>Magister Scientiae - MSc / Currently, non-renewable sources are mostly used to meet the ever-growing demand for energy. However, these sources are not sustainable. In addition to these energy sources being not sustainable, they are bad for the environment although the energy supply sectors highly depend on them. To address such issues the use of renewable energy sources has been proven to be beneficial for the supply of energy for the global population and its energy needs. Advantageous over non-renewable sources, renewable energy plays a crucial role in minimizing the use of fossil fuel and reduces greenhouse gases. Minimizing use of fossil fuels and greenhouse gases is important, because it helps in the fight against climate change. The use of renewable energy sources can also lead to less air pollution and improved air quality. Although solar energy is the most abundant source of renewable energy that can be converted into electrical energy using various techniques, there are some limitations. Among these techniques are photovoltaic cells which are challenged by low efficiencies and high costs of material fabrication. Hence, current research and innovations are sought towards the reduction of costs and increasing the efficiency of the renewable energy conversion devices.

We are facing an energy crisis because of the limitation of the fossil fuel and the pollution caused by burning it. Clean energy technologies, such as fuel cells and metal-air batteries, are studied extensively because of this high efficiency and less pollution. Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential in the process of energy storage and conversion, and noble metals (e.g. Pt) are needed to catalyze the critical chemical reactions in these devices. Functionalized carbon nanomaterials such as heteroatom-doped and molecule-adsorbed graphene can be used as metal-free catalysts to replace the expensive and scarce platinum-based catalysts for the energy storage and conversion. Traditionally, experimental studies on the catalytic performance of carbon nanomaterials have been conducted extensively, however, there is a lack of computational studies to guide the experiments for rapid search for the best catalysts. In addition, theoretical mechanism and the rational design principle towards ORR and OER also need to be fully understood. In this dissertation, density functional theory calculations are performed to calculate the thermodynamic and electrochemical properties of heteroatom-doped graphene and molecule-adsorbed graphene for ORR and OER. Gibb's free energy, overpotential, charge transfer and edge effect are evaluated. The charge transfer analysis show the positive charges on the graphene surface caused by the heteroatom, hetero-edges and the adsorbed organic molecules play an essential role in improving the electrochemical properties of the carbon nanomaterials. Based on the calculations, design principles are introduced to rationally design and predict the electrochemical properties of doped graphene and molecule-adsorbed graphene as metal-free catalysts for ORR and OER. An intrinsic descriptor is discovered for the first time, which can be used as a materials parameter for rational design of the metal-free catalysts with carbon nanomaterials for energy storage and conversion. The success of the design principle provides a better understanding of the mechanism behind ORR and OER and a screening approach for the best catalyst for energy storage and conversion.

Nanodiamonds are a promising platform for quantum technologies due to the combinations of their inherent properties and the properties of the fluorescent color centers hosted in diamond. They can be employed as quantum sensing devices with spatial resolution in the range of the nanometer and capable of withstanding harsh conditions while also being biocompatible, allowing applications with sensitive biological systems; but they also find application in quantum computing and photonics fields. For all these applications the central features are the properties of the photoluminescent color centers employed, the color centers on which this thesis is focused are the Nitrogen-Vacancy (NV) and Silicon-Vacancy (SiV) centers of diamond. Both centers are of high interest due to spin dependent properties of their fluorescent emission which can be accessed at room temperature. The development of quantum technologies based on such fluorescent nanodiamonds is stifled by the the lack of production techniques that can be easily scaled to industrial levels. In fact most of the more prominent techniques found in literature exhibit drawbacks both in terms of control of particle properties and of scalability. This thesis focuses on the synthesis of nanodiamonds by Pulsed Laser Ablation in Liquid, with particular interest in the possibility of producing continuously nanodiamonds containing NV and SiV centers. For the NV center the technique of choice have been Pulsed Laser Ablation in liquid nitrogen focusing on the yield of the process as the technique has already been experimentally validated. For the SiV centers the ablation process was performed in water and the graphite precursor have been substituted for a composite graphite and silicon carbide precursor.

Atualmente, os estudos envolvendo nanomateriais como aditivos em propantes são o foco das companhias e universidades norte-americanas para o desenvolvimento de propantes que possam sofrer alterações químicas e mecânicas dentro do reservatório ou para permitir a rastreabilidade e direcionamento. Este trabalho apresenta um desenvolvimento de grânulos de metacaulim capazes de incorporar nanomateriais em sua estrutura. O método adotado para sua produção foi a mistura intensiva da matéria-prima (MP) com nanomateriais dispersados e adicionados em resina para revestimento. A rota de produção tem potencial para produzir grânulos com grau de K&S variando entre 0,7 e 0,9 tanto para esfericidade como para o arredondamento. Os ensaios de resistência ao esmagamento resultaram em valores entre 3 K e 4 K (x 1.000 psi) para algumas das amostras sinterizadas a 1.300 ºC. As análises de MEV comprovam a incorporação dos nanomateriais de carbono, na estrutura interna dos propantes. / Today, studies on nanomaterials that are used as additives in proppants are the focus of North America\'s companies and universities in order to develop either proppants that can suffer mechanical and chemical changes inside the reservoir or that enable their traceability and direction. This work presents a development on the microspheres of metakaolin\'s capacity to incorporate nanomaterials to their structure. The production route has the potential to produce K & S grade microspheres ranging from 0.7 to 0.9 for both sphericity and rounding. Crush strength tests resulted in values between 3 K and 4 K (x 1,000 psi) for some of the samples sintered at 1300 °C. The SEM analyzes prove the integration of carbon nanomaterials into the proppant structures.

Doctor of Philosophy / Department of Chemical Engineering / Placidus B. Amama / The continued depletion of fossil fuels and concomitant increase in greenhouse gases have encouraged worldwide research on alternative processes to produce clean fuel. Fischer-Tropsch synthesis (FTS) is a heterogeneous catalytic reaction that converts syngas (CO and H₂) to liquid hydrocarbons. FTS is a well-established route for producing clean liquid fuels. However, the broad product distribution and limited catalytic activity are restricting the development of FTS. The strong interactions between the active metal catalyst (Fe or Co) and support (Al₂O₃, SiO₂ and TiO₂) during post-synthesis treatments of the catalyst (such as calcination at ~500°C and reduction ~550°C) lead to formation of inactive and unreducible inert material like Fe₂SiO₄, CoAl₂O₄, Co₂SiO₄. The activity of FTS catalyst is negatively impacted by the presence of these inactive compounds. In our study, we demonstrate the use of a modified photo-Fenton process for the preparation of carbon nanotube (CNT)-supported Co and Fe catalysts that are characterized by small and well-dispersed catalyst particles on CNTs that require no further treatments. The process is facile, highly scalable, and involves the use of green catalyst precursors and an oxidant. The reaction kinetic results show high CO conversion (85%), selectivity for liquid hydrocarbons and stability. Further, a gaseous product mixture from FTS (C1-C4) was utilized as an efficient feedstock for the growth of high-quality, well-aligned single-wall carbon nanotube (SWCNT) carpets of millimeter-scale heights on Fe and (sub) millimeter-scale heights on Co catalysts via chemical vapor deposition (CVD). Although SWCNT carpets were grown over a wide temperature range (between 650 and 850°C), growth conducted at optimal temperatures for Co (850°C) and Fe (750°C) yielded predominantly SWCNTs that are straight, clean, and with sidewalls that are largely free of amorphous carbon. Also, low-temperature CVD growth of CNT carpets from Fe and Fe–Cu catalysts using a gaseous product mixture from FTS as a superior carbon feedstock is demonstrated. The efficiency of the growth process is evidenced by the highly dense, vertically aligned CNT structures from both Fe and Fe–Cu catalysts even at temperatures as low as 400°C–a record low growth temperature for CNT carpets obtained via conventional thermal CVD. The use of FTS-GP facilitates low-temperature growth of CNT carpets on traditional (alumina film) and nontraditional substrates (aluminum foil) and has the potential of enhancing CNT quality, catalyst lifetime, and scalability. We demonstrate growth of SWCNT carpets with diameter distributions that are smaller than SWCNTs in conventional carpets using a CVD process that utilizes the product gaseous mixture from Fischer-Tropsch synthesis (FTS-GP). The high-resolution transmission electron microscopic (HR-TEM) and Raman spectroscopic results reveal that the use of a high melting point metal as a catalyst promoter in combination with either Co (1.5 nm ± 0.7) at 850ºC or Fe (1.9 nm ± 0.8) at 750ºC yields smaller-diameter SWCNT arrays with narrow diameter distributions. Scalable synthesis of carbon nanotubes (CNTs), carbon nanofibers (CNFs), and onion like carbon (OLC) in a batch reactor using supercritical fluids as a reaction media is demonstrated. The process utilizes toluene, ethanol, or butanol as a carbon precursor in combination with ferrocene that serves as a catalyst precursor and a secondary carbon source. The use of supercritical fluids for growth does not only provide a route for selective growth of a variety of carbon nanomaterials, but also provides a unique one-step approach that is free of aggressive acid treatment for synthesis of CNT-supported metallic nanoparticle composites for catalysis and energy storage applications.

Hat sections, single and double, made of steel are frequently encountered in automotive body structural components such as front rails, B-Pillar, and rockers of unitized-body cars. These thin-walled components can play a significant role in terms of crashworthiness and impact energy absorption, through a nonlinear phenomenon called as progressive dynamic buckling. As modern vehicle safety design relies heavily on computer-aided engineering, there is a great need for analysis-based predictions to yield close correlation with test results. Although hat sections subjected to axial loading have been studied widely in the past, there is scanty information in published literature on modeling procedures that can lead to robust prediction of test responses. In the current study, both single-hat and double-hat components made of mild steel are studied extensively experimentally and numerically to quantify statistical variations in test responses such as peak load, mean load and energy absorption, and formulate modeling conditions for capturing elasto-plastic material behavior, strain rate sensitivity, spot-welds, etc. that can lead to robust predictions of force-time and force-displacement histories as well as failure modes. In addition, keeping initial stages of vehicle design in mind, the effectiveness of soft computing techniques based on polynomial regression analysis, radial basis functions and artificial neural networks for quick assessment of the behaviors of steel hat sections has been demonstrated. The study is extended to double-hat sections subjected to eccentric impact loading which has not been previously reported. A lightweight enhancement of load carrying capacity of steel hat section components has been investigated with PU (polyurethane) foam-filled single and double hat sections, and subjecting the same to quasi-static and axial impact loading. Good predictions of load-displacement responses are again obtained and shortening of fold lengths vis-à-vis hollow sections is observed. Finally, the performance of hat sections made of glass fiber-reinforced composites is studied as a potential lightweight substitute to steel hat section components. The challenging task of numerical prediction of the behaviors of the composite hat sections has been undertaken using a consistent modeling and analysis procedure described earlier and by choosing an appropriate constitutive behavior available in the popular explicit contact-impact analysis solver, LS-DYNA.

No description available.

No description available.

The biggest hurdle in success of gene and drug therapy is designing and preparation of suitable bio-nanomaterials to carry the desired nucleic acid and drug to the targeted site. The work described in the present thesis encompasses two different approaches for the delivery of bioactive oligo/polynucleotides and drugs in vitro and in vivo using either cationic lipids or their nanocomposites with different carbon nanomaterials. The idea of using carriers for oligo/polynucleotides and drugs came into existence because of numerous physiological barriers in pathway of delivery of naked oligo/polynucleotides or drugs which reduces the overall activity of these bioactives in biological systems. These barriers trigger scientific research toward the preparation of appropriate biomaterials which can overcome the physiological barriers and improve the activity of bioactive oligo/polynucleotides and drugs in cellular systems. Toward this end, the design and synthesis of different cationic lipids and carbon nanomaterials were undertaken as described in seven chapters of the thesis. A series of novel cationic lipids with structural variability was prepared and used for gene delivery in vitro. They were further tuned chemically to sustain delivery efficiency in high serum percentage during in vitro transfection. These serum compatible lipids were used to perform transfection of reporter gene plasmid and found to be more efficient compared to the some well known commercial products for the same purpose. Another series of novel lipids were synthesized for the targeted gene delivery in vitro. These tryptophan based cholesteryl lipids were used to prepare mixed liposomes. These mixed liposomes were highly efficient in targeting sigma receptor rich HEK293T over sigma receptor negative HeLa cells. Mixed liposomes were also prepared for selective targeting of αvβ3 and αvβ5 integrins in gene transfection protocol using a palmitoyl-RAFT-RGD4 template. A mixed liposomal formulation was developed to carry out anti-sense siRNA mediated knockdown of Smad-2 protein with better efficiency compared to some of the best known commercial products for the same purpose. These mixed liposomes were also highly efficient for regression via induction of p53 mediated apoptosis in xenograft tumors developed in nude mice. Carbon nanomaterials have been extensively explored as nanoscale gene/drug carriers for potential applications. But the challenge is to solubilize these highly hydrophobic materials in aqueous medium for use in biological systems. Although there are reports for covalent modifications of such nanomaterials but it could be done only with the loss of some beneficial features of these materials. Herein a non-covalent technique has been efficiently used to suspend single walled carbon nanotubes in water using biocompatible cationic lipids. These nanosuspensions were used to complex plasmid DNA and transfect them in vitro. They proved to be highly serum compatible DNA carriers which did not drop the efficiency even in very high percentage of serum. Similarly exfoliated graphene was modified with cationic lipid and serum components to improve IC50 of Tamoxifen citrate and Methotrexate to a considerable extent in vitro. The improved Methotrexate formulations were highly efficient for regression in size of xenograft tumors developed in nude mice. Thus, the present thesis entails generation of cationic lipids and carbon nanomaterials based nanocomposites which were not only highly biocompatible themselves but their efficiency was found many fold better compare to some of the best commercial delivery agents. These were useful for the delivery of various bioactive oligo/polynucleotides and drugs in vitro and in vivo.