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The effectiveness of titanium dioxide (TiO?) in polyethylene films at preventing the photooxidation of riboflavin in a model solution was evaluated. Five different TiO? loads (0.5-8.0 wt%), each at 3 different thicknesses (50-100 um) were evaluated. A photochemical reactor, equipped with a 350W mercury lamp, provided full spectrum light or narrow bandwidth wavelength exposure, using filters allowing transmission at 25 nm wavebands at maximum peak height at 450, 550, or 650 nm. Riboflavin concentration was measured by HPLC over 8 hours of exposure. Increased TiO? load and thickness significantly affected riboflavin photooxidation (p<0.05). TiO? load had more influence on protection provided to riboflavin than did film thickness. Film opacity correlated linearly with decreased photooxidation (R2 of 0.831 & 0.783 for full spectrum and 450 nm bandpass-filter sets, respectively). Riboflavin photooxidation proceeded most rapidly with the full spectrum exposure (light intensity 118 ° 17.3 mW). Photooxidation occurred in the 450 nm bandpass-filter, but not for 550 & 650 nm sets (light intensities of 2.84 °0.416, 3.36 °0.710, and 0.553 ° 0.246 mW, respectively). Effect of fluorescent light-exposure (2020-1690 lux) on the same system was monitored over 2 days. Riboflavin degradation in the photoreactor proceeded ~300 times faster than under fluorescent lighting. Riboflavin degradation was found to significantly increase with the addition of chlorophyll-like tetrapyrroles (p<0.05). Riboflavin was found to significantly decrease the degradation rate of the tetrapyrroles pyropheophytin a and pheophytin a (p<0.05). The decrease in rate was not significant for chlorophyll a (p>0.05). / Master of Science in Life Sciences

No / Despite the extensive utilization of biomolecule-titania interfaces, biomolecular recognition and interactions at the aqueous titania interface remain far from being fully understood. Here, atomistic molecular dynamics simulations, in partnership with metadynamics, are used to calculate the free energy of adsorption of different amino acid side chain analogues at the negatively-charged aqueous rutile TiO2 (110) interface, under conditions corresponding with neutral pH. Our calculations predict that charged amino acid analogues have a relatively high affinity to the titania surface, with the arginine analogue predicted to be the strongest binder. Interactions between uncharged amino acid analogues and titania are found to be repulsive or weak at best. All of the residues that bound to the negatively-charged interface show a relatively stronger adsorption compared with the charge-neutral interface, including the negatively-charged analogue. Of the analogues that are found to bind to the titania surface, the rank ordering of the binding affinities is predicted to be "arginine" > "lysine" ≈ aspartic acid > "serine". This is the same ordering as was found previously for the charge-neutral aqueous titania interface. Our results show very good agreement with available experimental data and can provide a baseline for the interpretation of peptide-TiO2 adsorption data. / Veski

This dissertation concerns the synthesis of ultra-fine titania particles starting with titanium ethoxide as a precursor. The particle size and morphology was controlled using polymeric stabilizers which imparted in-situ steric stability during the particle growth. An attempt was made to elucidate the factors which govern the particle size and morphology by studying the solvent-polymer-particle surface interactions. For this purpose, the effects of polymer concentration, molecular weight, structure, and the solvent system were studied. Titanium dioxide particles were synthesized via the hydrolysis of tetraethylorthotitanate in ethanol in the presence of hydroxypropylcellulose, HPC, as an in-situ steric stabilizer. The effects of HPC concentration, molecular weight, and water concentration on TiO₂ particle size and morphology were determined along with the effect of HPC on the particle growth rate. The particle size decreased by ten-fold upon the addition of HPC at high water concentrations due to the combined effects of increased HPC adsorption and increased nucleation rates. Water was shown to segregate at the TiO₂ surface and to promote HPC adsorption through enhanced hydrogen bonding. Mean particle diameters as small as 70 nm were obtained. The particles grown with HPC had surface morphologies that suggest the particles aggregated by flocculating initially into a secondary energy minimum followed by condensation reactions that welded the aggregates together. Particle growth rate studies show that HPC can undergo an alcoholysis reaction with tetraethylorthotitanate when mixed in the absence of water. Electrophoresis measurements show the absence of any significant electrostatic stabilization effects under conditions giving the smallest particle sizes. In another related study, titanium dioxide particles were synthesized via the hydrolysis of tetraethylorthotitanate, TEOT, in mixtures of ethanol and tetrahydrofuran, THF, in the presence of hydroxypropylcellulose, HPC, as an in-situ steric stabilizer. The effects of THF concentration on the particle size and growth rate were studied at fixed concentrations of water, TEOT, and HPC. Particles grown in the absence of HPC were highly aggregated while the size of the primary particles comprising the aggregates decreased with THF concentration. The particle growth rate increased significantly with THF concentration due to the decrease in the hydrogen bonding capability of the solvent system which increased the activity of the water. In the presence of HPC, both the growth rate and the particle size decreased dramatically with increasing THF concentration. The decrease in the solubility of HPC with THF concentration presumably enhanced HPC adsorption at the particle surface which led to increased colloid stabilization. Particles as small as 50 nm in diameter were obtained when the particles were grown in 1:1 THF:ethanol volume mixtures. In an attempt to study the effect of polymer structure and structure on particle size and morphology, a low molecular weight (Mw = 2000) polymer with poly(propylene oxide) back-bone was end functionalized to make it a suitable in-situ steric stabilizer. Effects of polymer concentration, functionality at chain-ends, and molecular weight on the particle size were studied. The polymer functionalized at both ends imparted in-situ steric stability at C_p > 8 g/l. Particles having mean size of 0.2 microns were obtained at C_p = 16 g/l. This work demonstrated that end-functionalized low molecular weight polymers offer a novel way to synthesize in-situ steric stabilizers. An application of the synthesized ultra-fine titania particles was studied. For this purpose, novel thin films of ultra-fine titanium dioxide particles dispersed in a matrix of hydroxypropylcellulose polymer were made on quartz and silicon substrates. The TiO₂/HPC composite films were transparent in the visible region and completely blocked ultraviolet radiation at 300 nm. These films were crack-free and uniform in composition and thickness. Transparent films of amorphous TiO₂ were made by burning out the HPC at 500°C. These films were highly uniform and had no macroscopic cracks. X-ray diffraction revealed a transition to the anatase form upon sintering at 600°C. A film sintered at 700°C had a porosity of 38%. The crystalline films remained transparent until they densified at 800°C. / Ph. D.

Thesis (P.hD (Physics)) --University of Limpopo, 2013 / Titanium dioxide (TiO2) nanoparticles, nanowires, nanosheets and nanoporous are of great interest in many applications. This is due to inexpensive, safety and rate capability of the material. It has being considered as a replacement of graphite anode material in rechargeable lithium batteries. Much experimental work on pure and lithiated nanostructures of TiO2 has been reported, mostly with regards to their complex microstructures. In this work we employ molecular dynamics (MD) simulation to generate models of TiO2 nano-architectures including: nanosheet, nanoporous, nanosphere and bulk. We have successfully recrystallised all four nanostructures from amorphous precursors; calculated radial distribution functions (RDFs), were used to confirm crystallinity. Configuration energies, calculated as a function of time, were used to monitor the recrystallisation. Calculated X-Ray Diffraction (XRD) spectra, using the model nanostructures, reveal that the nanostructures are polymorphic with TiO2 domains of both rutile and brookite in accord with experiment. Amorphisation and recrystallisation was successful in generating complex microstructures. In particular, bulk and nanoporous structures show zigzag tunnels (indicative of micro-twinning) while nanosphere and nanosheet shows zigzag and straight tunnels in accord with experiment. All model nanostructures of TiO2 were lithiated with different lithium content. RDFs, microstructures, configuration energies, calculated as a function of time and XRDs of all lithiated structures are presented. / University of Limpopo Research Office,The Royal Institution(Ri),Granfield University,Materials Modelling Centre,UCL,and the CHPC

Semiconducting properties and related defect disorder for well defined TiO2 single crystal were studies. Semiconducting properties have been determined using simultaneous measurements of two independent electrical properties, including electrical conductivity, ??, and thermoelectric power, S, at elevated temperatures (1073-1323 K) in the gas phase of controlled oxygen activity (10-10 Pa &lt p(O2) &lt 75 kPa). Measurements of s and S were conducted (i) in the gas/solid equilibrium and (ii) during equilibration. Oxygen vacancies have been identified as the predominant defects in TiO2 over a wide range of p(O2). Individual conductivity components related to electrons, electron holes and ions, were determined from the obtained ?? data. The effect of p(O2) on these individual components was considered in the form of a diagram. This work led to the discovery of the formation and diffusion of Ti vacancies. However, the obtained diffusion data indicate that, in the temperature ranges commonly used in studies of semiconducting properties (1000-1400K), the Ti vacancies concentration is quenched and may thus be assumed constant. In addition it was shown that Ti vacancies in appreciable concentrations form only during prolonged oxidation. It was determined that the discrepancies in the reported n-p transition point are related to the concentration and spectrum of impurities as well as the concentration of Ti vacancies. It has been shown that the n-p transition point in high-purity TiO2 is determined by the Ti vacancy concentration. A well defined chemical diffusion coefficient, Dchem, was determined using kinetic data obtained during equilibration. A complex relationship between p(O2) and Dchem was observed. These data showed a good agreement between the obtained diffusion data and defect disorder. Examination of the determined equilibration kinetics, led to the discovery of two kinetic regimes, the result of the transport of defects at different mobilities. The determined data are considered well defined due to the following reasons: 1. The studied specimen was of exceptionally high purity and free of grain boundaries (single crystal) 2. The specimen was studied in the gas phase of controlled and well defined oxygen activity which was continuously monitored. 3. Whenever the experimental data were measured in equilibrium, the gas/solid equilibrium has been verified experimentally. 4. A good agreement between the two, self-confirmatory, electrical properties, including ?? and S has been determined simultaneously and independently. The defect disorder model derived in the present work may be used for tailoring controlled semiconducting properties through the selection of annealing conditions involving the temperature and oxygen activity.

Graduation date: 1995

Semiconducting properties and related defect disorder for well defined TiO2 single crystal were studies. Semiconducting properties have been determined using simultaneous measurements of two independent electrical properties, including electrical conductivity, ??, and thermoelectric power, S, at elevated temperatures (1073-1323 K) in the gas phase of controlled oxygen activity (10-10 Pa &lt p(O2) &lt 75 kPa). Measurements of s and S were conducted (i) in the gas/solid equilibrium and (ii) during equilibration. Oxygen vacancies have been identified as the predominant defects in TiO2 over a wide range of p(O2). Individual conductivity components related to electrons, electron holes and ions, were determined from the obtained ?? data. The effect of p(O2) on these individual components was considered in the form of a diagram. This work led to the discovery of the formation and diffusion of Ti vacancies. However, the obtained diffusion data indicate that, in the temperature ranges commonly used in studies of semiconducting properties (1000-1400K), the Ti vacancies concentration is quenched and may thus be assumed constant. In addition it was shown that Ti vacancies in appreciable concentrations form only during prolonged oxidation. It was determined that the discrepancies in the reported n-p transition point are related to the concentration and spectrum of impurities as well as the concentration of Ti vacancies. It has been shown that the n-p transition point in high-purity TiO2 is determined by the Ti vacancy concentration. A well defined chemical diffusion coefficient, Dchem, was determined using kinetic data obtained during equilibration. A complex relationship between p(O2) and Dchem was observed. These data showed a good agreement between the obtained diffusion data and defect disorder. Examination of the determined equilibration kinetics, led to the discovery of two kinetic regimes, the result of the transport of defects at different mobilities. The determined data are considered well defined due to the following reasons: 1. The studied specimen was of exceptionally high purity and free of grain boundaries (single crystal) 2. The specimen was studied in the gas phase of controlled and well defined oxygen activity which was continuously monitored. 3. Whenever the experimental data were measured in equilibrium, the gas/solid equilibrium has been verified experimentally. 4. A good agreement between the two, self-confirmatory, electrical properties, including ?? and S has been determined simultaneously and independently. The defect disorder model derived in the present work may be used for tailoring controlled semiconducting properties through the selection of annealing conditions involving the temperature and oxygen activity.

Thesis (Ph. D. (Physics)) -- University of Limpopo, 2016. / Single and double doped nanometric powders of Single and double doped nanometric powders of titanium dioxide (TiO2) were synthesised by the sol-gel process using titanium isopropoxide (TTIP) as the precursor. For comparison, an undoped sample was also prepared. The metal dopants, Ag and Cu, were used at doping levels of 5% molar weight. The samples were dried at 100°C in air and post annealing was done at 300°C, 600°C, 900°C and 1100°C. Structural characterisation of the samples was carried out by X-ray Diffraction (XRD), Raman Spectroscopy, Scanning Electron Microscopy (SEM) and Energy dispersive X-ray Spectrometry (EDS) techniques. Most samples annealed at the 300°C temperature (and lower) revealed the predominantly-anatase phase, while those annealed at 900°C and above were rutile-only. The double-doped powder that was annealed at 300°C was found to be constituted by anatase and brookite phases (with the dopants incorporated into the TiO2 matrix), and the one annealed at 600°C was a mixture of brookite and rutile. The results suggest that multiple doping of titania may favour a two-phase structure at lower temperatures than singly-doped powders. The co-existence of brookite with anatase is believed to be responsible for the enhancement of anatase to rutile transformation in the double-doped sample. UV-visible (UV-vis) and Photoluminescence (PL) measurements were also carried out to study the optical properties of the TiO2 nanoparticles. This revealed the active PL band at around 440 nm. By narrowing the band gap, the double-doped powders that exhibited the brookite phase, again showed improved visible light photo absorption over the other samples, with a significant shift of the absorption edge to shorter wavelengths. Further, PL spectra revealed a change in PL intensity with phase change, as well as the presence of exciton energy levels at the base of the conduction band. The changes in the electrical conductivities of representative anatase and rutile TiO2 nanopowders upon exposure to water-vapour, ammonia (NH3) and hydrogen (H2) were also investigated. Sensing measurements for water-vapour was done at room temperature for various humidity levels ranging from 5.4% RH to 88.4% RH. The detection of NH3 and H2 gases were carried out at temperatures extending from room temperature to 350°C and over concentration ranges of 25 sccm to 500 sccm and 15 v sccm to 200 sccm respectively. The gas-sensing results show that the sol-gel fabricated TiO2 nanoparticles (particularly in anatase form), has excellent fast and stable dynamic responses to humidity, NH3 and H2. They feature good sensitivities, even at a low operating temperatures. However, acceptor behaviour, for which there was a conductivity switch from n-type to p-type, was recorded for the Ag-doped rutile powders at operating temperatures of 300ºC and 350ºC. Overall, the double-doped sample annealed at 300ºC was deemed the most promising candidate for gassensing. (TiO2) were synthesised by the sol-gel process using titanium isopropoxide (TTIP) as the precursor. For comparison, an undoped sample was also prepared. The metal dopants, Ag and Cu, were used at doping levels of 5% molar weight. The samples were dried at 100°C in air and post annealing was done at 300°C, 600°C, 900°C and 1100°C. Structural characterisation of the samples was carried out by X-ray Diffraction (XRD), Raman Spectroscopy, Scanning Electron Microscopy (SEM) and Energy dispersive X-ray Spectrometry (EDS) techniques. Most samples annealed at the 300°C temperature (and lower) revealed the predominantly-anatase phase, while those annealed at 900°C and above were rutile-only. The double-doped powder that was annealed at 300°C was found to be constituted by anatase and brookite phases (with the dopants incorporated into the TiO2 matrix), and the one annealed at 600°C was a mixture of brookite and rutile. The results suggest that multiple doping of titania may favour a two-phase structure at lower temperatures than singly-doped powders. The co-existence of brookite with anatase is believed to be responsible for the enhancement of anatase to rutile transformation in the double-doped sample. UV-visible (UV-vis) and Photoluminescence (PL) measurements were also carried out to study the optical properties of the TiO2 nanoparticles. This revealed the active PL band at around 440 nm. By narrowing the band gap, the double-doped powders that exhibited the brookite phase, again showed improved visible light photo absorption over the other samples, with a significant shift of the absorption edge to shorter wavelengths. Further, PL spectra revealed a change in PL intensity with phase change, as well as the presence of exciton energy levels at the base of the conduction band. The changes in the electrical conductivities of representative anatase and rutile TiO2 nanopowders upon exposure to water-vapour, ammonia (NH3) and hydrogen (H2) were also investigated. Sensing measurements for water-vapour was done at room temperature for various humidity levels ranging from 5.4% RH to 88.4% RH. The detection of NH3 and H2 gases were carried out at temperatures extending from room temperature to 350°C and over concentration ranges of 25 sccm to 500 sccm and 15 v sccm to 200 sccm respectively. The gas-sensing results show that the sol-gel fabricated TiO2 nanoparticles (particularly in anatase form), has excellent fast and stable dynamic responses to humidity, NH3 and H2. They feature good sensitivities, even at a low operating temperatures. However, acceptor behaviour, for which there was a conductivity switch from n-type to p-type, was recorded for the Ag-doped rutile powders at operating temperatures of 300ºC and 350ºC. Overall, the double-doped sample annealed at 300ºC was deemed the most promising candidate for gassensing.