Effects of annealing on the structural and optical properties of nanostructured TiO2
- Authors: Talla, Assane , Urgessa, Zelalem
- Date: 2023-12
- Subjects: Titanium dioxide , Nanostructured materials , Nanotubes
- Language: English
- Type: Doctorial theses , text
- Identifier: http://hdl.handle.net/10948/62655 , vital:72907
- Description: In this thesis, the structural, morphological and optical properties of titanium dioxide (TiO2) are investigated. Titanium dioxide (TiO2) nanotubes are prepared by anodic oxidation of titanium foil. The as-anodised samples are thermally annealed at various temperatures in nitrogen, air, oxygen and vacuum. The purpose is to study how the annealing conditions affect the properties of the nanostructures, including the anatase to rutile phase transformation. In all annealing atmospheres, except in vacuum, the dominant phase is found to be anatase when annealing is performed up to 600 oC. Above 700 oC the rutile phase becomes dominant. The anatase phase is stable above 600 oC in vacuum and does not evolve significantly up to 900 oC. The morphologies of the tubes tend to deteriorate with increased annealing temperature, in nitrogen, air and oxygen atmospheres, due to sintering effects. However, the integrity of the nanotubes is maintained up to 900 oC in vacuum. The photoluminescence (PL) spectra suggest mainly the presence of oxygen vacancies and self-trapped excitons, with respective emission bands around 2.5 eV and 2.3 eV. The results show that both the annealing temperature and atmosphere strongly influence the crystalline and optical properties of the TiO2 nanotubes. In addition, the phase transformation from anatase to rutile for samples annealed in an oxygen-rich environment is investigated in detail. Complementary structural information obtained from transmission electron microscopy and Raman analysis for oxygen-annealed samples reveals that the nucleation of the rutile phase starts from the titanium substrate and then propagates along the tubes. The results provide suitable annealing conditions to control the phase content and morphology of anodic TiO2 nanotubes. The PL characteristics of bulk crystalline anatase TiO2, namely virgin and hydrogen-annealed at 600 oC for 1 h, are studied. The low temperature PL spectra at 5.5 K shows near band edge (NBE) emissions with two dominant lines ascribed to shallow donor bound exciton and possibly free to bound recombination. The two main transitions are assisted by optical phononmodes. Temperature-dependent PL measurements performed on these anatase crystals reveal that the donor bound exciton is stable below 90 K. Hydrogen trapped in oxygen vacancies is proposed to be the shallow donor. In addition, two activation processes are involved for the thermal quenching of donor bound excitons. The total activation energy is found to correlate well with the localisation energy of the bound exciton. Site-selective PL spectra obtained from anodic TiO2 tubes reveals that the luminescence of the nanostructures depends on the morphology. The result shows unusual near-band edge emission (NBE) for these structures, which is rarely observed in indirect band gap TiO2. , Thesis (PhD) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2023
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- Date Issued: 2023-12
Potential use of carbon nanotubes as a nanofiller for natural rubber latex condoms
- Authors: Agbakoba, Victor Chike
- Date: 2018
- Subjects: Nanotubes , Rubber chemistry Nanocomposites (Materials) Nanostructured materials
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/23393 , vital:30538
- Description: The recent advancement in the field of nano-technology has raised much interest in the area of natural rubber latex (NRL) processing. This interest stems from the exceptional properties of nano-material and the promising results obtained by several researchers. Studies have shown that very low loadings of inorganic nanomaterials such as carbon nanotube (CNT) in NRL matrix leads to enhanced tensile strength, tensile modulus, tear resistance and aberration resistance. Thus providing a great prospect for reinforcement of thin film NRL articles such as condom. In this research, prevulcanised natural rubber latex (PvNRL) composite blends containing single walled carbon nanotubes (SWCNTs) were prepared via direct mixing. A progressive discolouration of PvNRL was observed with increased loadings of CNTs. Thermal analysis revealed faster drying rates for the composite blends containing SWCNT. Results from equilibrium swelling experiments also suggested a slight increase in crosslink density in the presence of SWCNT. There was a significant influence on flow behaviour of PvNRL as a result of varying loadings of SWCNT suspension. This was reflected as a change in pseudoplasticity and apparent viscosity. For Instance, apparent viscosity at a shear rate of 1 s-1 at 25°C for PvNRL with ~0.08% SWCNT was 2.5 Pa.s, compared to 0.49 Pa.s for the blends with 0.02% SWCNT. Condoms were moulded via the straight dipping technique using custom made glass formers. A series of dilutions was performed to correct the viscosity differences. This also ensured good consistency and promoted uniform deposition of PvNRL on the glass former. The average dimensions of the condoms produced in terms of length and width were ~191.17 ± 5.17 mm and 52.67 ± 5.17 mm respectively. Thickness measurement varied slightly according to the method of determination. The water leakage test suggested the absence of holes in the condoms produced. However, results from electrical leakage test contradicted those from water leak test. The results from infrared spectroscopy (FTIR) did not confirm the presence of chemical interactions between the SWCNT and PvNRL matrix. Glass transition temperature (Tg) was also unaffected across the blends. The stiffness (or modulus) was unaffected in all the condoms, as revealed by results from indentation hardness analysis. The SWCNT showed no significant influence on thermal decomposition temperatures of the condoms. Nonetheless, images from optical microscopy revealed increased surface roughness corresponding to higher loadings of SWCNT. Results from stress relaxation studies revealed improved retention of modulus under constant strain for condom samples containing SWCNT.
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- Date Issued: 2018
Synthesis and characterization of titanium dioxide nanotubes on fluorine-doped tin oxide (FTO) glass substrate using electro-anodization technique
- Authors: Zinya, Simcelile https://orcid.org/0000-0001-5864-0957
- Date: 2017-12
- Subjects: Titanium dioxide , Nanotubes , Nanostructured materials
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10353/23979 , vital:62201
- Description: One-dimensional (1-D) titanium dioxide nanotubes (TNTs) have attracted much attention as a promising alternative electrode material for dye sensitized solar cell (DSSC). As compared to the randomly packed and disordered TiO2 nanoparticles (TNPs) network with numerous particle-particle interfaces, TNTs prove to have fascinating features than make them suitable candidates in DSSCs. Well-structured TNTs arrays are of great potential among the various types of 1D TiO2 nano-materials owing to their superior electron transport properties with limited grain boundaries. Vectorial transport of photon generated electrons along the TNTs has been reported to lead to higher charge mobility which is crucial for improvement of DSSC performances. In this work, highly adhesive titanium films were deposited on functional substrates (FS) using radio frequency (RF) sputtering technique at a sputtering output power of 1kW, operating pressure of 1.5 Pa and at a deposition temperature of 200 °C to obtain a thickness of 10 μm under an inert argon atmosphere. The duration period for sputter coating 10 μm thickness of titanium film layer was 122 minutes with sputter rate for titanium target of about 82 nm per minutes. Subsequently, the RF sputtered titanium films were anodized with 0.5 wt. percent ammonium fluoride + 0.35 wt. percent deionised water and 96 wt. percent glycerol electrolyte solution at room temperature at 60 V for 72 hours. The resulting TNTs on functional substrates (TNTs-FS) were subjected to thermal treatment at 350 °C, 450 °C, 550 °C and 650 °C for 3 hours under oxygen atmosphere. The effect of annealing temperature on the morphological, and structural properties have been scrutinized. The as prepared and thermally treated TNTs-FS were characterized using scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and Confocal Raman Spectroscopy (CRS). SEM and HRTEM techniques were employed to confirm the presence of the TNTs-FS and also to study the structural-morphology of the TNTs as the annealing temperature increases. SEM revealed improvement in morphology with increase in sample annealing temperature, even at high temperatures such as 650 °C with no collapsing and sintering of the TNTs-FS occurring. SEM images revealed TNTs-FS with pore diameter sizes in the range between 85-170 nm. This is in compliance with HRTEM analysis, which revealed smooth and straight tube walls and improved surface morphology with increase in annealing temperature. In addition HRTEM images revealed pore diameter of TNTs-FS in the range between 85-165 nm. Furthermore, HRTEM revealed lattice fringes of 0.351, 0.352 and 0.353 nm between the neighbouring lattice fringes. All corresponding to (101) planes of anatase phase TNTs at different annealing temperatures (350-650 °C). The crystallographic structure of TNTs-FS was characterized by XRD measurements after thermal treatment at 350 °C, 450 °C, 550 °C and 650 °C. The XRD pattern revealed peaks in the wide angle range of 2θ (20° < 2θ > 80°) discovered at 29.43°, 45.10°, 56.52°, 63.5°, 64.92° and 74.81° corresponding to the planes (101), (112), (200), (105), (211) and (204) crystalline structures of the anatase TNTs. The intensity of the peaks increased with increasing annealing temperature. The strong sharp peaks indicate the large quantities and higher degrees of crystallinity of anatase phase of the TNTs. CRS Large Area Scan (LAS) and Depth profiling (DP) were employed to evaluate the crystallinity and phase distribution of TNTs-FS thermally treated at different temperatures. CRS LAS in the XY direction of TNTs-FS revealed the presence of differently crystallized anatase phases of TiO2 with Raman vibrational modes of 159.38 cm-1 (Eg), 208.37 cm-1 (Eg), 399.67 cm-1 (B1g), 514.25 cm-1 (A1g) and 641.58 cm-1 (Eg) for the samples annealed at 350 °C. The effect of annealing temperature on TiO2 phase evolution was meticulously evaluated using CRS for TNTs-FS for the samples annealed at 350 °C, 450 °C, 550 °C and 650 °C. The FWHM was estimated from CRS and decreases with increasing annealing temperature resulting in increasing crystallinity. Increase in anatase FWHM and anatase peak intensity implies higher degree of crystallinity and increasing crystallite sizes were also confirmed by XRD. Growing of titanium dioxide on functional substrates one novel contribution towards the fabrication of efficient electrode materials for solar cell development. Our method of characterizing TNTs-FS from a large area scan along the surface of the samples and depth profiling along the TNTs tube walls using confocal Raman spectroscopy prove to be a pivotal step in the development of efficient photoelectrode materials of the solar devices. , Thesis (MSc) -- Faculty of Science and Agriculture, 2017
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- Date Issued: 2017-12
Nanomaterial modified electrodes : optimization of voltammetric sensors for pharmaceutical and industrial application
- Authors: Brimecombe, Rory Dennis
- Date: 2011
- Subjects: Voltammetry , Electrochemistry , Nanotubes , Nanostructured materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4101 , http://hdl.handle.net/10962/d1009721
- Description: Nanomaterials, in particular carbon nanotubes have been shown to exhibit favourable properties for the enhancement of electrochemical detection of target analytes in complex matrices. There is however scope for improvement in terms of the optimization thereof in electrochemical sensors surface modification. The aim of this thesis was to examine methods that would result in increased current response, lowered passivation and application of such modified surfaces with application to pharmaceutically and industrially relevant analytes. Current methods for enhancing the performance of carbon nanotubes include acid functionalization which not only increases the hydrophilicity of the nanotubes, and consequently their ability to provide stable (aqueous) suspensions, but also introduces electrochemically active sites. This particular approach is however not normalized in the literature. Over-exposure to acid treatment results in loss of structural integrity of the carbon nanotubes, and as such a fine balance exists between achieving these dual outcomes. Guided by high resolution scanning electron microscopy, atomic force microscopy, voltammetric and impedance studies, this thesis examined the role of the length of time of the acid functionalization process as well as the impact of activation of carbon nanotubes and fullerenes on electrochemical sensor performance. Based on desired charge transfer resistances, rate transfer coefficients and sensitivity towards redox probes the optimal length of acid functionalization for multiwalled carbon nanotubes was 9 hours and 4 hours for single-walled carbon nanotubes. Further improvements in the desired outcomes were achieved through electrochemical activation of the modified electrode surface by cycling in the presence of catechol, in a novel approach. By employing electrochemical impedance spectroscopy it was observed that catechol activation resulted in lowered charge transfer resistance, before and after activation, with functionalized multi-walled carbon nanotubes (9 hours) exhibiting the greatest decrease of 90 % and functionalized single-walled carbon nanotubes (4 hours), a 50 % decrease. Corresponding increases in the heterologous rate transfer coefficient showed a 770 % increase for functionalized multi-walled carbon nanotubes (9 hours), following catechol activation. Comparative observations for fullerenes following partial reduction in potassium hydroxide yielded a 30 % decrease in charge transfer resistance, with an increased heterologous rate transfer coefficient at a fullerene modified surface The performance of the nanomaterial modified electrodes was applied to the detection of wortmannin with applications in bioprocess control and in the pharmaceutical sector as well as to the detection and monitoring of the industrial dye Reactive red. Of particular relevance to these analytes was the assessment of the nanomaterial modified electrodes for enhanced stability, reproducibility, sensitivity and decreased passivation effects. In this study the first known account of wortmannin detection through electrochemical methods is reported. Voltammetric characterization of wortmannin revealed an irreversible cathodic process with a total number of 4 electrons and a diffusion coefficient of 1.19 x 10-7 cm².s⁻¹. At a functionalized multiwalled carbon nanotubes modified glassy carbon electrode a limit of detection of 0.128 nmol.cm⁻³ was obtained, and with limited surface passivation the detection scheme afforded pertinent analyses in biological media representing a substantial improvement over chromatographic detection methods. This study also provided the first account of the voltammetric detection of reactive red, competing favourably with traditional spectroscopic methods for monitoring biodegradation of this compound in real time.
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- Date Issued: 2011
Nanostructures and metallophthalocyanines : applications in microbial fuel cells
- Authors: Edwards, Sean
- Date: 2011
- Subjects: Microbial fuel cells , Waste products as fuel , Nanostructured materials , Electrochemistry , Nanotubes
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4107 , http://hdl.handle.net/10962/d1011742 , Microbial fuel cells , Waste products as fuel , Nanostructured materials , Electrochemistry , Nanotubes
- Description: Microbial fuel cells (MFCs) are a promising form of alternative energy capable of harnessing the potential energy stores in organic waste. The oxygen reduction reaction (ORR) forms an integral role in the generation of electricity in MFCs however it is also a potential obstacle in enhancing the performance of MFCs. Platinum, a commonly used catalyst for the ORR, is expensive and rare. Significant research has been conducted into developing alternative catalysts. Metallophthalocyanines (MPc) have garnered attention for use as catalysts. Iron phthalocyanine (FePc) has been shown to have catalytic activity towards the reduction of oxygen. Coupling of the catalyst to nanostructured carbon materials, such as multi-walled carbon nanotubes, has been observed to have several advantages as nanostructures have a high surface-to-volume ratio. In this study, we have attempted to assess the suitability of FePc, both its bulk and nanostructured form, as an oxygen reduction catalyst and acid functionalized multi-walled carbon nanotubes for use as a catalyst support using electrochemical techniques such as cyclic voltammetry and electrochemical impedance spectroscopy. We showed, for the first time, the catalytic nature of nanostructured FePc towards the ORR. Applying the data obtained from the electrochemical analyses, electrodes were modified using FePc and MWCNTs and applied to an Enterobacter cloacae-based MFC. Several operational parameters of the MFC, such as temperature and ionic strength, were optimized during the course of the study. We showed that optimized FePc:MWCNT-modified electrodes compared favourably to platinum-based electrodes in terms of power densities obtained in a microbial fuel cell.
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- Date Issued: 2011