Thesis (M.S.)--University of Hawaii at Manoa, 2007. / Includes bibliographical references (leaves 145-146). / vi, 146 leaves, bound ill., maps 29 cm

A thesis submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy Johannesburg, 2016 / Technologies for the separation of CO2 from flue gas require a feat of engineering for efficient achievement. Various CO2 capture technologies, including absorption, adsorption, cryogenics and membranes, have been investigated globally. The absorption technology uses mainly alkanolamine aqueous solutions, the most common being monoethanolamine (MEA); however, further investigation is required to circumvent its weakness due to degradation through oxidation, material corrosion and high energy costs required for regeneration. Attractive advantages in adsorption technology, including the ability to separate the more diluted component in the mixture with a low energy penalty, have been a motivation for many researchers to contribute to the advancement of adsorption technology in CO2 capture. The challenge in CO2 adsorption technology is to design a hydrophobic and biodegradable adsorbent with large CO2 uptake, high selectivity for CO2, adequate adsorption kinetics, water tolerance, and to require low levels of energy for regeneration processes. The existing adsorbent such as activated carbon, silica gel, zeolites, metal organic frameworks and others, have been ineffective where moisture occurs in flue gas. This work provides an advanced adsorption technology through a novel adsorbent, MWNT-PAA, designed from the noncovalent functionalization of multi-walled carbon nanotubes (MWNTs) by polyaspartamide (PAA) as product of amine grafted to polysuccinimide (PSI). Three types of PAA were prepared using ethylenediamine (EDA), 1, 3 propanediamine (PDA) and monoethanolamine (MEA) drafted to PSI to give PSI-EDA, PSI-PDA and PSI-MEA respectively. The CO2 adsorption capacity was 13.5 mg-CO2/g for PSI-PDA and 9.0 mg-CO2/g for PSI-MEA, which decreased significantly from PSI where the CO2 adsorption capacity was 25 mg-CO2/g. PSIEDA was selected as PAA, because the CO2 adsorption capacity was 52 mg-CO2/g which doubled from PSI. The polymer polyethylenimine (PEI), the most commonly polymer used in CO2 capture, was found to be non-biodegradable, while the polymer PAA showed the presence of CONH as a biodegradable bond functionality, occurring in the MWNT-PAA, as confirmed through Fourier Transform Infrared (FTIR) analysis. The adsorbent MWNT-PAA was demonstrated to have a water tolerance in the temperature range 25-55 ℃, where CO2 adsorption capacity increased with the increase of water in the adsorbent. The highest CO2 adsorption capacity recorded was 71 mg-CO2/g for the moist MWNT-PAA using 100% CO2 and 65 mg-CO2/g for the mixture of 14% CO2 with air. Under the same conditions, the dry MWNT-PAA adsorbed 70 and 46 mg-CO2/g respectively (100%, 14% CO2). The 2 regenerability efficiency of the MWNT-PAA absorbent was demonstrated at 100 ᵒC; after 10 cycles of adsorption-desorption 99% of adsorbed gas was recovered in the desorption process. The heat flow for the thermal swing adsorption system resulted in the net release of heat over the complete cycle; a cycle includes adsorption (heat release) and desorption (heat absorbance). Thus, this MWNT-PAA adsorbent demonstrates an advantage in terms of overall energy efficiency, and could be a competitive adsorbent in CO2 capture technology.

Block copolymers containing pendant pyrene, terpyridine and poly(3- hexylthiophene) moieties with different block ratios and chain lengths were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. The block copolymers obtained had narrow molecular weight distribution. The applications of these polymers for non-covalent functionalization of carbon nanotubes and in photovoltaic devices were studied. The molecular weight distribution and block sizes of the block copolymers could be controlled quite well. The polydispersities measured were below 1.25. The block copolymers could be functionalized on the surface of CNTs. The functionalized CNTs had an improved dispersing ability and a maximum dispersing ability of 0.30 mgmL-1 in DMF was achieved. The photosensitizing properties of an individual functionalized CNT were studied by conductive atomic force microscopy. In the presence of the photosensitizing unit, the photocurrent was measured to be 6.4 nAμW-1 at 580 nm. This suggests the role of metal complexes in the photosensitizing process in the block copolymer. Poly(3-hexylthiophene)-block-pendant pyrene copolymers were synthesized by Grignard metathesis and RAFT polymerization. Different loadings of the block copolymers functionalized CNT were employed as the electron accepting materials in bulk heterojunction photovoltaic devices. A maximum power conversion efficiency of 0.77 × 10-3 % was achieved for the poly(3- hexylthiophene): 0.5% polymer functionalized CNT devices. The poor efficiency was attributed to the low CNT loadings that limited the electron transport in the devices. The poly(3-hexylthiophene)-block-pendant pyrene copolymer were employed as compatibilizer for poly(3-hexylthiophene): [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) bulk heterojunction photovoltaic devices. With the addition of 20 % of the block copolymer, a maximum power conversion efficiency of 1.62 % could be achieved. The long term stability of the encapsulated photovoltaic devices was studied. There was more than 30 % reduction in the degradation of performance after 30 days when the block copolymer was added as compatibilizer. These results suggested the role of the block copolymer compatibilizers in improving both the photovoltaic performances and stability of the devices. Differential scanning calorimetry results suggested that the improved photovoltaic performances may be attributed to the enhanced compatibility between poly(3- hexylthiophene) and PCBM. / published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Application of carbon nanomaterials like fullerene, carbon nanotubes, and graphene in solar cells using solution processable methods presents a great potential to reduce the cost of producing electricity from solar energy. However, carbon nanotubes and graphene materials are predominantly metallic and this limits their function in organic photovoltaic devices (OPVs) where semiconducting behavior is required. Doping of carbon nanomaterials is a well-known method for making them semiconducting. Doping of carbon nanomaterials with nitrogen and boron can tune their properties to suit the requirements for use in photovoltaic applications as n-type and p-type semiconducting materials, respectively. Indeed, the use of nitrogen doped and boron doped carbon nanotubes in organic solar cells together with fullerene acceptors can improve the current density of the OPV devices. Nitrogen doping of carbon nanotubes can be achieved by using nitrogen-containing precursor materials during chemical vapor deposition. However the doping of carbon nanotubes with nitrogen does not automatically make them n-type materials; they remain metallic unless a large amount of quaternary type nitrogen is incorporated in the carbon nanotubes. In this work we have developed a method to control the type of nitrogen that is incorporated in CNTs by using an appropriate synthesis temperature and use of oxygen-containing carbon precursors during the chemical deposition of carbon nanotubes. Quaternary N was incorporated in a CVD process when high temperatures and a high concentration of O in the precursor materials were used. We also showed that the type and amount of N can be changed from pyrrolic and pyridinic-N-oxide to pyridinic N and quaternary N by annealing N doped carbon nanotubes at temperatures above 400°C. At temperatures above 800°C most of the nitrogen is converted to quaternary nitrogen. N-CNT thin films were used in OPVs so as to modify the ITO electrode and transform it into a 3D electrode. The resulting effect was an improved short circuit current density in the devices containing an N-CNT thin film that was placed on top of the ITO electrode. A reduction in efficiency losses in OPVs at increasing light intensity was observed in the NCNT ITO modified electrode OPVs. This is a remarkable finding when considering that one of the main problems hindering commercialization of OPVs is the loss of efficiency at high light intensities. We related these effects to the efficient charge collection by the modified ITO electrode. Incorporation of N-CNTs in the bulk heterojunction layer of the OPV device resulted in poor performance when compared to an OPV device made without N-CNTs. This effect is caused by shorting of the OPVs. We used a method of incorporating N-CNTs whilst minimizing shorting and this showed potential for better performance. A study on the attempted doping of graphene with B to make it a p-type material showed that in the presence of a nitrogen carrier gas, BN instead of B was incorporated in graphene. This remarkable finding enabled us to grow a p-type graphene with a possible a band gap opening. This was corroborated by XPS and Raman spectroscopy studies of the material. This BN doped graphene material showed potential as a possible replacement of PEDOT:PSS as a hole transport material in OPVs. The BN doped graphene material can match the performance of PEDOT:PSS when the level of BN doping in graphene is increased.

A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy. / A comprehensive experimental study on alternating current (AC) electrical transport in the three forms of carbon nanotubes (CNTs) and nanodiamond films is presented. It is termed dynamic electrical transport to differentiate it from direct current measurements, which may be referred as static transport. The results and analysis are based on the scattering parameter measurements of a few horizontally aligned single, double, multi-walled carbon nanotubes and nanodiamond films. Which were measured in the frequency range 10 MHz to 65 GHz, at room and cryogenic temperatures using a vector network analyser. The work is motivated by the fact that AC transport in 1D systems has not been fully studied and is not well understood. From direct current measurements, it is known that one dimensional (1D) electrical transport is very different from its two or three dimensional counterpart. This is because adding an electron to a 1D system tends to affect the whole system in ways which to date cannot be fully explained theoretically. CNTs present an ideal platform to study the AC or dynamic transport behaviour of 1D systems because of the high mobility and electrical conductivity at nano-scale. Therefore from the AC complex impedance and conductance, this work demonstrates quantum effects of collectively excited strongly interacting electrons (Luttinger Liquid), which had been predicted theoretically but not observed experimentally using this technique. Ballistic transport at room temperature is also demonstrated by setting the stimulus frequency higher than the scattering rate in the CNTs. A crossover from capacitive to inductive behaviour in the imaginary component of impedance has been shown by improving the CNT-electrode coupling. Furthermore the effect of metal contacts on microwave/ radio frequency transmission is also demonstrated. The results are consolidated by RF simulations, as strong conclusions are drawn. Studies on the dynamic transport in nanodiamond films revealed a crossover from the insulating to semi-metallic regime by nitrogen incorporation. The crossover is explained by considering the changes of the grain boundary morphology. This work shows that AC transport in polycrystalline nanodiamond films is similar to DC transport.

Current research in the field of nano-electronics is directed towards device miniaturization in order to find ways to increase the speed of electronic devices. The work presented in this dissertation is on the electronic transport properties of single walled carbon nanotube (SWNT) ropes synthesized by laser ablation. The measurements were performed on devices with different geometries; namely SWNT mats, metal incorporated (aligned individual and bundled) SWNTs and lastly on aligned pure SWNTs from low temperatures up to room temperature. The work was performed so as to gain an understanding on how best to utilize SWNTs in the semiconductor industry towards miniaturization. Such an understanding would ultimately highlight if SWNTs can be considered as a viable alternative to the current silicon-based technology, which seems to be approaching its physical limit. For a mat of SWNTs, 3D-Variable range hopping is the principal conduction mechanism from 2 K – 300 K. The magneto-resistance was found to be predominantly negative with a parabolic nature which converts to a linear nature as the temperature is increased. The negative MR is a consequence of quantum interference and the positive upturn is attributed to wave function shrinkage at low temperatures as described by the Efros-Shklovskii model. The hopping ranges of the electrons for a SWNT mat increases as the temperature decreases due to manifestation of quantum effects and reduced scattering. It was also found that metal incorporation does not alter the properties of the SWNT significantly. SWNT ropes aligned by di-electrophoresis across a 1 micron gap between gold micro-electrodes, exhibit Tomonaga-Luttinger liquid (TLL) like behaviour, within the 80 K – 300 K temperature range. The effects of confinement and electron-electron interaction unique to one dimension were identified in electronic transport as a non-universal power law dependence of the differential conductance on temperature and source-drain voltage. Ballistic conductance at room temperature was confirmed from the high frequency transport of the SWNT devices. The complex impedance showed some oscillatory behaviour in the frequency range 6 to 30 GHz, as has been predicted theoretically in the Tomonaga-Luttinger Liquid model. The observation of Luttinger Liquid behaviour demonstrates the outstanding nature of these one-dimensional molecular systems. In these devices the charging Coulomb energy of a single particle played a critical role in the overall device performance. This study can be used to understand the nature of dynamics of plasmons which are the charge carriers in a TLL system and how Coulomb interactions can be used to design highly tuneable systems for fabrication of single molecule devices. The incorporation of metal onto individual SWNT ropes does not alter its electronic properties significantly but the properties of the bundled metal incorporated SWNT ropes are altered. This study has found that under optimized conditions SWNTs might be a viable option for incorporation in nano electronics devices. Individual SWNT ropes promise better devices compared to SWNT mats and further work should be done on individual SWNTs.

by Jia, Jiangying. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves ). / Abstracts in English and Chinese. / ABSTRACT --- p.i / 摘要 --- p.ii / ACKNOWLEDGEMENTS --- p.iii / TABLE OF CONTENTS --- p.iv / LIST OF FIGURES --- p.vii / LIST OF TABLES --- p.ix / Chapter CHAPTER ONE --- INTRODUCTION --- p.1 / Chapter 1.1 --- Background --- p.2 / Chapter 1.1.1 --- Vibration damping --- p.2 / Chapter 1.1.2 --- Carbon nanotubes --- p.4 / Chapter 1.1.3 --- Fabrication of carbon nanotube composites --- p.8 / Chapter 1.1.4 --- Literature review on carbon nanotube composites --- p.10 / Chapter 1.2 --- Research Objective --- p.13 / Chapter 1.3 --- Thesis Organization --- p.14 / Chapter CHAPTER TWO --- FABRICATION OF CNT AND CNT/EPOXY COMPOSITES --- p.15 / Chapter 2.1 --- Fabrication of CNT --- p.16 / Chapter 2.1.1 --- Fabrication requirements --- p.16 / Chapter 2.1.2 --- Substrate and catalyst preparation --- p.17 / Chapter 2.1.3 --- Aligned CNT film grown by PECVD method --- p.18 / Chapter 2.2 --- Fabrication of CNT/Epoxy Composite --- p.25 / Chapter 2.3 --- Measurement of CNT/Epoxy Composites --- p.31 / Chapter 2.4 --- Chapter Summary --- p.34 / Chapter CHAPTER THREE --- MODELLING OF THE CNT COMPOSITES --- p.35 / Chapter 3.1 --- Geometrical Configuration of Composites --- p.36 / Chapter 3.2 --- Critical Shear Stresses and “Stick-Slip´ح Behavior --- p.38 / Chapter 3.3 --- Nonlinear Viscoelastic Composite Model --- p.40 / Chapter 3.3.1 --- Maxwell model --- p.40 / Chapter 3.3.2 --- Three-parameter standard solid model --- p.45 / Chapter 3.4 --- Stress and Strain Evaluation --- p.50 / Chapter 3.5 --- Effective Moduli and Loss Factor of Composite --- p.56 / Chapter 3.6 --- Chapter Summary --- p.60 / Chapter CHAPTER FOUR --- PARAMETRIC STUDY OF THE CNT COMPOSITES --- p.61 / Chapter 4.1 --- Carbon Nanotube Dimensions --- p.62 / Chapter 4.2 --- Parametric Study --- p.65 / Chapter 4.3 --- Summary --- p.69 / Chapter CHAPTER FIVE --- CONCLUSIONS AND FUTURE WORK --- p.70 / Chapter 5.1 --- Conclusions --- p.70 / Chapter 5.2 --- Future Work --- p.72 / BIBLIOGRAPHY --- p.73 / APPENDIX --- p.78 / Chapter A. --- Epoxy Resin Datasheet --- p.78 / Chapter B. --- Matlab Program for Young´ةs Modulus Calculation --- p.80 / Chapter C. --- Matlab Program for Loss Factor Calculation --- p.82

Typescript (photocopy) / xii, 149 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--Dept. of Soil Science, University of Adelaide, 1982

No description available.

It has been found that the composites of carbon nanotubes (CNTs) and epoxy resin could greatly enhance damping ability while the stiffness is kept at a very high level. In this research, carbon nanotube enhanced epoxy resin is fabricated. The dynamic properties of the nanotube composites are evaluated. A testing apparatus for obtaining composite dynamic properties is set up and measurement procedures are given. Multiple groups of specimens are made for investigations. In particular, the loss factors together with dynamic stiffness are measured for the specimens with different CNT weight ratio. Experimental results show that CNT additive can provide the composite with several times higher damping as compared with pure epoxy. The composite is much stiffer than viscoelastic material (VEM) while the damping is comparable when strain is above certain level. In order to further study the damping mechanism of the CNT composite, models are developed. Composite unit cell models containing single CNT segments are built by using finite element method (FEM). Models with varying CNT orientations are considered in order to describe the behaviors of the randomly oriented CNTs inside the epoxy matrix. Composite loss factors are calculated based on the average ratio of the unit cell energy loss to the unit cell energy input. Calculated loss factors under different strain levels are compared to experimental results. With the validated model, parametric study is thereafter performed. Parameters such as CNT dimensions and CNT alignment orientation are studied. Those factors lead to higher composite damping capacity are identified. / by Dai, Ruoli. / "September 2007." / Adviser: Wei-Hsin Liao. / Source: Dissertation Abstracts International, Volume: 69-08, Section: B, page: 4978. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references (p. 93-97). / 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.