Projection Stereolithography (PSL) is an Additive Manufacturing process that digitally patterns light to selectively expose and layer photopolymer into three dimensional objects. Nanomaterials within the photopolymer are therefore embedded inside fabricated objects. Adding varying concentrations of multi-walled carbon nanotubes (MWCNT) to the photopolymer may allow for the engineering of an objects tensile strength and electric conductivity. This research has two goals (i) the fabrication of three-dimensional structures using PSL and (ii) the material characterization of nanocomposite photopolymers. A morphological matrix design tool was developed and used to categorically analyze published PSL systems. These results were used to justifying design tradeoffs during the design and fabricate of a new PSL system. The developed system has 300μm resolution, 45mm x 25mm fabrication area, 0.23mW/cm2 intensity, and 76.2mm per hour vertical build rate. Nanocomposite materials were created by mixing Objet VeroClear FullCure 810 photopolymer with 0.1, 0.2, and 0.5 weight percent MWCNT using non-localized bath sonication. The curing properties of these nanocomposite mixtures were characterized; adding 0.1 weight-percent MWCNT increases the critical exposure by 10.7% and decreases the depth of penetration by 40.1%. The material strength of these nanocomposites were quantified through tensile testing; adding 0.1 weight-percent MWCNT decreases the tensile stress by 45.89%, the tensile strain by 33.33%, and the elastic modulus by 28.01%. Higher concentrations always had exaggerated effects. Electrical conductivity is only measurable for the 0.5 weight-percent nanocomposite with a 8k/mm resistance. The 0.1 weight-percent nanocomposite was used in the PSL system to fabricate a three-dimensional nanocomposite structure. / Master of Science

Within this research, factors affecting the orientation of injection molded long fiber composites in an end-gated plaque were investigated. Matrix viscosity was found to have a small effect on fiber orientation. The impact matrix viscosity had on orientation was dependent on fiber loading. At lower fiber loadings, the higher viscosity material had a more asymmetric orientation profile throughout the samples and less of a shell-core-shell orientation. At higher fiber loadings, there were few differences in orientation due to matrix viscosity. Fiber concentration was found to have a larger influence on fiber orientation than matrix viscosity. Increased fiber concentration led to a lower degree of flow alignment and a broader core region at all locations examined, following the trend previously reported for short fiber composites. The orientations of three different fiber length distributions of glass fiber (GF) were compared. The longer fibers in the fiber length distribution were shown to have a disproportionate effect on orientation, with weight average aspect ratio being better than number average aspect ratio at indicating if the GF and CF samples orientated comparably. To improve properties transverse to the main flow direction, the super critical carbon dioxide aided deagglomeration of multi-walled carbon nanotubes (CNTs) was used to create injection molded multiscale composites with CNT, CF, and polypropylene. The addition of CNTs greatly improved the tensile and electrical properties of the composites compared to those without CNTs. The degree of improvement from adding CNTs was found to be dependent on CF concentration, indicating that the CNTs were most likely interacting with the CF and not the polymer. A CNT concentration of 1 wt% with a tenfold degree of expansion at 40 wt% CF proved to be optimum. A large improvement in the tensile properties transverse to the flow direction was found implying that the CNTs were not highly flow aligned. Tensile and electrical properties began to fall off at higher CNT loadings and degrees of expansion indicating the importance of obtaining a good dispersion of CNTs in the part. / Ph. D.

The unique electronic properties of single-walled carbon nanotubes (SWNTs) have sparked interest for using such nanomaterials in the nuclear industry and within radiation detection devices. To explore the application of SWNTs in the nuclear industry, it was first deemed necessary to study how SWNTs respond to the two main types of radiation occurring in nuclear environments, neutrons and gamma rays. SWNT samples were irradiated in the High Flux Isotope Reactor (HFIR) at Oak Ridge National Laboratory with neutrons and gamma rays at incremented lengths of time allowing for multiple fluence intensities to be received by the samples. After irradiation, Raman spectroscopy was used to monitor the damage incurred from neutron and gamma irradiation. It was found that disorder within the SWNT lattice network increased with increasing irradiation intensity. The results indicated that the gamma irradiation was causing the majority of the damage with little to no damage caused by the neutron irradiation. Further investigation showed that the non-linearity of the disorder increase with increasing irradiation intensity was typical of sample doping instead of the expected particle impacts. It was concluded that the gamma irradiation was generating dopants within the SWNTs by the process of water radiolysis. Water vapor trapped between the SWNT film layer and the substrate that the film layer was placed on was identified as the source of the sample dopants. Although unexpected, the results from this experiment have provided insight into a potential gamma radiation detection technique using SWNTs that has never been considered until now. / Master of Science

This dissertation investigates the fundamental behavior of multifunctional materials for energy conversion. Multifunctional materials exhibit two or more functional properties, such as electrical, thermal, magnetic etc. In this dissertation, the emphasis is on understanding the principles for energy conversion from one domain to another (e.g. thermal to electrical; or mechanical to electrical) by utilizing nanomaterials and nanostructured materials such as carbon nanotubes, shape memory alloy (SMA), and flexible piezoelectric materials. Carbon nanotubes (CNTs) are known for their unique electrical and thermal properties. Development of solid-state suspended CNT sheets having extremely low heat capacity per unit area opens an opportunity for utilizing thermoacoustic phenomenon (electrical to thermal to acoustic energy conversion) that results in sound generation over a wide range of frequencies. Detailed theoretical modeling and experiments were conducted for understanding the acoustics generation from multi-wall carbon nanotubes (MWNTs) sheets. The sound pressure level (SPL) of CNT-based thermoacoustic projector (TAPs) is proportional to the frequency and hence the performance reduces in low frequency (LF) region which could be used for noise cancellation, SONAR and oceanography applications. Extensive analytical modeling in conjunction with experiments were conducted involving structure-fluid-acoustic interaction to determine the operational physical behavior of TAPs. Numerical model combines all the controlling steps from power input to acoustic wave generation to the propagation in outer fluid media. Power input to the computational domain is used to determine the frequency dependent thermal diffusive length which governs the generation of TA wave. MWNT yarns/fibers/threads were also designed to harvest ocean wave energy (mechanical to electrical energy conversion). These yarn-based harvesters electrochemically convert tensile or torsional mechanical energy into electrical energy without requiring an external bias voltage. Harvesters were developed by spinning sheets of forest-drawn MWNTs into high-strength yarns. SMA wires exhibit two unique properties: thermally induced martensite to austenite phase transformation and super-elasticity (stress-induced martensitic transformation). These properties were implemented for developing the low-grade thermal energy harvesters (thermal to electrical energy conversion). More than half of the energy generated worldwide is lost as unused thermal energy because of the lack of efficient methodology for harnessing the low-grade heat. A systematic study is presented here that takes into account all the key steps in thermal to electrical conversion such as material optimization, thermal analysis and electrical conditioning to deliver the efficient harvester. Next using thin sheets of piezoelectric materials, strain energy harvesting from automobile tires is studied (strain to electrical conversion. Flexible organic piezoelectric material was utilized for transduction in the harvester for continuous power generation and simultaneous sensing of the variable strain experienced by tire under different driving conditions. Using sensors mounted on a real tire of a mobile test rig, measurements were conducted on different terrains with varying normal loads and speeds to quantify the sensitivity and self-powered sensing operation. / Doctor of Philosophy / This dissertation studies the potential of carbon nanotubes yarns and sheets, piezoelectric sheets and shape memory alloy wires for energy conversion applications. Multiwalled carbon nanotubes (MWNTs) are known for their unique electrical and thermal properties. Large surface area, solid state self-suspended carbon nanotube sheets having extremely low heat capacity per unit area were utilized for design of thermoacoustic projectors operating over a wide range of frequencies. Detailed numerical modeling and experiments were conducted for understanding the acoustics generation from MWNT sheets. Another potential application for MWNT yarns is in ocean wave energy harvesting, where these yarn based harvesters convert tensile mechanical energy into electrical energy. Harvesters were developed by spinning sheets of MWNTs into high-strength yarns. SMA exhibits unique phase change behavior on mechanical and thermal loading, which were utilized for converting low-grade thermal energy into electrical energy. At low temperature gradients, where there is lack of methodologies for converting thermal energy into electrical energy, SMA wire-based energy harvesters are shown to provide ultra-high power density. Extensive experimentation in conjunction with multi-physics modeling is conducted to provide understanding of energy losses occurring during the thermal to electrical conversion. Lastly, this dissertation investigates the mechanical to electrical conversion using organic piezoelectric materials. Self-powered strain sensing mechanism for autonomous vehicle will provide new capabilities in monitoring the dynamics and allow developing additional automated controls to assist the driver performance.

No / Simply melt blended polypropylene/carbon nanotubes composites (PP/CNTs) usually present mechanical deterioration. In this work, multilayered sheet of PP/CNTs with improved tensile property was obtained by solid-phase orientation and hot compression. The initially blended PP/CNTs were highly orientated by employing a constrained slit die and hot compressed under a certain temperature and pressure by stacking eight layers together. The effects of compression temperature and pressure on the tensile property and AC conductivity of the multilayered sheets were examined to explore the evolution of hierarchical crystallization morphology and CNT networks. The multilayered sheet which was hot compressed at 184°C and 5 MPa demonstrated an optimum tensile strength of ∼132.5 MPa and an elongation at break ∼52.7%, respectively, raised by almost 3-fold compared with those initially blended PP/CNTs. By increasing compression temperature and decreasing pressure, the AC conductivity showed an increase of 2 to 4 orders of magnitude. / China Scholarship Council. Grant Number: 201806465028.

2023 / Single-walled carbon nanotubes (SWCNTs) are promising optoelectronic materials due to their low cost, flexibility, and dopant-tunable photoluminescence and electrical properties. Confined in 1D, electron-hole interactions in SWCNTs become more significant compared with traditional semiconductors, as evidenced by high exciton binding energies. Additionally, an exciton trapping potential may be introduced by the presence of sp3 defects in a tube, increasing exciton lifetime and photon luminescence conversion efficiency. These defects can introduce unpaired spins with strong spin-orbit coupling, leading to correlated spin and excitonic behaviors that are difficult to understand but important for understanding the role of this class of materials for many applications such as quantum communication. In this dissertation, we study the electronic and spin structure of doped (6,5) SWCNT within first-principles density functional theory and many-body perturbation theory, connecting our simulation to observed phenomena from experiments. For a series of unpassivated sp3 defects, we predict the formation of a singly-occupied mid-gap electronic state centered at the sp3 site, with little spin density on the aromatic rings of the defect. We propose a new synthetic route for creating a doped system with significant density on Pd, and therefor an increase in spin-orbit coupling and intersystem crossing. We then utilize a spin diffusion model to demonstrate the long spin lifetime of up to μs. Lastly, we demonstrate that low-energy excited-state associated with single-phonon emission consist of a mixture of defect-like and symmetry broken band-like transitions. Overall, we have demonstrated the potential of sp3-doped (6,5) SWCNT as a molecular-scale qubits with long coherence times for use in quantum sensing, information / 2025-08-03T00:00:00Z

Lithium-sulfur (Li-S) batteries are faced with practical drawbacks of poor cycle life and low charge efficiency which hinder their advancements. Those drawbacks are primarily caused by the intrinsic issues of the cathodes (sulfur) and the anodes (Li metal). In attempt to resolve the issues found on the cathodes, this work discusses the method to prepare a binder-free three-dimensional carbon nanotubes-sulfur (3D CNTs-S) composite cathode by a facile and a scalable approach. Here, the 3D structure of CNTs serves as a conducting network to accommodate high loading amounts of active sulfur material. The efficient electron pathway and the short Li ions (Li+) diffusion length provided by the 3D CNTs offset the insulating properties of sulfur. As a result, high areal and specific capacities of 8.8 mAh cm−2 and 1068 mAh g−1, respectively, with the sulfur loading of 8.33 mg cm−2 are demonstrated; furthermore, the cells operated at a current density of 1.4 mA cm−2 (0.1 C) for up to 150 cycles. To address the issues existing on the anode part of Li-S batteries, this work also covers the novel approach to protect a Li metal anode with a thin layer of two-dimensional molybdenum disulfide (MoS2). With the protective layer of MoS2 preventing the growth of Li dendrites, stable Li electrodeposition is realized at the current density of 10 mA cm−2; also, the MoS2 protected anode demonstrates over 300% longer cycle life than the unprotected counterpart. Moreover, the MoS2 layer prevents polysulfides from corroding the anode while facilitating a reversible utilization of active materials without decomposing the electrolyte. Therefore, the MoS2 protected anode enables a stable cycle life of over 500 cycles at 0.5 C with the high sulfur loading amount of ~7 mg cm−2 (~67 wt% S content in cathode) under the low electrolyte/sulfur (E/S) ratio of 6 μL mg−1. This translates to the specific energy and power densities of ~550 Wh kg-1 and ~300 W kg−1, respectively. Additionally, such values far exceed the electrochemical performance of the current Li-ion batteries. Therefore, the synergetic effect of utilizing the 3D CNT-S cathode and the MoS2 protected Li anode will allow the Li-S batteries to become applicable for the transportation and the large-scale energy grid applications.

The first part of this dissertation is an introduction describing a brief historical background of carbon nanotubes (CNTs) and their pseudo 1D structure responsible for many exotic electronic properties. The second part describes our experimental setup. The third part is about the growing of Multi-Walled Carbon Nanotubes (MWCNTs) by the chemical vapor deposition (CVD) method. Then the fourth part demonstrates a simple but reliable method to make firm contact junctions between MWCNTs and metals such as tungsten (W). The novel point of our method consists, after making a mechanical preliminary contact at a selected MWCNT, in applying a series of voltage pulses across the contact. Thin oxide layers that may form between the MWCNT and the W wire, are removed in steps by the resistive heating and electron impact during the application of each voltage pulse. Furthermore, this simple process of contact welding in steps does not bring about any permanent change in the electronic transport properties of the MWCNTs. The fifth part discusses our bending experiments. We apply a uniform and continuous bending to a selected MWCNT at room and liquid nitrogen temperatures to study the strain effect on the electrical transport in the MWCNT. There are a few published experimental works related to the bending deformation; however, this is the first study of electronic transport properties in continuous bending and releasing deformations. We observed a saturation behavior with the MWCNT and also found the bending deformation causing an anomalous change in the saturation behavior. In the sixth part we depict some interesting phenomena due to the stretching deformation of MWCNT, where we were able to propose a simple model for electron localization induced by the deformation. The last part deals with the formation of the "X-junction" between two MWCNTs. A strong X-junction can be formed simply by means of the e-beam inside the Scanning Electron Microscope (SEM). The X-junctions may form the basic elements of nano-electronic circuits such as various metal-insulator junctions, quantum dots, and similar devices. / text

Measurement of all the mechanical properties of carbon nanotubes is extremely difficult because of its small size. In the present work, all the five transverse isotropic properties of single wall carbon nanotubes (SWCNTs) and double wall carbon nanotubes are estimated through molecular structural mechanics for different chirality, length and assumed thickness. Armchair, zigzag & chiral SWCNTs and polychiral DWCNTs are considered for the analysis. Longitudinal and lateral Young’s modulus; longitudinal and lateral Poisson’s ratio and shear modulus are estimated for 1080 SWCNTs and 1170 polychiral DWCNTs. Effect of temperature on all the properties of SWCNT are investigated. Modal characterization of SWCNT is carried out in base fixed condition and different mode shapes viz. axial, torsion and bending mode shapes are identified based on the effective mass. Once the transverse isotropic properties of SWCNTs are estimated, these are used to estimate the transverse isotropic properties of nanocomposites embedded with SWCNT agglomerates. During the manufacturing of nanocomposite, SWCNT agglomerates are formed due to sticking of number of SWCNTs. Parametric studies are carried out to see the effect of SWCNT length on the properties of nanocomposite. Empirical formulae for all the transverse isotropic properties of SWCNT at room temperature and elevated temperature; frequency of SWCNT are derived. Empirical formulae for polychiral DWCNT transverse isotropic properties are estimated. Input for these empirical formulae are the length, chirality and assumed thickness. Empirical formulae were also derived for nanocomposite embedded with different number of SWCNTs having different chirality. The derived empirical formulae were validated with available analytical and experimental results for some sample cases.

M-Tech. (Department of Chemistry, Faculty of Applied and Computer Science), Vaal University of Technology. / The commercial flake graphite was prepared into functionalized graphite oxide (GO) by adopted chemical treatment. After the exfoliation and intercalation of graphite into functionalized graphene oxide that formed stable colloidal dispersion in polar aprotic solvent, the reduction process was undertaken by continuous stirring with hydrazine hydrate in a microwave at 35 oC for two hours. The reduced material was characterized by X-ray diffraction (XRD), attenuated total reflectance (ATR) FT-IR, Ultra-violet visible (UV-vis), atomic force microscopy (AFM), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman microscopy and magnified optical microscopy that confirm the oxidation of graphite and reduction of graphene oxide into graphene sheets. Carbon nanomaterials were synthesized from Co-Sn, Co-Sr and Co-Zn as catalysts supported on Al2O3, CaCO3 and MgO. The as-prepared nanomaterials were characterized by thermogravimetric and derivative thermogravimetric analysis (TGA & DTA), Raman spectroscopy, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) and the transmission electron microscopy. The intensity ratios (ID/IG) of the D- and G- bands were found to be the same that is averagely at 0.83. The TGA & DTA curves have shown Co-Sn/Al had significant weight loss, Co-Sr/Mg weight loss and decomposition, Co-Sr/Al decomposition and Co-Zn/Mg weight loss. However these weight losses were not significant. The EDS analysis showed all elements which took part in the reaction confirming the success of each synthesis. The SEM images show carbon nanotubes only on samples that have been synthesized on MgO as confirmed by TEM images. Finally the XRD showed some characteristic peaks at desired peaks except that they were other peaks attributed to impurities and armophous carbon. It was also observed that Co-Sn/Ca and Co-Sn/Mg XRD curves showed broad peaks at theta = 24.3o & 42.6o and theta = 23.9o & 43.1o respectively which are lattice structure characteristic peaks.