This thesis aims to utilize graphene nanoplatelets (GNPs) in biobased and biodegradable thermoplastic polylactide (PLA) matrix for improved properties and multifunctionalities. A comprehensive comparative study was carried out on the effect of the addition of GNPs with different sizes. The mechanical, electrical, thermal and barrier properties of resulting PLA/GNP nanocomposites and their inter-relationship with the microstructure of the composites is revealed. The effect of annealing on dynamic percolation and conductive network formation of PLA/GNP composites including the effect of hybrid GNP fillers of different size is reported, indicating the underlying mechanisms for different behaviours of GNP fillers of different size. Multifunctional engineering biopolymers with improved performances (mechanical and electrical) and added functionalities (barrier properties) were successfully developed through controlled filler distribution and orientation using multilayer co-extrusion technology. Changes in mechanical properties of the PLA/GNP multilayer nanocomposites were successfully correlated with GNP orientation in the filled layers. Multilayer PLA/GNP nanocomposites demonstrated excellent mechanical and barrier properties with low filler loadings compared to traditional mono-extruded films.

Nanowire structure plays an important role in the development of nanotechnology. However, further study shows that the shape of nanowires may not be the ideal morphology for some applications such as solar cells and sensors. Thus, the purpose of this thesis is to find a low cost and high yield approach to the synthesis of other morphologies of nanostructures in order to further improve the performance of these nanodevices. To this end, a chemical approach has been extended to the synthesis ZnO nanocones and platelets. With UV illumination, the synthesis of ZnO nanocones was achieved on GaN films on sapphire and gold films on silicon substrates. Both TEM and XRD results show that as-grown ZnO nanocones are single crystals. The formation of ZnO nanocones could be explained by the absorption process of photons. The UV light induced thermal gradient modifies the heat distribution as well as the reagent transport. The chemical reaction system is kinetically limited and results in ZnO nanocones. If the UV light is blocked, the ZnO nanowires result. In addition, the density of ZnO nanocones is higher than ZnO nanowires grown without UV illumination. By this chemical approach, ZnO platelets could also be obtained on GaN films deposited by PLD, whose c-axis is parallel to the surface of the substrate. The diameters and the thickness of the platelets depend on the quality and thickness of GaN film. TEM results illustrate that the obtained ZnO platelets are single crystals grown along the <0 1 1 0> direction within the {0 0 0 1} planes. Relative growth rates of various facets were altered by the presence of [1 0 0] textured GaN film. The suppression of the growth along c axis can also be achieved by citrate anions as a structure-directing agent to adsorb selectively on ZnO basal planes. Electrical measurement shows that the resistance of ZnO platelets is about 20-40 GΩ¸ and it is higher than that of ZnO nanowires. Piezoelectric potential calculation results also indicate that the piezoelectric potential is higher than for ZnO nanowires with the same external applied stress. These procedures and results demonstrate an easy and low cost way to fabricate ZnO nanocones and platelets, which may aid the utilization of nanostructures in solar cells, sensors and other applications to further improve their performance.

Graphene Nanoplatelets (GNP) was incorporated into polyamide 6 (PA6) matrix by melt compounding method and the enhancements in the properties of the nanocomposites were studied. Response Surface Methodology (RSM) was employed to assist in the study of processing conditions in melt compounding. RSM analysis revealed that the GNP concentrations to be the most significant term to affect the tensile modulus and crystallinity followed by the screw speed whereas the residence time was found to be non-significant. GNP with 5 Î1⁄4m (G5) and 25 Î1⁄4m (G25) were used in the GNP aspect ratio study. The average flake size of G5 and G25 to was measured to be 5.07 Î1⁄4m and 22.0 Î1⁄4m, respectively with the G5 distributed narrowly whereas the G25 exhibit broad distribution. TGA analysis shown that HT25 is more thermally stable compared to G25 due to some remnants lost during thermal treatment and this was confirmed by EDX and CHNS analysis. XRD profiles of the PA6-G-NC illustrate typical peaks of PA6 crystals phase as well as pure graphite characteristic peak. PA6-G25-NC observed to exhibit slightly higher peak intensity compared to PA6-G5-NC suggesting more formation of PA6 crystals. Similar improvement was observed on PA6-HT25-NC compared to PA6-G25-NC indicating more formation of PA6 crystals due improved dispersion of HT25. DSC on PA6-G25-NC showed higher cooling temperature and crystallinity compared to PA6-G5-NC due to larger surface area of the G25. Similarly, PA6-HT25 showed better improvement in crystallinity over PA6-G25-NC due to increase nucleation sites by the HT25. The thermal conductivity of PA6-G25-NC is slightly higher than the thermal conductivity of PA6-G5-NC but not significant considering the G25 is 5 times larger than G5. Instead, no significant difference was observed between PA6-HT25-NC and PA6-G25-NC. Addition of GNP increased the thermal stability of the PA6-G-NC systems under both nitrogen and air atmospheres regardless of the GNP aspect ratio. The viscoelastic properties showed insignificant difference between PA6-G5-NC and PA6-G25-NC. The inefficient improvement by G25 might be due to agglomeration formed during processing. The storage modulus and tan Î ́ of PA6-HT25-NC decreased but the Tg significantly improved compared to PA6-G25-NC. This was assumed to be because of improved dispersion of HT25 but reduced interfacial interaction after the heat treatment. The shear storage modulus, G’ and complex viscosity, |η*| were observed to increase with increasing GNP content with more pronounced improvement seen on PA6-G25-NC compared to PA6-G5-NC. However, no network percolation threshold was observed until 20 wt.% of GNP. The poor interfacial interaction of HT25 resulted in lower G’ and |η*| compared to G25. Tensile test results showed typical improvement with PA6-G25-NC having higher tensile modulus compared to PA6-G5-NC. Further enhancement was obtained with PA6-HT25-NC suggesting improved dispersion and volume of constrained chains mobility despite the poor surface interaction. Comparison with Halphin-Tsai modulus revealed that the effective modulus to be 150 GPa for G5 and 200 GPa for G25. The water uptake measurement results showed that GNP reduced the water uptake percentage and diffusion coefficient especially with G25. The test conducted on saturated PA6-G-NC results in improved thermal conductivity due to the high thermal conductivity of water but the viscoelastic and tensile properties severely reduced due to plasticisation effect.

In the last decade, carbon nanotubes (CNTs) and Graphene nanoplatelets (GNPs) have attracted a lot of attentions in various polymeric and ceramic composite systems, in an effort to improve their mechanical and functional properties. Al2O3 has attracted considerable interests in ceramics community, in particular as a matrix material for composite fabrications. The high stiffness, excellent thermal stability and chemical resistance of Al2O3 make it practically a very important engineering material, and if we can overcome its brittleness issue, its applications will be much wider. Adding CNTs as a reinforcement to the Al2O3 matrix to improve the toughness is one of the most promising methods. Similarly, GNPs have recently also been shown to be very promising for the same purpose. It has been demonstrated that by adding a mixture of the 2D-GNPs and 1D-CNTs into a polymer matrix, the toughest or strongest man-made ropes have been made. However, the homogenous dispersion of CNTs or GNPs is more of a challenge in a ceramic matrix than in polymeric matrices, owing to the tendency of CNT agglomerations and more steps are needed to completely transfer the useful properties of CNTs and GNPs into ceramics. In this thesis, nanocomposites of Al2O3 reinforced with a hybrid of GNTs (a blend of GNPs and CNTs) were first fabricated. The hybrid GNT reinforcements were mixed with the Al2O3 using a wet chemical technique under ultrasonic treatment. The effects of varied GNT contents on the microstructural features and mechanical properties of the nanocomposites were then investigated. It is found that the well-dispersed GNT fillers resulted in high sintered densities (>99%) in the composites, whilst the fracture mode alteration, grain refinement and improved flexural strength of the composites are all associated with the inclusion of CNTs and GNPs. The average fracture toughness of the nanocomposites reached up to 5.7 MPa·m1/2, against 3.5 MPa·m1/2 of the plain Al2O3, and the flexural strength improved from 360 MPa to 424 MPa respectively, at a hybrid addition of 0.5 wt% GNPs and 1 wt% CNTs. The toughening mechanisms attributed with the unique morphologies and structures of the GNT fillers were also discussed based on analyses on the morphology, grain sizes and fracture mode. The effects of hot-pressing (HP) and spark plasma sintering (SPS) methods on the grain size, microstructural features, and mechanical behaviour of GNT-reinforced Al2O3 nanocomposites were then comprehensively studied. Identical overall reinforcement contents at various GNP/CNT ratios were selected to prepare the composites using both HP and SPS. Highly densified samples (>98%) were obtained at 1650°C under 40 MPa in Ar atmosphere, with dwell times of 1 h and 10 min for HP and SPS respectively. Both types of sample showed a mixture of inter- and trans-granular fracture behaviour. A 50% grain size reduction was observed for samples prepared by HP, compared with the SPS samples. Both types of samples achieved a high flexural strength and fracture toughness of > 400 MPa and 5.5 MPa·m1/2, respectively, whilst the properties of the SPS samples peaked at relatively lower GNT contents than those of the HP samples. Based on analyses of the morphology, grain sizes and fracture mode, similar toughening mechanisms for both types of sample were observed, involving the complex characteristics of the combined GNT fillers. The tribological performance of the HPed pure Al2O3 and its composites containing various hybrid GNT contents was further evaluated under different loading conditions using a ball-on-disc method. Benchmarked against the pure Al2O3, the composite reinforced with a 0.5 wt% GNP exhibited a 23% reduction in the friction coefficient along with a promising 70% wear rate reduction, and a hybrid reinforcement consisting of 0.3 wt.% GNPs + 1 wt.% CNTs resulted in even better performance, with a 86% reduction in the wear rate. The extent of damage to the reinforcement phases caused during wear was studied using Raman spectroscopy. The wear mechanisms for the composites were analysed according to the mechanical properties, brittleness index and microstructural characterization. The combination between GNPs and CNTs contributed to the excellent wear resistance properties for the hybrid GNT-reinforced composites. The GNPs played an important role in the formation of a tribofilm on the worn surface by exfoliation; whereas the CNTs contributed to the improvement in fracture toughness and prevented the grains being pulled out during the tribology test. Finally, Graphene Oxide (GO) was used to replace the GNPs in the hybrid, to prepare Al2O3-GONT nanocomposites, by adopting a new sol-gel processing, in addition to powder mixing. It has been found that sol-gel process leads to an impressive grain size reduction of 62%, the fracture toughness and flexural reached 6.2 MPa·m1/2 and 420 MPa (i.e. 70% and 14% improvement), respectively, than those of pure Al2O3, which even marginally outperformed the previously optimised Al2O3-GNP nanocomposites by 8% in fracture toughness. The success of our new sol-gel strategy opens up new opportunities for choosing hybrid reinforcements for the fabrication of advanced ceramic nanocomposites.

No description available.

Yes / Semiconductor nanostructures like CdSe quantum dots and colloidal nanoplatelets exhibit remarkable optical properties, making them interesting for applications in optoelectronics and photocatalysis. For both areas of application a detailed understanding of the electronic structure is essential to achieve highly efficient devices. The electronic structure can be probed using the fact that optical properties of semiconductor nanoparticles are found to be extremely sensitive to the presence of excess charges that can for instance be generated by means of an electrochemical charge transfer via an electrode. Here we present the use of potential modulated absorption spectroscopy (EMAS) as a versatile spectroelectrochemical method to obtain absolute band edge positions of CdSe nanostructures versus a well-defined reference electrode under ambient conditions. In this the spectral properties of the nanoparticles are monitored dependent on an applied electrochemical potential. We developed a bleaching model that yields the lowest electronic state in the conduction band of the nanostructures. A change in the band edge positions caused by quantum confinement is shown both for CdSe quantum dots as well as for colloidal nanoplatelets. In the case of CdSe quantum dots these findings are in good agreement with tight binding calculations. The method presented is not limited to CdSe nanostructures but can be used as a universal tool. Hence, this technique allows the determination of absolute band edge positions of a large variety of materials used in various applications.

In this study, composite system was developed to enhance mechanical properties of plastic pallets. The potential of graphite nanoplatelets (GnP)/PP composites for the application in packaging was scrutinized by examining mechanical properties, thermal properties, flow properties, and morphology as a function of GnP loading and by comparison of two mixing methods: physical melt compounding (PMC) and chemical pretreatment compounding (CPC) processes. Incorporation of the GnP into PP resulted in a significant enhancement in the mechanical strength (tensile, impact, and flexural strength) and thermal decomposition temperature compared to the neat PP specimen. The CPC process clearly shows good exfoliation and better distribution on the PP matrix compared to the PMC method based on morphological evaluation measured by SEM. The impact test at low temperature revealed that the composites made by the CPC process showed 64% higher impact strength than neat PP due to higher even-distribution of GnP molecules into the PP matrix. We attempted to discover the degree of dispersion of natural fiber (kenaf) and graphite nanoplatelets (GnP) into the polypropylene (PP) polymer matrix and the effect of filler-adding sequence on physical and mechanical properties. Tensile strength of the composites was increased up to 25%. In the case of Young's modulus, composites showed a 56% enhancement compared to the control. However, the impact strength decreased as a result of the increased brittleness when kenaf fiber was added. Another study investigated the effects of hybrid filler systems (graphite nanoplatelets (GnP)/commercially available modified calcium carbonate (mCaCO3) nanoparticles) on mechanical and physical properties of polypropylene nanocomposites with three variables, filler loading amount, the number of compounding processes, and the compounding order of two different fillers. The impact strength of composite samples, containing 1wt% of GnP and mCaCO3 nanoparticles, increased up to 64% compared to neat PP. Among all tested samples, the highest tensile strength was found at 1wt% of mCaCO3 nanoparticles regardless of the presence or absence of GnP addition. There was no significant difference in flexural strength regardless of any nano-filler addition. However, both the flexural modulus and Young's modulus increased significantly when 10wt% of mCaCO3 nanoparticles were added. The number of compounding processes did not affect any strength, and the single compounding process was found to be more effective than the double compounding process. It may be contributed by thermal degradation of polymeric structure by double heat processing. This study can be able to provide a solution for value-added high-end products in various industries such as application in logistics, aerospace or electric automobile, where carbon-based nanomaterials are more affordable. / Doctor of Philosophy / Pallets are the basic structure of a unit load which allows handling and storage efficiency. The advantages of plastic pallets are durability, cleanliness, and performance reliability, However, those are expensive and have lower mechanical properties than that of wood, such as low strength, creeps and deformation. Therefore, hybrid composites were fabricated using various fillers, such as graphite nanoplatelets, kenaf fiber or calcium carbonate on polypropylene matrix to enhance mechanical properties for plastic pallets. In order to fabricate the composites, two methods were utilized and compared: physical melt compounding (PMC) and chemical pretreatment compounding (CPC) processes. Graphite nanoplatelets (GnP) reinforced polypropylene (PP) composites made by both PMC and CPC process showed significance in the mechanical process compared to the neat PP. Moreover, the CPC process showed better dispersion on the PP matrix resulting in higher impact strength in low temperature. Based on the first chapter, we attempted to focus on reducing weight and sustainability using natural fiber. At the same time, when two or more fillers are reinforced in a polymer matrix, I wondered if the order in which the fillers were added could affect properties. Kenaf fiber and GnP were reinforced in the PP matrix through the CPC process to discover the degree of dispersion of fillers and the effect of filler-adding sequence on physical and mechanical properties. Tensile strength of the composites was increased up to 25%. In the case of Young's modulus, composites showed a 56% enhancement compared to the control. However, the impact strength decreased as a result of the increased brittleness when kenaf fiber was added. Another study investigated the effects of hybrid filler systems (GnP/commercially available modified calcium carbonate (mCaCO3) nanoparticles) on mechanical and physical properties of polypropylene nanocomposites with three variables, filler loading amount, the number of compounding processes, and the compounding order of two different fillers. This study was concentrating on the impact strength based on the result that the material adding sequence affects the mechanical strength when manufacturing the hybrid composites. The hybrid composite system on GnP/mCaCO3/PP resulted in enhancement of impact strength, tensile strength, flexural modulus and Young's modulus. The number of compounding processes did not affect any strength, and the single compounding process was found to be more effective than the double compounding process. Enhancement of impact strength in low temperature, and effect of filler-adding sequence on mechanical properties in hybrid composite system can be able to provide a solution for value-added high-end products in various industries such as application in logistics, aerospace or electric automobiles, where carbon-based nanomaterials are more affordable.

This thesis reports the effects of incorporating graphite nanoplatelets (GNPs) to epoxy-carbon fibre (CF) laminates to produce multiscale composites. A grade of epoxy resin typical for the application in aerospace engineering, triglycidyl-p-aminophenol (TGPAP), was used in this work cured with 4,4'-diaminodiphenyl sulfone (DDS). To improve the processability of TGPAP, a diluent, the diglycidyl ether of bisphenol F (DGEBF), was added to formulations. Compositions of TGPAP/DGEBF/DDS were optimised using response surface methodology (RSM) with the target response being to obtain high glass transition temperature (Tg) and low resin viscosity. From RSM, the optimum values were obtained at 55.6 wt. % of DGEBF and a stoichiometric ratio of 0.60. Before addition into epoxy, GNPs were treated either covalently using 3-aminopropyltriethoxysilane (APTS) or non-covalently using a commercial surfactant, Triton X-100 (abbreviated as A-GNPs and T-GNPs, respectively). After treatment, XPS analysis showed a new peak at 100 eV for A-GNPs indicating silicon and the C/O ratio increased from 11.0 to 26.2 for T-GNPs relative to unmodified GNPs (U-GNPs), suggesting attachment of the modifier molecules had occurred. Nanocomposites (NCs) were prepared by incorporate GNPs into epoxy using mechanical mixing. Rheological percolation threshold of GNP-epoxy suspensions were determined using oscillatory-shear rheometry as 3.9 wt. % for AR-GNPs, 3.6 wt. % for U-GNPs, 3.2 wt. % for A-GNPs and 3.5 wt. % for T-GNPs, suggesting surface treatment improved dispersion. At 4 wt. % of GNPs, flexural strain of NCs was decreased relative to neat epoxy by 46% for AR-GNPs, 48.6% for U-GNPs, 4.6% for A-GNPs and 30.8% for T-GNPs but flexural moduli showed small increases of 6.1-7.4%. Fracture toughness (K1C) also improved. For example, the K1C increased from 0.80 ± 0.04 MPa.m1/2 for neat epoxy to 1.32 ± 0.01 MPa.m1/2 for NCs containing 6 wt. % of U-GNPs possibly due to the branching of cracks resulting from the embedded GNPs. Due to their mechanical performance, A-GNPs were used to fabricate epoxy/CF/A-GNPs multiscale composites. Multiscale composites showed inferior properties relative to a comparable conventional composite in flexural testing, interlaminar shear strength (ILSS) and interlaminar fracture toughness mode II (G11C) due to weaker bonding at the matrix-CF interface. However, multiscale composites showed ~40% higher capability than conventional composite to absorb energy during impact due to greater interfaces formed by the inclusion of A-GNPs into the system.

Grâce à leurs propriétés optiques et électroniques uniques, les nanocristaux de semi-conducteurs colloïdaux bidimensionnels tels que les nanoplaquettes de chalcogénure de cadmium ont émergé comme une nouvelle classe de nanomatériaux. Tout comme les puits quantiques, ces nanocristaux ont un confinement electronique limité à une seule direction, l'épaisseur qui est contrôlée au niveau atomique. Ces nanoplaquettes colloïdales apparaissent ainsi comme de bons candidats pour la fabrication de dispositifs optoélectroniques. Cependant, leur mécanisme de formation reste sujet à discussion. Ainsi, cette thèse se concentre tout d’abord sur l'étude de la synthèse de nanoplaquettes de CdSe zinc blende et l’effet de la longueur de la chaine aliphatique des carboxylates sur ces dernières, ouvrant ainsi la voie à une meilleure compréhension de la croissance des nanocristaux bidimensionnels.Par la suite, la nature et la localisation de ces ligands carboxylates en surface des nanoplaquettes a été étudié par des techniques de RMN. Cette étude semble confirmer l’effet de la gêne stérique sur la croissance des nanoplaquettes. La RMN du solide en corrélation 13C-1H 2D, se basant sur l’interaction dipolaire, indique que les acétates et les carboxylates à longue chaîne sont très probablement distribués de manière homogène à la surface des nanoplaquettes de CdSe. Dans une dernière partie, j’explore la possibilité d’améliorer les propriétés optiques de nanoplaquettes synthetisées par déposition de couches atomiques en voie colloïdale (c-ALD) en utilisant des recuits, visant à améliorer la structure et la surface des matériaux. / Colloidal two-dimensional semiconductor nanocrystals such as nanoplatelets of cadmium chalcogenides, have emerged as a new class of nanomaterials due to their unique optical and electronic properties. These nanocrystals possess exciton confinement along one direction in analogy to quantum wells, with their thickness controlled at atomic level.Although colloidal two-dimensional nanoplatelets have been considered as potential candidates for the fabrication of optoelectronic devices, their formation mechanism e.g. zinc blende CdSe nanoplatelets is still under debate. Thereby this thesis first focuses on the study of CdSe nanoplatelets synthesis and size of the aliphatic chain in the carboxylate, paving the way to a better understanding of two-dimensional nanocrystals’ growth.Successively surface carboxylate ligands are investigated by NMR techniques which gives us an idea of how surface ligands are composed and relocated. Our study of ligand quantification on nanoplatelets’ surface appears to support the proposed effect from steric hinderance on NPLs growth. 13C-1H 2D correlation solid state NMR based on the dipolar interaction indicates that acetates and long alkyl chain carboxylates should be distributed homogenously on the surface of the CdSe NPLs. In the last part, I explore the possibility of improving the optical features of nanoplatelets synthesized from colloidal atomic-layer-deposition technique through optimizing both interior and surface structures by an annealing process.

Polymer-nanoplatelet hybrid membranes show promise as the next generation of membranes, but in order to make these realizable, methods to produce these materials on a large scale are necessary. Some authors have successfully produced these types of gas separation membranes. Typically these reports have utilized melt blending and in situ polymerization. Few, however, have utilized solution blending for creating membranes via phase inversion (asymmetric membranes). And to date, there have not been any reports regarding the fabrication of asymmetric membranes containing nanoplatelet filler materials. In this work we have developed a solution-based procedure for the formation of hybrid polymer-nanoplatelet dopes for dense film and asymmetric hollow fiber membrane formation. Dense film membrane studies were used to prove the effectiveness of our exfoliation and dispersion process developed for this work. Permeation measurements showed the hybrid membranes have desirable transport properties that are on par with mathematical model predictions. Additionally, TEM characterization provided strong evidence supporting the efficacy of our preparation procedures to produce an exfoliated system of nanoplatelets. We also showed that these procedures are applicable to different polymer systems (cellulose acetate and Torlon) of commercial relevance. Demonstrating the successful production of dense films set the stage for asymmetric hollow fiber membrane formation. We report the first production of asymmetric hollow fiber membranes containing nanoplatelet fillers; indicating that the process can be applied in a realistic membrane formation platform. These accomplishments serve as the groundwork for future nanocomposite formation.