation creates defects and damages to the substrate. Annealing process was used to heal these damages and to activate the dopants. In this study, we introduced several species such as alkali metals (Li, Na, K), alkali earth metals (Be, Ca,), transition metals (Ti, V, Cr, Mn) and other metals (Ga, Ge) into semiconductor substrates using ion implantation. The implantation energy varies form 70 keV to 200 keV and the dosages vary between ~ 1.0x1012 and ~5.0x1015 atoms/cm2. The samples are annealed at different temperatures from 300°C to 1000°C and for different time intervals. The redistribution behaviors of the implanted ions are studied experimentally using secondary ion mass spectrometry (SIMS). We observed some complex distribution behaviors due to the defects created during the process of ion implantation. The diffusivities of some impurities are calculated and compared to previous data. It was found that the diffusivities of implanted impurities is related to the dosages, annealing temperatures and the defects and damages caused by ion implantation. Additionally, as we go from one type of semiconductor to another, the diffusion behavior of the impurities shows a different trend.

Passivating-contact technologies fabricated from polycrystalline-silicon (poly-Si) are increasingly considered by the crystalline silicon (c-S) PV industry to be key enablers towards record performance. This is largely thanks to their ability to provide excellent carrier collection and surface passivation, while being compatible with industrial scale production. Poly-Si based passivating contacts consist of a stack of an ultrathin silicon oxide (SiOx) film on the surface of crystalline silicon (c-Si), covered by a doped silicon film. Thin films of SiOx can be grown by several different methods: chemically, thermally, or via UV-ozone exposure. However, each of these methods presents challenges towards industrial implementation. Here, we report an alternative method to grow SiOx films using an in-situ plasma process, where we subsequently deposit the doped poly-Si layer in the same process chamber by plasma enhanced chemical vapor deposition (PECVD). This process presents several advantages, such as ease of fabrication, inherently single-side oxide growth and poly-Si deposition, and the combined deposition in one chamber, lowering capital expenditure. Subsequently, we studied the structure of the SiOx films and the doped poly-Si(p+) capping layers using X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) in order to determine the films’ elemental composition, and the band alignment at the semiconductor/oxide interfaces. A less p-type polysilicon was observed grown on top of a wet SiOx/c-Si with the origin tentatively attributed to depletion of the boron dopant via pin holes evidenced by AFM. A surface photo-voltage (SPV) was observed by XPS under in-situ light bias (AM 1.5) and a representation of the band alignment of the c-Si/SiOx/p-polysilicon under illumination is derived. The SPV was attributed to the photo accumulation of holes at the p-polysilicon and a splitting of quasi-fermi levels with its magnitude correlated to the device measured iVoc . Finally, a valuable application for this contact technology is the integration of silicon with perovskite solar cells, in the so-called monolithic tandem configuration. This approach is very promising to develop a new generation of PV with unmatched performances. Here, poly-Si contacts offer a variety of advantages, thanks to their broader material selection and to the stability at high processing temperature.

Proper functioning of instruments requires precise calibration and routine quality assurance. In a clinical setting, this is achieved through the use of phantoms, which mimic the physical characteristics of tissues. Polyvinyl alcohol (PVA), a non-toxic, water-soluble polymer is well-suited for use as clinical phantom material. Through successive freezing and thawing, solutions of PVA in water can be solidified into rigid cryogels (PVA-C). The number of freeze-thaw cycles affects the properties of the material, including its optical characteristics. A double integrating sphere system was used in conjunction with the Inverse Adding Doubling (IAD) algorithm to characterize the optical properties of thin slab samples. The setup was evaluated using liquid phantoms. Liquid emulsion and food colouring were used to impart scattering and absorbing properties in the range characteristic of human tissue. Measured values of normalized reflectances and transmittances were entered into IAD, and a set of optical properties (μ′s,μa,g) retrieved. The reduced scattering coefficient was found to increase linearly with increasing lipid concentration, while a consistent overestimation of the absorption coefficient was observed. Measurements of PVA cryogels revealed a linear increase in the reduced scattering coefficient with an increasing number of freeze-thaw cycles up to five cycles. Scattering was also observed to increase with concentration up to PVA concentrations of 15%, and to spontaneously increase during the lifetime of the slab samples. These findings suggest it is possible to tune the optical scattering of PVA-C via different purely physical mechanisms. / Thesis / Master of Science (MSc)

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No description available.

The adhesion of poly(dimethyl siloxane) (PDMS) to silica substrates was measured by 90 degree peel testing of PDMS strips cast on silica substrates. The objective of this work was to investigate the effects of silica surface chemistry on the adhesion between PDMS and silica substrate. Silica substrates with different surface chemistry were prepared by both chemical modification and physical adsorption. Silane coupling agents were used to provide octyl chains and primary amino groups on the silica surfaces. Also silica surfaces were coated with cetyltrimethylammonium bromide (CTAB), polyvinylamine (PVAm) or poly(N-isopropylacrylamide) (PNIPAM) by physical adsorption. The adhesion samples were prepared by casting Sylgard® 184 silicone elastomers on silica surfaces followed by thermal curing. Water contact angle measurements, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared microscopy (FTIR) were performed to measure the surface properties of the peel test samples. It is believed that hydrogen bonding between siloxane bonds in PDMS and silanol groups on silica substrate contributes to the strong adhesion of PDMS and silica surface. The adhesion forces significantly reduced by the adsorption of PVAm and PNIPAM onto silica surfaces. In addition, the introduction of primary amino groups on silica surface would poison the catalyst during the curing of PDMS, which causes the formation of low crosslinking PDMS in the outer surface and is expected to decline the adhesion force. Lastly, the slightly reduce of adsorbed PVAm (340 kDa) on the silica substrate after peel test is considered to be useful for long-term lubrication. / Thesis / Master of Applied Science (MASc)

Copolymer-cobalt complexes have been formed by thermolysis of dicobalt octacarbonyl in solutions of copolysiloxanes. The copolysiloxane-cobalt complexes formed from toluene solutions of PDMS-b-[PMVS-co-PMTMS] block copolymers were annealed at 600-700 °C under nitrogen to form protective siliceous shells around the nanoparticles. Magnetic measurements after aging for several months in both air and in water suggest that the ceramic coatings do protect the cobalt against oxidation. However, after mechanical grinding, oxidation occurs. The specific saturation magnetization of the siliceous-cobalt nanoparticles increased substantially as a function of annealing temperature, and they have high magnetic moments for particles of this size of 60 emu g⁻¹ Co after heat-treatment at temperatures above 600 °C. The siliceous-cobalt nanoparticles can be re-functionalized with aminopropyltrimethoxysilane by condensing the coupling agent onto the nanoparticle surfaces in anhydrous, refluxing toluene. The concentration of primary amine obtained on the surfaces is in reasonable agreement with the charged concentrations. The surface amine groups can initiate L-lactide and the biodegradable polymer, poly(L-lactide), can be polymerized directly from the surface. The protected cobalt surface can also be re-functionalized with poly(dimethylsiloxane) and poly(ethylene oxide-co-propylene oxide) providing increased versatility for reacting polymers and functional groups onto the siliceous-cobalt nanoparticles.Phthalonitrile containing graft copolysiloxanes were synthesized and investigated as enhanced oxygen impermeable shell precursors for cobalt nanoparticles. The siloxane provided a silica precursor whereas the phthalonitrile provided a graphitic precursor. After pyrolysis, the surfaces were silicon rich and the complexes exhibited a substantial increase in Ms. Early aging data suggests that these complexes are oxidatively stable in air after mechanical grinding. Aqueous dispersions of macromolecule-magnetite complexes are desirable for biomedical applications. A series of vinylsilylpropanol initiators, where the vinyl groups vary from one to three, were prepared and utilized for the synthesis of heterobifunctional poly(ethylene oxide) oligomers with a free hydroxy group on one end and one to three vinylsilyl groups on the other end. The oligomers were further modified with carboxylic acids via ene-thiol addition reactions while preserving the hydroxyl functionality at the opposite terminus. The resulting carboxylic acid heterobifunctional PEO are currently being investigated as possible dispersion stabilizers for magnetite in aqueous media. / Ph. D.

Statistical copolymers of acrylonitrile (AN) and methyl acrylate (MA) were successfully prepared and characterized using reversible addition-fragmentation chain transfer (RAFT) copolymerization. A typical copolymer was charged with 15 wt. % MA content. This thesis describes a systematic variation of the RAFT copolymerization variables to optimize this system. In particular, the effects of chain transfer agent, initiator, temperature, and solvent on the copolymer properties were studied. / Master of Science

Polylactide-siloxane triblock copolymers with pendent carboxylic acid functional groups have been designed and synthesized for study as magnetite nanoparticle dispersion stabilizers. Magnetic nanoparticles are of interest in a variety of biomedical applications, including magnetic field-directed drug delivery and magnetic cell separations. Small magnetite nanoparticles are desirable due to their established biocompatibility and superparamagnetic (lack of magnetic hysteresis) behavior. For in-vivo applications it is important that the magnetic material be coated with biocompatible organic materials to afford dispersion characteristics or to further modify the surfaces of the complexes with biospecific moieties. The synthesis of the triblock copolymers is comprised of three reactions. Difunctional, controlled molecular weight polymethylvinylsiloxane oligomers with either aminopropyl or hydroxybutyl endgroups were prepared in ring-opening redistribution reactions. These oligomers were utilized as macroinitiators for ring-opening L-lactide to provide triblock materials with polymethylvinylsiloxane central blocks and poly(L-lactide) endblocks. The molecular weights of the poly(L-lactide) endblocks were controlled by the mass of L-lactide relative to the moles of macroinitiator. The vinyl groups on the polysiloxane center block were further functionalized with carboxylic acid groups by adding mercaptoacetic acid across the pendent double bonds in an ene-thiol free radical reaction. The carboxylic acid functional siloxane central block was designed to bind to the surfaces of magnetite nanoparticles, while the poly(L-lactide)s served as tailblocks to provide dispersion stabilization in solvents for the poly(L-lactide). The copolymers were complexed with magnetite nanoparticles by electrostatic adsorption of the carboxylates onto the iron oxide surfaces and these complexes were dispersible in dichloromethane. The poly(L-lactide) tailblocks extended into the dichloromethane and provided steric repulsion between the magnetite-polymer complexes. / Master of Science