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<p>The development of finely dispersed powders and superfine-grained materials intended for application in various areas of science and engineering is one of the challenges facing modern nanotechnology. Thus, specific fundamental and applied research was required in order to consolidate advancement made in preparing nano- and submicron crystalline composite materials.</p> <p><br /> Useful templates for electrochemical deposition of nanowires include porous alumina films formed by anodic oxidation of aluminium, nuclear track-etched porous membranes, nanochannel array-glass and mesoporous channel hosts. The properties of the nanowires are directly related to the properties of the nanoporous templates such as, the relative pore orientations in the assembly, the pore size distribution, and the surface roughness of the pores. The template synthesis method, based on the use of porous polymeric and inorganic matrixes, is now actively used for synthesis of such composite materials. The method allows the chemical and/or electrochemical synthesis of nano- and microstructured tubes and wires consisting of conducting polymers, metals and semiconductors.</p> <p><br /> In this study various technological challenges relating to template synthesis and development of nickel nano- and microstructures on adequately strong and durable substrates were investigated. The two methods used were the electrochemical and chemical deposition. &ldquo / Hard nickel&rdquo / bath solution was used for optimal nickel deposition. This optimization included investigating variables such as the template structure, type of electrolyte and form of electrolytic deposition. Scanning Electron Microscopy was used to investigate the structures of template matrixes and the resultant materials. The cyclic voltammetry method was applied for the analysis of electrochemical properties and hydrogen evaluation reaction of nano- and microstructured nickel based electrodes. The activity of composite nano- and microstructured materials in various configurations resulting from pore filling of template matrices by nickel was explored. Studies of the physical structure and chemical properties of the nanostructured materials included investigating the necessary parameters of template matrices. The optimum conditions of synthesis, which allowed development of materials with the highest catalytic activity, were determined.&nbsp / The effect of the template structure on microcrystallinity of the catalyst particles was established using the XRD method. Different new types of non-commercial asymmetric ion track membranes has been tested for nanostructure preparation. The catalytic activity of the new developed nanomaterials is higher as compared to materials using commercial templates. The procedures to modify the newly developed nickel catalyst with Pt, Pd and Pt-Pd alloy have been developed. The Pt and Pt-Pd alloy containing catalyst showed the best performance in water electrolysis. In this work, the promising role for specific application of the new materials in hydrogen economy has been demonstrated.</p>

The aim of this project was to investigate methods for purification and modification of Single Wall and Multi Wall Carbon Nanotubes. Covalent and noncovalent approaches to functionalization were studied. The dispersibility, structure and electronic properties of modified tubes were characterized by Raman, UV-vis-NIR and XPS. Fluorescence, NMR and TEM were further employed to characterize the interaction between nanotubes and non-covalent modifiers. The effects of five different purification methods on the dispersibility, and degree of carboxylic acid functionality of SWCNTs, along with the level of defects on the tube side walls, and the resulting electronic properties of SWCNTs have been investigated. It was found that all oxidation treatments successfully removed metallic oxides and amorphous carbon impurities, while different oxidation treatments introduced different levels of oxidized sites on the SWCNTs. Heat treatment after oxidation eliminated some of the carboxylic groups introduced by oxidation. SWCNTs covalently functionalized by aromatic diazonium salts containing nitro, carboxylate and fluoro groups on the aromatic ring were prepared. Heating of these tubes in vacuum at 350_C for 5 h partially reversed the effects of functionalization. However, due to the low degree of functionalization achieved in the preliminary studies, the dispersibility/solubility of functionalized tubes did not greatly improve. The interaction in stable suspensions of CNTs with positively or negatively charged pyrene derivatives via noncovalent functionalization, was extensively studied. 1-pyrene methylamine hydrochloride gave most stable dispersions. 1H and 2H NMR spectroscopy of MWCNTs/1-pyrene methylamine hydrochloride dispersion in DMF-d7 showed that the broadened signals are associated with weakly or unbound pyrene, while strongly bound pyrene is not observable in solution-state NMR. The strong pyrene attachment on MWCNTs by π-π stacking can be reversed by dialysis and/or extensive washing. Biological molecules such as polypeptides and amino acids also dispersed MWCNTs into solvents by noncovalent modification. It is found that polytryptophan demonstrated the greatest ability to disperse MWCNTs. Digestion with chymotrypsin enabled polytryptophan binding to be reversed. A combination of tube cutting and non-covalent functionalization by pyrenes or peptides enables tubes to be suspended/dissolved in solvents such as DMF and ethanol, and significantly allows tubes to be manipulated for practical device applications.

Philosophiae Doctor - PhD / The development of finely dispersed powders and superfine-grained materials intended for application in various areas of science and engineering is one of the challenges facing modern nanotechnology. Thus, specific fundamental and applied research was required in order to consolidate advancement made in preparing nano- and submicron crystalline composite materials. Useful templates for electrochemical deposition of nanowires include porous alumina films formed by anodic oxidation of aluminium, nuclear track-etched porous membranes, nanochannel array-glass and mesoporous channel hosts. The properties of the nanowires are directly related to the properties of the nanoporous templates such as, the relative pore orientations in the assembly, the pore size distribution, and the surface roughness of the pores. The template synthesis method, based on the use of porous polymeric and inorganic matrixes, is now actively used for synthesis of such composite materials. The method allows the chemical and/or electrochemical synthesis of nano- and microstructured tubes and wires consisting of conducting polymers, metals and semiconductors.In this study various technological challenges relating to template synthesis and development of nickel nano- and microstructures on adequately strong and durable substrates were investigated. The two methods used were the electrochemical and chemical deposition. &ldquo;Hard nickel&rdquo; bath solution was used for optimal nickel deposition. This optimization included investigating variables such as the template structure, type of electrolyte and form of electrolytic deposition. Scanning Electron Microscopy was used to investigate the structures of template matrixes and the resultant materials. The cyclic voltammetry method was applied for the analysis of electrochemical properties and hydrogen evaluation reaction of nano- and microstructured nickel based electrodes. The activity of composite nano- and microstructured materials in various configurations resulting from pore filling of template matrices by nickel was explored. Studies of the physical structure and chemical properties of the nanostructured materials included investigating the necessary parameters of template matrices. The optimum conditions of synthesis, which allowed development of materials with the highest catalytic activity, were determined.&nbsp; The effect of the template structure on microcrystallinity of the catalyst particles was established using the XRD method. Different new types of non-commercial asymmetric ion track membranes has been tested for nanostructure preparation. The catalytic activity of the new developed nanomaterials is higher as compared to materials using commercial templates. The procedures to modify the newly developed nickel catalyst with Pt, Pd and Pt-Pd alloy have been developed. The Pt and Pt-Pd alloy containing catalyst showed the best performance in water electrolysis. In this work, the promising role for specific application of the new materials in hydrogen economy has been demonstrated. / South Africa

Plasmonic nanostructures, like noble metal, have gained large attention due to their plasmonic properties so they can reach areas like electronics, photo-catalysis, biomedicine, and sensing. Plasmonic nanomaterials are known for their local surface plasmon resonance and enhanced electromagnetic field and wavelength dependence. The higher the electromagnetic field at the surface of the nanoparticles can interact with nearby molecules, the bigger the influence is on the intensity of the molecule signals. This phenomenon is called surface-enhanced Raman scattering (SERS) and plasmonic enhanced fluorescence (PEF), which enable the plasmonic nanomaterials as a signal amplifier. By using these plasmonic nanostructures as a signal amplifier, SERS and PEF have become ultrasensitive methods in biomedicine and biosensing. Plasmonic biosensing is fast and label-free detection of biologically relevant analytes in real time. The objective of my doctoral dissertation focusses on developing new plasmonic nanostructures for detecting biomarkers related to cancers and some other diseases based on hybrid platforms. In this work, a newly spiky nanostructure was developed, internal standard Raman molecules were embedded into the nanostructure for quantitative SERS detection of polycyclic aromatic hydrocarbons molecules. Then the morphology and dispersity of this nanostructure were optimized to get an approximately fusiform shape, which showed a stable, reproducible and high SERS signals. This nanostructure was furtherly functionalized by double strand DNA and aptamer, showing a good performance in drug delivery and detecting circulating tumor cells. Inspired by the mechanism of SERS, a SERS and PEF dual model sensor based on plasmonic nanostructures and newly synthesized probe molecules was developed. This dual model sensor combined the advantages of SERS and PEF and exhibited a lower limit of detection of γ-glutamyl transferase in living cells. This dissertation contains the fabrication of newly plasmonic nanostructures and utilizing them in bioanalysis.

Magnetoelectric (ME) materials are attracting increasing attention due to the achievable reading/writing source (electric field and magnetic field in most cases), fast response time, and larger storage density. Therefore, nanocomposites featuring both magnetostriction and piezoelectricity were investigated to increase the converse magnetoelectric (CME, α) coefficient. Among all the nanocomposites, vertically/horizontally-integrated heterostructures were investigated; these materials offer intimate lattice contact, lower clamping effect, dramatically enhanced α, easier reading direction, and the potential to be patterned for complicated applications. In the present work, we focused on three principal goals: (a) creating two-phase vertically integrated heterostructures with different ME materials that provide much larger α, and enhanced strain-induced magnetic shape anisotropy compared with the single-phased ME nanomaterials; (b) creating a vertically integrated heterostructure with large α, lower loss, and higher efficiency; and (c) investigating the stable magnetization states that this heterostructure could achieve, and how it can be used in advanced memory devices and logic devices. Firstly, a BiFeO3-CoFe2O4 (BFO-CFO) heterostructure was epitaxially deposited on Pb(Mg1/3Nb2/3) O3-x at%PbTiO3 (PMN-xPT). The resulting PMN-xPT was proven to have a large piezoelectric effect capable of boosting the CME in the heterostructure to create a much higher α. Secondly, a novel material, CuFe2O4 (CuFO), featuring lower coercivity and loss, was chosen to be self-assembled with BFO. This low-loss could increase the efficiency of the ME effect. Also, our findings revealed a much larger α in the vertically integrated heterostructure compared to single-layer CuFO. Accordingly, the self-assembled structure represents a convenient method for increasing the CME in multiferroic materials. Thirdly, the magnetization states for all these vertically integrated heterostructures were studied. Note that vertically integrated heterostructures are typically fabricated using materials with volatile properties. However, these composites have shown a non-volatile nature with a multi-states (N≥4), which is favored for multiple applications such as multi-level-cell. Moreover, several self-assembled heterostructures were created that are conducive to magnetic anisotropy/coercivity manipulation. One such example is Ni0.65Zn0.35Al0.8Fe1.2O4 (NZAFO) with BFO, which forms a self-assembled nanobelt heterostructure that exhibits high induced magnetic shape anisotropy, and is capable of manipulating magnetic coercivity (from 2 Oe to 50 Oe) and magnetic anisotropy directions (both in-plane and out-of-plane). Finally, we deposited a SrRuO3-CoFe2O4 (SRO-CFO) vertically integrated composite thin film on the single crystal substrate PMN-30PT, with a CFO nanopillar and SRO matrix. In such a heterostructure, the SRO would serve as the conductive materials, while CFO offers the insulated property. This unique conductive/insulating heterostructure could be deposited on PMN-PT single crystals, thus mimicking patterned electrodes on the PMN-PT single crystals with enhanced dielectric constant and 33. / Doctor of Philosophy / Multi-ferroic materials, which contain multiple ferroic orders like ferromagnetism/ferroelectricity order, were widely studied nowadays. These orders are coupled together, which could manipulate one order via another one through the coupling. Due to the achievable reading/writing source (electric field and magnetic field in most of the case), fast response time and larger storage density, magnetoelectric (ME) materials aroused most interests to-date. To be used in different applications, such as memory devices and logic devices, a high transfer efficiency, or say a high coupling coefficient, is required. However, single-phase materials have nearly neglectable ME effect. Therefore, a nanocomposite that contents both magnetostriction and piezoelectricity were investigated to increase the converse magnetoelectric (CME, α) coefficient. Amongst all the nanocomposite, a vertically integrated heterostructure was revealed, which has intimate lattice contact, lower clamping effect, dramatically enhancedα, easier reading direction, and potential to be patterned for complicated applications. In this present work, we focused on several different aspects: (a) creating two-phase vertically integrated heterostructure with different ME materials, which provides much larger α, large strain-induced magnetic shape anisotropy comparing with the single-phased ME nanomaterials; (b): creating a vertically integrated heterostructure with large α and lower losses and higher efficiency; (c) investigate the stable magnetization states that this heterostructure could achieve, which shows the potential of being used in advanced memory devices and logic devices. Firstly, in this work, a BiFeO3-CoFe2O4 (BFO-CFO) heterostructure was epitaxially deposited on the Pb(Mg1/3Nb2/3) O3-x at%PbTiO3 (PMN-xPT), which could boost the CME in the heterostructure to create a much higher α. Then, a novel materials CuFe2O4 (CuFO), was chosen to be self-assembled with BFO, which has lower losses and higher efficiency of the ME effect. Secondly, several self-assembled heterostructures were created, such as Ni0.65Zn0.35Al0.8Fe1.2O4 (NZAFO) with BFO, which manipulated the magnetic coercivity (from 2 Oe to 50 Oe) and magnetic anisotropy directions (Both in-plane and out-of-plane). And a heterostructure: SrRuO3 with CFO, created a vertically integrated heterostructure, could be used as patterned electrodes in different applications. Moreover, magnetization states were studied in all these vertically integrated heterostructures. A multi-states (N≥4) was revealed, which was favored by multiple applications such as multi-level-cell or logical devices. Finally, we deposited a SrRuO3-CoFe2O4 (SRO-CFO) vertically integrated composite thin film on the single crystal substrate PMN-30PT, with a CFO nanopillar and SRO matrix. In such a heterostructure, the SRO would serve as the conductive materials, while CFO offers the insulated property. This unique conductive/insulating heterostructure could be deposited on PMN-PT single crystals, thus mimicking patterned electrodes on the PMN-PT single crystals with enhanced dielectric constant and d_33.

Ce travail de thèse porte sur les liens entre les conditions opératoires du procédé de mise en œuvre par mélange à l'état fondu et la structure de nanocomposites polypropylène/argile, ainsi que sur l'influence de l'état de dispersion de l'argile sur les propriétés mécaniques des matériaux obtenus. L'étude est basée sur des essais expérimentaux. Les analyses structurales sont réalisées en s'appuyant sur la rhéologie, la diffraction de rayons X ainsi que sur des observations en microscopie électronique.Les études en mélangeur interne ont montré, d'une part, que l'augmentation de la concentration en agent compatibilisant (PP-g-MA) favorise la dispersion de l'argile à l'échelle manométrique tout en augmentant la fragilité des nanocomposites, et d'autre part, que le mélange par voie mélange maître permet d'améliorer considérablement l'état de dispersion comparativement à la voie directe. Les essais réalisés en extrusion bivis corotative ont permis de mettre en évidence l'impact de la vitesse de rotation des vis (N), du débit d'alimentation (Q) et de la température de régulation (Trég) sur l'état de dispersion. L'influence de ces trois variables peut être décrite à l'aide d'un paramètre unique : l'énergie mécanique spécifique (EMS). L'accroissement de l'EMS entraîne une augmentation du niveau d'exfoliation jusqu'à une valeur critique au-delà de laquelle les conditions opératoires ne semblent plus influencer l'état de dispersion. Une relation entre le module de Young des nanocomposites et le niveau d'exfoliation a été établie. Le logiciel LUDOVIC© nous a permis de montrer que l'EMS permet également une bonne description de la progression de l'état de dispersion le long du profil d'extrusion. Enfin, l'étude du comportement thixotrope des nanocomposites à l'état fondu a notamment permis de comprendre que le principe de superposition temps-température ne s'applique pas systématiquement aux nanocomposites étant donné leur caractère évolutif. / The present PhD work deals with the relationships between melt processing conditions and the structure of polypropylene-layered silicate nanocomposites, as well as the influence of the dispersion state on the mechanical properties of nanocomposites. This study is based on experimental results. Structural analysis are performed using rheology, X-ray diffraction and electron microscopy.Internal mixer studies revealed that the increase of compatibilizer (PP-g-MA) content simultaneously leads to enhanced nanoscale dispersion and increased brittleness of the nanocomposites. A significantly higher dispersion was stated using a masterbatch method, as opposed to direct blending method. Co-rotating twin screw extrusion experiments allowed to highlight the effect of screw rotation speed (N), feed rate (Q) and barrel temperature (TrÈg) on the degree of dispersion. The influence of these three parameters on the nanocomposites structure can be described using the specific mechanical energy (SME) as a single processing parameter. Exfoliation is clearly promoted by the increase of the SME until it reaches a critical value. Above that threshold, the degree of exfoliation levels off and improvement of the dispersion state cannot be obtained through the optimization of processing conditions anymore. A relationship between the Youngís modulus of the nanocomposites and the exfoliation level has been established. Twin screw extrusion simulation software (LUDOVIC©) was used to calculate the evolution of processing data along the screw profile. From these results, a correlation between the progression of the dispersion state along the extrusion profile and the SME was found. Eventually, rheological investigation on the thixotropic behaviour of nanocomposites enabled to emphasize that time-temperature superposition principle doesn't systematically hold true for nanocomposites because of their structure aging.