This dissertation describes the development of a processing route for fabricating conventional and doped multi-wall carbon nanotube (MWCNT)/polymer composite films for dielectric applications. Previous research has shown that such composites are promising dielectric materials, but their commercial development has been impeded by the nanotube agglomeration in the polymer matrix and the inefficiency in forming uniform films. Moreover, the harsh fabrication treatments often disrupt the structure of the nanotubes, hence damaging their inherent electrical properties. This work presents safer routes for forming non-aqueous, surfactant free dispersions of conventional and doped MWCNTs, which can be readily mixed with polymers and formed into films through aerosol spraying. Dispersibility behaviour of in-house synthesised conventional, nitrogen doped (N-MWCNTs), and boron doped (B-MWCNTs) MWCNTs was studied in 22 organic solvents. Based on thermodynamic theories it was suggested that doping, in particular nitrogen doping, significantly reduced the surface energy of the nanotubes. This aspect was crucial to understand the dispersibility of N-MWCNTs in low surface energy solvents and to achieve dispersions with high nanotube concentrations (0.82 mg/ml). Also, a "destruction reduced sonication protocol" involving mild sonication was suggested for forming MWCNT dispersions in organic solvents. Dispersions formed using this protocol were homogeneous and showed high stability of at least 2.5 years. Furthermore, the effect of ultrasonic probes on MWCNT lengths was studied and a decrease of 96–99% for MWCNTs and 85–95% for N-MWCNTs was observed. A numerical value for the nanotube length decrease during sonication has been reported for the first time. Preliminary studies to generate dielectric films of MWCNT/perfluoro alkoxy polymer were performed using aerosol spraying. An improvement in the dielectric constant (3.56) with a low dissipation factor (0.003) was observed in 0.3 wt.% B- MWCNT/PFA composite films. Consistency in the test results from various parts of the films confirmed the uniformity of the nanotube distribution within the composite. Future work should concentrate on the effects of B-MWCNTs and N-MWCNTs at the percolation threshold due to their inherent electric properties.

Yes / Owing to their small size, good wettability, uniform dispersion ability and high thermal properties, the nickel-plated carbon nanotubes (Ni-CNTs) with different aspect ratios are used to reinforce reactive powder concrete (RPC) through modifying the nano/micro- structural units of concrete. Incorporating only 0.075 vol% of Ni-CNTs (0.03 vol% of CNTs) can significantly increase mechanical properties of RPC. The enhancement effect on compressive strength caused by the incorporation of Ni-CNTs with aspect ratio of 1000 reaches 26.8%/23.0 MPa, mainly benefiting from the high polymerization C-S-H gels, low porosity, and refined pore structure. The 33.5%/1.92 MPa increases of flexural strength can be attributed to the decrease of large pore, original cracks, molar ratio of CaO to SiO2, and gel water content when Ni-CNTs with aspect ratio of 125 are added. Ni-CNTs with aspect ratio of 1500 have the largest utilization rate of being pulled-out, resulting from the improvement of dispersibility and the pining effect of nickel coating and then leading to the increased toughness. Therefore, incorporating Ni-CNTs can fundamentally modify the nano/micro- scale structural nature of RPC, providing a bottom-up approach for controlling the properties of RPC. / Funding supported from the National Science Foundation of China (51908103 and 51978127) and the China Postdoctoral Science Foundation (2019M651116).

Carbon nanotubes have now been a subject of intense research for approaching two decades. Although a short time relative to most conventional materials, much hype about the intrinsic properties of this material has now been substantiated by experiment. The results are conclusive that carbon nanotubes are truly phenomenal materials with highly desirable mechanical, electrical and thermal properties. Furthermore, multiwall carbon nanotubes (MWNTs) have emerged as the most economically viable and abundant form of carbon nanotubes, and therefore the most likely candidate for application. The key materials engineering challenge remains in effectively transferring their properties to macro-scale materials in the form of composites. It is here that research merges with application. This dissertation has therefore been directed to focus on carbon nanotube composites in an applied sense. Here, the state of the art is reviewed, and experimental results of carefully selected composite systems, studied in detail for (1) mechanical, (2) electrical and (3) thermal properties, are presented and discussed. In terms of mechanical properties, the effects of MWNTs for augmentation of the tensile properties of PAN-based carbon fiber, and fatigue performance of poly(methyl methacrylate) are investigated and reported. In MWNT composite PAN-based carbon fiber, the formation of an ordered interphase layer sheathing the nanotubes was observed in fracture surfaces, which indicated a clear importance of their function to template the growth of carbon formation in the PAN-based matrix fiber. These structures open up a route to nano-scale tailorability of the crystallographic morphology of the composite fibers. Large improvements in fatigue performance were observed in MWNT/PMMA composites compared to MWNT/chopped carbon fiber composites, and attributed to the nanometer scale dimensions of the MWNTs enabling them to mitigate submicron damage such as polymer crazing. In terms of electrical and thermal properties, MWNT/epoxy composites were superior to MWNT/carbon black composites. Furthermore, extremely large improvements in the thermal conductivity of epoxy were observed for epoxy-infiltrated aligned MWNT arrays. The alignment of the MWNTs was shown to play a dominant role in enabling the improvement. Finally, these results, in concert with the literature are discussed in terms of the application of carbon nanotubes in engineering materials.

Carbon nanotubes have been found to have extraordinary properties, such as ballistic electrical conductivity, extremely high thermal conductivity and they can be metallic or semiconducting with a wide range of band gaps. There are however several issues that have to be solved before these properties can be fully utilised. One of these issues is that the nanotube growth temperature must be lowered in order to make the synthesis compatible with the fabrication processes used in electronics. The whole environment is heated to temperatures typically higher than 500 °C in the standard growth techniques whereas only a very localised area is heated in the technique developed here. This technique thus provides a way around the temperature issue. In the method developed here, the catalyst is deposited on top of a small metal (molybdenum) wire on the substrate. The high temperature required for nanotube growth is then reached by Joule heating by sending a current through the metal wire. This process eliminates the furnace which is used in conventional chemical vapour deposition and localises the high temperature to a very small and controlled area of the sample. Consequently, this technique is compatible with the semiconductor technology used today. Another advantage of this technique is that, since no furnace is required, a small growth chamber, which fits under a microscope, can be used. This allows in situ studies of the growth by optical microscopy and by Raman spectroscopy. By changing the carbon precursor, single- or multiwalled nanotubes can be grown. This can be important when producing devices since single-walled nanotubes predominantly are semiconducting whereas multi-walled mainly are metallic. The multi-walled nanotubes grow in a rapid and concerted process. This growth was monitored through an optical microscope. It was found that the thickness of the support layer and especially the catalyst are even more crucial parameters for nanotube growth using this local heating technique than in conventional processes. The activation energy could be extracted and was found to be 1.1-1.3 eV. The carbon nanotube growth was investigated by in situ Raman spectroscopy. The growth evolution could be well described by a model using the initial growth rate and the catalyst lifetime as parameters. The process was found to be limited by the mass transport of the carbon precursor. It was found that the molybdenum wire creates an additional pathway for the carbon cycle from gas to nanotube formation. The Raman spectra were studied at elevated temperatures. A decrease in intensity and a shift towards lower wavenumbers with increasing temperature was observed for the Stokes signal. It was found that the laser used for the Raman measurements could heat the nanotubes to high temperatures without any other heat source. Vertically aligned arrays of nanotubes were grown by conventional CVD. These arrays were actuated by applying a DC voltage between them. An effective Young's modulus of the arrays was found to be similar to that of rubber, which is orders of magnitude lower than for individual nanotubes. The capacitance between the arrays was measured to be tens of fF with a tunability of over 20%.

<p>In this study we report on the effect of the deposition parameters on the morphology and structural properties of CNTs, synthesized by means of the hot-wire chemical vapour deposition technique. SEM, Raman and XRD results show that the optimum deposition conditions for the HWCVD synthesis of aligned MWCNTs, with diameters between 50 and 150 nm and lengths in the micrometer range are: Furnace temperature of 500 &ordm / C, deposition pressure between 150 and 200 Torr, methane/hydrogen dilution of 0.67 and a substrateto- filament distance of 10 cm.</p>

PhD. (Chemistry) / This project assessed the toxicity of double-walled carbon nanotubes to three aquatic organisms belonging to different trophic levels, namely Pseudokirchneriella subcapitata (algae), Daphnia pulex (macro-invertebrate) and Poecilia reticulata (fish). Prior to the toxicity testing, the dry DWCNTs were characterised using scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy and Raman spectroscopy. Dynamic light scattering was used to characterise DWCNT suspensions. Natural water parameters such as increased ionic strength (Ca2+ and Na+) and increased humic acid affected the agglomeration potential of DWCNTs in aquatic medium. Increased ionic strength increased the agglomeration of DWCNTs while humic acid decreased agglomeration. The study explored the lethal/effective concentrations and sublethal effects of DWCNTs on the three organisms. The LC50/EC50 of DWCNTs for the three organisms differed in order of magnitude with D. pulex being the most sensitive and P. reticulata being the least sensitive. The LC50 for D. pulex was 2.81 and 4.45 mg/L for pristine and oxidised DWCNTs, respectively. Pseudokirchneriella subcapitata had an average EC50 of 10.01 mg/L and 10.93 mg/L for pristine and oxidised DWCNTs, respectively. Poecilia reticulata had an LC50 of 113.64 mg/L and 214.0 mg/L for pristine and oxidised DWCNTs, respectively. Exploring the effects of natural water parameters such as humic acid and ionic strength revealed that the acute toxicity of DWCNTs to D. pulex and P. reticulata was increased with increasing humic acid concentrations in exposure media, but increased ionic strength decreased the toxicity of both pristine and oxidised DWCNTs. However, these water parameters all decreased the toxicity of DWCNTs to P. subcapitata. The acute toxicity of DWCNTs was found to be directly linked to their agglomeration state in aquatic systems. Humic acid decreased the hydrodynamic sizes of DWCNT agglomerates making the engineered nanomatrials (ENMs) more available to the organisms while the cations increased the hydrodynamic sizes of DWCNT agglomerates, thereby reducing the probability of interactions with organisms. Time-based survival plots revealed that for P. reticulata and P. subcapitata, there were steady mortality/growth inhibitions throughout the duration of the exposures. For D. pulex, however, the plots revealed that there was a high initial die-off, whereafter mortalities proceeded at different rates. An assessment of whether DWCNTs cause oxidative stress in the three organisms revealed that DWCNTs caused significantly high oxidative stress in D. pulex and P. reticulata but not in P. subcapitata. In D. pulex and P. reticulata, DWCNTs were found to also cause DNA damage. The sublethal toxicity of DWCNTs was affected differently by the humic acid and increased cation concentration in exposure experiments. The sublethal effects were linked to the mode of interaction between DWCNTs and organisms. In P. subcapitata, the interaction was mainly physical with DWCNTs entrapping the algal cells in agglomerates and depriving the algal cells of light for normal photosynthesis to take place. For the other two organisms, the interaction was through intestinal cells as the organisms ingested DWCNTs and through accumulation of nanotubes on the exterior or organisms. The intestinal cell/DWCNT interaction resulted in the excessive generation of reactive oxygen species (ROS) and led to the death of the organism. Humic acid induced the highest antioxidant responses in both D. pulex and P. reticulata and this led to increased DNA damage in both organisms. Increased ionic strengths induced increased antioxidant responses at some DWCNT concentrations but the DNA damage was not significantly increased. These results suggested that with humic acid, the ROS production was excessive and sustained and had an effect on the DNA. The ROS production in increased ionic strengths was not excessive and was not prolonged, reducing their impact on DNA. The use of three organisms to assess the toxicity of DWCNTs provided comprehensive information on the potential effects of these ENMs in the aquatic food chain. Moreover, a multi-tier approach provided information on the potential effect of DWCNTs on populations at sublethal concentrations.

Doctor of Philosophy / Department of Chemistry / Duy H. Hua / Carbon nanotubes are allotropes of carbon comprising of one or more grapheme sheets seamlessly joined together to form a cylinder. They are classified as single-walled carbon nanotubes (SWNTs) or multi-walled carbon nanotubes (MWNTs). They have potential applications ranging from conductive and high reinforcement material components, nano interconnection in electronic devices to drug delivery in biological systems. Current methods of production are high temperature arc-discharge, laser ablation of graphitic materials and chemical vapor deposition. These methods give tubes that are impure and highly heterogeneous in length, diameter and chirality thus leading to mixture metallic and semiconducting tubes. Effective application of such carbon nanotubes requires cumbersome, harsh and expensive purification and sorting into like forms. Such treatments usually compromised the structural integrity of the tubes and hence their mechanical and electrical properties. Also pristine carbon nanotubes are insoluble in most solvents. Solubility in basic organic solvents is crucial prior to their application, which requires some level of chemical manipulation or functionalization on the tubes. Currently methods of functionalization are unpredictable and limited to few oxidation reactions. A novel rational synthetic chemical approach to [12, 12] arm-chair carbon nano tube with pre-defined diameter and length has been explored utilizing cheap and simple organic building blocks and results achieved so far have been presented in this dissertation. Two approaches were employed to form the carbon-rich beltene (32) before its final conversion to the target single-walled carbon nanotube (SWNT) 1. A survey on carbon nanotubes and their related structures including their potential applications and properties are presented in chapter 1. In the second chapter an iron template-assisted olefin metathesis via a ferrocene intermediate served as an anchor for an effective cyclization. In chapter 3, an un-assisted olefin metathesis pathway was explored. Both approaches use a series of benzyl halide carbonylation coupling and Diels-Alder reactions to synthesize some of the key intermediates. The protocol presented in this dissertation may be used to produce functionalized carbon nanotubes with predefined length and diameter tailored for specific applications to be produced in kilogram scale for the first time since its discovery in 1991. Such an approach is expected to address most if not all of the problems associated with the traditional methods of producing carbon nanotubes.

Thesis advisor: Lawrence T. Scott / The work described herein stems from an effort to develop a method for growing single-chirality carbon nanotubes from small hydrocarbon templates using a Diels-Alder cycloaddition/rearomatization strategy. Current technologies are incapable of producing significant amounts of homogeneous carbon nanotubes; therefore, much research has been put into the development of aromatic templates (belts and bowls), from which one type of nanotube might be grown (Chapter 1). Since no such functional template had yet been synthesized, the work in this dissertation developed reagents and methods for forming new benzene rings on aromatic test systems that would be analogous to the rim of a growing nanotube (Chapters 2 and 4). Theoretical investigations relating to nanotube dimensions (Chapter 3) were undertaken and paired with experimental work that would take into consideration the changing properties of growing tubes (Chapter 5). The test systems used for discovering new reagents for growth also became functional platforms for studies of new reactivity of polycyclic aromatic hydrocarbons (PAHs), such as bay-region oxidation (Chapter 6) and progress toward the synthesis of soluble graphene ribbons (Chapter 7). This PAH work also resulted in the observation of unique solid state properties in the crystal form (Chapter 8) and novel reactivity, generating five-membered rings by Scholl reactions of tethered PAHs (Chapter 9). Additional considerations for future nanotube templates and fullerene precursors also bore scrutiny (Chapter 10). / Thesis (PhD) — Boston College, 2010. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

We report a method of increasing fracture toughness (KIc) and strain energy release rate (GIc) of vinyl-ester (VE) matrix by adopting a hybrid (dual) reinforcement strategy. The idea of using this strategy was to trigger intrinsic polymer-nanoparticle interaction such as carbon nanotube (CNT) pull-out and interface sliding to enhance energy absorption during fracture. Additionally, we included a second reinforcement, graphene nanoplatelets (GNP), to promote crack-deflection, crack bridging and cross-linking density. Both reinforcements were dispersed into the polymer in three states: non-functionalized (nf>); functionalized with COOH (f>); surface-treated with Triton X-100 (TX100). We embarked on numerous experiments with many combinations of these variables. We measured KIc and GIc using ASTM D5045-14. We conducted an exhaustive iterative investigation with three systems (f>CNT-VE; f>GNP-VE; f>CNT-f>GNP-VE) to determine the best weight-percentage for the nanocomposite system that produced the highest KIc and GIc values when compared to neat-VE. We found that 0.5wt% f>CNT with 0.25wt% f>GNP in the VE matrix resulted in the highest fracture toughness values and was termed the optimized hybrid nanocomposites (OHN) system. Subsequently, we explored further increasing the KIc and GIc of OHN through altering the nanoparticle surface characteristics, which led to four OHN groups: f>CNT-f>GNP-VE; f>CNT-f>GNP-TX100-VE; nf>CNT-nf>GNP-TX100-VE; nf>CNT-nf>GNP-VE. We discovered that the OHN group with non-functionalized nanofillers that were TX100 surface treated (0.5wt%nf>CNT-0.25wt%nf>GNP-TX100-VE) generated the greatest improvements in KIc and GIc. Ultimately, we observed that the KIc of neat-VE increased by 65%, from 1.14 to 1.88 MPa*(m½). The improvement in GIc was even greater with an increase of 166%, from 370 to 985 J/(m2). Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) studies showed a minor shift in glass transition temperature (Tg) by up to 8°C when comparing neat-VE specimens to OHN specimens. A similar increase in maximum thermal decomposition temperature (Tp) of up to 8°C was observed through thermogravimetric analysis (TGA) and derivative TGA (DTG). Scanning electron microscope (SEM) studies revealed that the source of improvements in fracture toughness and thermal properties was primarily the three-dimensional hybrid nanostructures (3DHN) that formed by binding CNT and GNP together, which caused an increase in nanoparticle surface area and inhibited agglomerations. / Includes bibliography. / Dissertation (Ph.D.)--Florida Atlantic University, 2018. / FAU Electronic Theses and Dissertations Collection

This thesis presents the utilisation of giant piezoresistance of carbon nanotubes (CNTs) for high resolution pressure sensing. The nanoscale diameter of CNTs, used as sensing elements, increases the resolution of piezoresistive sensing by three orders of magnitude to that of silicon based sensors. The design of the sensor is based on sensing the strain in CNTs induced by the flow of gas and can be adapted to benefit cross-disciplinary fields like; flow and pressure sensing, microfluidics, Lab-on-chip and NEMS (nano-electromechanical systems). CNTs were grown inside silicon micro-cavities so as to bridge the gap between two silicon substrates. The nickel catalyst coated silicon substrates act as electrodes connected to the two ends of CNTs. The CNTs grow on the nickel nanoparticles, thus self-anchoring on to the substrate. Diffusion of nickel in silicon provides low resistive NiSi contacts to CNTs. Growth of CNTs in this form have not been reported before and presents several merits including no chemical treatment or post-growth alignment of CNTs, thus keeping the process simple and robust. CNT growth parameters; temperature, time and methane flow rate, were optimised in a custom designed chemical vapour deposition (CVD) rig, to control the CNT diameter. CNT diameter directly affects its piezoresistive coefficient, πL, and Young’s modulus, E, the factors that define piezoresistance in any material. Thus, optimised growth conditions allowed the direct tuning of piezoresistance of the sensor. Piezoresistance sensing was performed by inducing strain in CNTs with an applied differential pressure across the microcavity. Pressure loadings of as low as 0.1 atm (limited only by the gauge resolution) and a piezoresistance of as high as 16% at a pressure loading of 1 atm, were achieved. This piezoresistance is at least one order higher and the resolution is three orders higher than commercially available polysilicon and GaAs membrane based sensors. Piezoresistance was modelled by applying Euler-Bernoulli beam theory, assimilating CNTs to rigid beams with special boundary conditions, accounting for self-anchoring to Ni islands. The resulting theory is found to be in good agreement with our experimental results and estimates the E, πL and the average radius of the CNTs. This modelling, to our knowledge, is an original attempt to modify Euler-Bernoulli beam theory with the assumed boundary conditions.