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.

Micro-electro-mechanical Systems (MEMS) technology has revolutionized the micro/nano world by making micro/nano devices feasible. These devices allow more exploration and understanding of the micro/nano world. In this dissertation, we will discuss the measurement of wall shear stress in an integrated microfluidic system built by MEMS technology. Specifically, carbon nanotubes (CNTs) were used as the sensing element for gas-flow shear stress measurement in this work. CNTs have already been proven to have an excellent sensing response to temperature, pressure, and alcohol vapour. Based on the thermal sensing response of CNTs, the sensor was designed to operate using convective heat transfer principles in fluid flow. Dielectrophretic manipulation was used to batch fabricate CNTs on a PMMA substrate. The CNT sensor was then integrated into a PMMA microchannel, which was fabricated by a rapid prototyping technique using moulding/hot-embossing processes. The sensor responded to impinging flow as well as gas-flow shear stress. The sensor activation power was found to be linearly related to the 1/3 exponential power of the wall shear stress. With the measurements of an array of sensors, the flow profile of a microchannel with various types of flow could be studied. Compared with the conventional polysilicon sensor, the CNT sensor has the advantage of small dimensions, i.e. a greater spatial resolution for fluidic measurements, and low power consumption, i.e. it consumes ∼1,000 times less power than polysilicon sensors. Therefore, CNT sensors have a great potential to serve as an alternative to silicon-based sensors. / Chow, Wing Yin Winnie. / Adviser: Wen J. Li. / Source: Dissertation Abstracts International, Volume: 70-06, Section: B, page: 3743. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references (leaves 105-110). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

Self-assembly of nanomaterials over macroscopic dimensions and development of novel nano-electromechanical systems (NEMS) hold great promise for numerous nanotech applications. However, it has always been a great challenge to find a general route for controlled self-assembly of nanomaterials and generating electromechanical response at the nanoscale level. This work indicates that self-organized anisotropic nematic liquid crystals (LC) can be exploited for nanotemplating purposes to pattern carbon nanotubes (CNTs) and Quantum dots (QDs) over a macroscopic dimension. The pattern formed by the CNTs or QDs can be controlled by applying external electric and magnetic fields, developing novel nano-electromechanical and nano-magnetomechanical systems. Self-organizing nematic liquid crystals (LC) impart their orientational order onto dispersed carbon nanotubes (CNTs) and obtain CNT-self-assembly on a macroscopic dimension. The nanotubes-long axis, being coupled to the nematic director, enables orientational manipulation via the LC nematic reorientation. Electric field induced director rotation of a nematic LC+CNT system is of potential interest due to its possible application as a nano-electromechanical system. Electric field and temperature dependence of dielectric properties of an LC+CNT composite system have been investigated to understand the principles governing CNT-assembly mediated by the LC. In the LC+CNT nematic phase, the dielectric relaxation on removing the applied field follows a single exponential decay, exhibiting a faster decay response than the pure LC above a threshold field. Due to a strong LC-CNT anchoring energy and structural symmetry matching, CNT long axis follows the director field, possessing enhanced dielectric anisotropy of the LC media. This strong anchoring energy stabilizes local pseudo-nematic domains, resulting in nonzero dielectric anisotropy in the isotropic LC phase. These anisotropic domains respond to external electric fields and show intrinsic frequency response. The presence of these domains makes the isotropic phase electric field-responsive, giving rise to a large dielectric hysteresis effect. These polarized domains maintain local directors, and do not relax back to the original state on switching the field off, showing non-volatile electromechanical memory effect. Assembling quantum dots (QDs) into nanoscale configurations over macroscopic dimensions is an important goal to realizing their electro-optical potential. In this work, we present a detailed study of a pentylcyanobiphenyl liquid crystal (LC) and a CdS QD colloidal dispersion by probing the dielectric property  and relaxation as a function of an applied ac-electric field Eac. In principle, dispersing QDs in a nematic LC medium can direct the dots to align in nearly one-dimensional chain-like structures along the nematic director and these assemblies of QDs can be directed by external electric fields. In a uniform planar aligned cell, the Fréedericksz switching of the LC+QDs appears as a two-step process with the same initial switching field as the bulk but with the final value larger than that for an aligned bulk LC. The relaxation of  immediately following the removal of Eac follows a single-exponential decay to its original value that is slower than the bulk but becomes progressively faster with increasing Eac, eventually saturating. These results suggest that the arrangement of the QDs is mediated by the LC.

Thermoelectric generators are solid state machines used to convert temperature gradients into electrical energy. They are formed by several thermoelectric units connected electrically in series and thermally in parallel. These units are made by creating a junction between a p-type and an n-type conductor. This investigation documents the characterisation of the thermoelectric properties of carbon nanotube (CNT) films and the fabrication process of carbon nanotube-based thermoelectric devices. The Seebeck coefficient is a intrinsic property of a thermoelectric material that correlates the voltage produced by a conductor and the temperature gradient applied to it. To measure the Seebeck coefficient of films, an experimental set-up was fabricated and calibrated using constantan as standard material. CNT films of aligned nanotubes fabricated using a chemical vapour deposition method were analysed. The Seebeck coefficient along and across the samples did not show significant variations, with values between 40$\mu$V/K and 80$\mu$V/K. Using these CNT films, thermoelectric cells were fabricated with the CNT as the p-type conductor and constantan as the n-type. As a proof of concept, two hand-made thermoelectric generators were assembled by connecting hundreds of these thermoelectric cells. These devices were subjected to a temperature gradient of $\approx$200K, which was enough to produce enough power to light an LED. Other analytical techniques were used to characterise the materials used in this work. Electrical conductivity measurements, thermogravimetric analysis, Raman spectroscopy and scanning electron microscopy were performed. Using a deposition technique, films of nanotubes were produced from a liquid phase. The impact of the production method on their properties was evaluated. Characterisation equipment was developed to measure the Seebeck coefficient and thermal conductivity. Thermoelectric devices made with the carbon nanotube films were fabricated and characterised. The values of thermal conductivity of the CNT films analysed in this work are between 0.86Wm$^{-1}$K$^{-1}$. The electrical conductivity of these materials is between 3500Sm$^{-1}$ and 14100Sm$^{-1}$. The maximum figure of merit of the carbon nanotube thermoelectric devices fabricated in this work is $ZT$=0.35.

The main goal of this project was the development of carbon nanotubes as a candidate for dual-functioning magnetic hyperthermia structure and magnetic resonance imaging contrast agent. This was achieved by filling carbon nanotubes with continuous ferromagnetic α-Fe nanowires and surface functionalized with paramagnetic Gd(III). Also, length control of both nanotube and nanowire was investigated. Firstly, a low vapour flow-rate and constant evaporation temperature chemical vapour deposition method based on the thermal decomposition of ferrocene was employed which achieved continuous α-Fe nanowires on the same scale as the nanotube for lengths >10 m without the necessity of post-synthesis heat-treatment or introduction of other precursor elements. The low vapour flow-rate regime has the advantage of sustaining the intrinsic temperature gradient at the tip of the forming structure which drives the vapour feedstock to the growth front to guarantee continuous nanowire formation. For initially mixed-phase nanowires of length less than 10 μm, the continuous α-Fe nanowires were achieved by postsynthesis heat treatment. Secondly, a simple wet chemical method involving only sonication in aqueous GdCl3 solution was used for surface functionalization of iron-filled multiwalled carbon nanotubes with gadolinium. Functional groups on the sidewalls produced by the sonication provide active nucleation sites for the loading of Gd3+ ions. Characterization by electron paramagnetic resonance, electron energy loss spectroscopy, and high-resolution transmission electron microscopy confirmed the presence of Gd3+ ions on the sidewall surface. The ferromagnetic properties of the encapsulated iron nanowire maintained after surface functionalization. At room temperature a saturation magnetization of 40 emu/g and a coercivity of 600 Oe were observed. Heating functionality in an alternating applied magnetic field was quantified through the measurement of specific absorption rate: 50 W/gFe and the intrinsic loss power: 1.12 nHm²kg⁻¹ at magnetic field strength 8 kA/m and frequency of 696 kHz. These structures exhibited an extremely high relaxivity r₁ ~ 200 mM⁻¹ s⁻¹ at high magnetic field (9.4 T).

This thesis describes a detection system for single molecules based on individual single-walled carbon nanotube field-effect sensors. The sensitivity, spatial confinement and transducer gain of the sensor is derived from a conductance controlled electrochemically created defect, which is also chemically reactive. An automated microfluidic system is designed to enable long and stable measurements of the carbon nanotube device in aqueous environment with temperature control of ±0.1°C. A probe DNA can be covalently attached to the defect through an amide bond and the conductance is modulated when a target DNA binds to the probe. As a result, the conductance shows a traditional random telegraph signal and fluctuates between a hybridized and melted state. By monitoring the conductance as a function of temperature, the kinetics and thermodynamics can be extracted, which are comparable to previous fluorescent correlation spectroscopy studies using optical fluorescent resonant energy transfer. By studying the fluctuation amplitude as a function of charge proximity, buffer concentration and solution potential, it is shown that the sensor is based on a field-effect. The sensor has a temporal resolution of 200 μs and a signal to noise ratio of 3-8 when continuously measuring for 30 seconds. By further reducing the parasitics, the sensor has the capabilities to detect biomolecule kinetics down to microsecond resolution, which could make it an attractive tool for single-molecule experiments with fast kinetics.

Coulomb drag-induced ion current flow is reported, achieved through coupling of electronic charge carriers along the lattice of a narrow single-walled carbon nanotube to electrolytic charge within the confines of the nanotube. Solid-state electrical contacts to the nanotube induce ion transport through it in the absence of an axial electric field; in the presence of such a field, the device behaves as an n-type ionic transistor. Ionic currents as high as 1nA have been recorded without alternate driving forces. Asymmetric functionalization of single walled carbon nanotube end groups further enhances the rectifying behavior of the device, yielding a current rectification ratio as high as 10 at moderate axial field strengths. By achieving ion pumping through a solid-state electrical input, the system offers promising solutions to nanoscale applications including purification, drug delivery, and desalination.

No description available.