Wastewater from the textile industry is difficult to treat effectively due to the prevalent use and wide variety of synthetic dyes that are resistant to conventional treatment methods. White-rot fungi, such as Trametes versicolor, have been found to be effective in decolorizing many of these synthetic dyes and current research is focusing on their application to wastewater treatment. Although numerous studies have been conducted on the ability of both living and nonliving Trametes versicolor to separately decolorize textile dyes, no studies were found to have investigated the use of a mixture of live and dead fungus for decolorization. This study explored potential interactions between live and dead, autoclaved Trametes versicolor biomass in a mixed system by utilizing a series of batch tests with two structurally different synthetic textile dyes. Samples were analyzed by spectrophotometer and compared with controls to determine the effect of any interactions on decolorization. The results of this study indicate that an interaction between living and nonliving biomass occurred that affected the specific dye removal for both Reactive Blue 19, an anthraquinone textile dye, and Reactive Orange 16, an azo textile dye. This interaction was seen to improve the specific dye removal during the first 10-46 hours of experimentation but then diminish the specific dye removal after this period. This effect could be due to hydrophobins, which are surface-active proteins excreted by live fungi that may alter hydrophobicity. Additionally, the presence of adsorptive dead biomass could affect dye contact with degrading enzymes released from the live fungus. By expanding current knowledge of the interactions that take place in a fungal bioreactor and their effect on textile dye decolorization, this research aims to inspire more effective and less costly bioreactor designs for the treatment of textile wastewater.

No description available.

Master of Science / Department of Chemistry / Jun Li / With the increasing consumption of energy and the depletion of fossil fuels, finding an alternative energy source is critical. Solar energy is one of the most promising energy sources and solar cells are the devices that convert solar radiation into electricity. Currently, the most widely used solar cell is based on p-n junction formed with crystalline silicon materials. While showing high efficiency, the high fabrication cost limits its broad applications. Dye sensitized solar cell (DSSC) is a promising low-cost alternative to the Si solar cell, but its efficiency is much lower. Improvements in materials and interfaces are needed to increase the DSSC efficiency while maintain the low cost. In this thesis, three projects were investigated to optimize the DSSC efficiency and reduce the cost. The first project is to optimize the TiO[subscript]2 barrier layers on Fluorine-doped Tin Dioxide (FTO) surface. Two preparation methods, i.e. TiCl[subscript]4 solution treatment and thermal oxidation of sputtered Ti metal films, were employed and systematically studied in order to minimize electron-hole recombination and electron backflow during photovoltaic processes of DSSCs. TiCl[subscript]4 solution treatment method was found to create a porous TiO[subscript]2 barrier layer. Ti sputtering method created a very compact TiO[subscript]2 blocking layer. Two methods showed different characteristics and may be used for different DSSC studies. The second project is to reduce the DSSC cost while maintaining the efficiency by replacing the expensive Pt counter electrode with a novel vertically aligned carbon nanofiber (VACNF) electrode. A large specific electrode surface area (~125 cm[superscript]2 over 1 cm[superscript]2 geometric area) was obtained by using VACNFs. The relatively high surface area, good electric conductivity and the large numbers of active graphitic edges existed in cone-like microstructure of VACNFs were employed to improve redox reaction rate of I[subscript]3[superscript]-/I[superscript]- mediators in the electrolyte. Faster electron transfer and good catalytic activities were obtained with such counter electrodes. The third project is to develop a metal organic chemical vapor deposition (MOCVD) method to coat TiO[subscript]2 shells on VACNF arrays as potential photoanodes in the DSSC system in order to improve the electron transfer. Fabrication processes were demonstrated and preliminary materials were characterized with scanning electron microscopy and transmission electron microscopy. MOCVD at 300 mTorr vapor pressure at 550° C for 120 min was found to be the optimal condition.

The operating principles and design of an optical receiver for a Light Detection and Ranging (LIDAR) remote sensing instrument are addressed. The performance and limitations of a biaxial monostatic LIDAR system utilizing this design are investigated. The complete optical and structural design of the receiver, including specifications of components are outlined. The thermal stabilization of the detector assembly and the integration of control electronics are described. A detailed discussion of alignment procedures and possible improvements are made. A sample observation is presented with suggestions for fully automating the system.

Harnessing solar energy has become a promising clean and renewable energy source alternative to fossil fuels since the development of low-cost dye sensitized solar cells (DSSC) and organic photovoltaic solar cell devices. Their power-conversion efficiencies, below 13% and 9% respectively, still limit the economic viability of these technologies. The geometry and optical properties of photonic crystals can be used to improve the absorption and charge collection efficiencies of these devices. This thesis describes the fabrication of TiO2 DSSC and ZnO-polymer solar cell devices based on a three-dimensional photonic crystal structure. Photonic crystal polymer structures were produced by holographic lithography and thermally stabilized in order to be used as templates for atomic layer deposition (ALD) of various metal oxides. For this purpose, an ALD apparatus was built and ALD processes for the growth of TiO2, ZnO, Al2O3, ZnO:Al, and Zr3N4 were established and deposited on photonic crystal templates. After ALD, the template was removed by calcination at 500°C, at which ZnO:Al films lost their conductivity of 250 S/cm preventing their use as transparent conducting oxide (TCO) electrodes. The produced 90 nm TiO2 photonic crystal shell DSSC and TiO2 inverse replica devices based on the dye N-719 and iodine/iodide redox electrolyte provided power-conversion efficiencies of 0.9% and 0.49% respectively and their diffusion lengths were 2× and 3× longer than that of a nanocrystalline reference device respectively. ZnO-polymer devices, comprising a P3HT layer as absorber and PEDOT:PSS film as hole-transporter, were also investigated.

Thesis (PhD)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: A new class of nanocolorants is described for the use as a colorant in hot-melt ink application for ink-jet printing technology. An inverse miniemulsion polymerization process was utilized successfully as a one-step encapsulation process to encapsulate the highly hydrophilic water-soluble fluorescent Rhodamine B dye (RhB) by the hydrophilic water-soluble poly(acrylamide) (PAAm). Three types of Rhodamine B-based nanocolorants, PAAm/RhB, crosslinked-PAAm/RhB and poly(AAm-co-Sty)/RhB, were synthesized using inverse miniemulsion polymerization. The PAAm/RhB nanocolorants exhibited solid dark nanoparticles morphology, while crosslinked-PAAm/RhB and poly(AAm-co-Sty)/RhB showed a core-shell type of morphology. The nanocolorants showed improved light and dye migration fastness as well as high thermal stability, especially, nanocolorants with core-shell morphology. The synthesis of polymerizable RhB-based nanocolorants is described. Poly(AAm-co-RhB) nanocolorants were successfully synthesized for the first time via inverse miniemulsion polymerization. RhB dye was first functionalized by esterification reaction to introduce an acrylate polymerizable group. The RhB-acrylate dye was copolymerized with AAm monomer in an inverse miniemulsion polymerization to produce nanocolorants with superior light and migration fastness. Crosslinked-poly(AAm-co-RhB) nanocolorants could be obtained based on the incorporation of a crosslinking agent. Poly(AAm-co-RhB) and crosslinked-poly(AAm-co-RhB) nanocolorants exhibited a morphology of dark solid and core-shell particles, respectively. In both nanocolorants, the RhB-acrylate dye was completely integrated by copolymerization into the polymer matrix, and by that, the dye migration was completely supressed. Both poly(AAm-co-RhB) and crosslinked-poly(AAm-co-RhB) nanocolorants showed high thermal stability as well as high Tg values. The syntheses of PAAm/RhB nanocolorants-based solid inks were carried out successfully via inverse miniemulsion polymerization. An in situ inverse miniemulsion polymerization, with the paraffin wax as the organic phase, was utilized in making a crosslinked-PAAm/RhB nanocolorants-based solid ink. A crosslinked-poly(AAm-co-RhB) nanocolorants-based solid ink was prepared by the direct mixing of the readymade crosslinked-PAAm/RhB nanocolorants (suspended in cyclohexane) with paraffin wax at temperature above the melting temperature of the wax until all the cyclohexane evaporated. The obtained solid inks appeared as a solid homogenous waxy material with a deep bright colour reflecting that the nanocolorants were well dispersed in the wax. DSC thermograms showed that the solid inks have one sharp melting transition indicating the applicability of our nanocolorants for hot-melt ink applications. / AFRIKAANSE OPSOMMING: ‘n Nuwe reeks nonokleursels word beskryf vir die gebruik in ink-smelt drukker tegnologie. Inverse minie-emulsie polymerisasie was suksesvol gebruik om die kleurstof Rhodamine B (RhB) in die water oplosbare poly(akrielamied) (PAAm) te enkapsuleer. Die roete is gebruik om drie tipes kleurstof te produseer. Elk van die kleurstowwe was gebaseer op Rhodamine B en ‘n PAAm, naamlik PAAm/RhB, kruisgebonde PAAm/RhB en poli(akrielamied-ko-stireen)/RhB. PAAm/RhB nanokleursel was in die vorm van soliede donker nanopartikels. Die kruisgebonde PAAm/RhB en poli(akrielamied-ko-stireen) het bestaan uit nanoparikels met ‘n kern en skil morfologie. Die nanokleursels het ‘n verbetering in terme van lig en hitte stabiliteit getoon. Die migrasie van kleursel uit die nanopartikels, veral die met kern en skil morfologie, was baie minder. Die sintese van ‘n polimeeriseerbare nanokleursel gebaseer op RhB word beskryf. Poly(AAm-ko-RhB) nanokleursels was vir die eerste keer suksesvol gesintetiseer met behulp van ‘n inverse minie-emulsie polimerisasie. RhB kleursel was eers gefunksionaliseer deur middel van ‘n esterifikasie reaksie om ‘n polimeeriseerbare akrilaat groep te verkry. Die RhB-akrilaat kleursel was gekopolimeeriseer met AAm monomeer in ‘n inverse minie-emulsie polimerisasie om nanokleursels met verbeterde lig en migrasie stabiliteit te verkry. Kruisgebonde poli(AAm-ko-RhB) nanokleursels was verkry deur ‘n geskikte verbinding in die reaksie mengsel by te voeg. Beide poli(AAm-ko-RhB) and kruisgebonde poly(AAm-ko-RhB) nanokleursels was verkry as donker partikels met ‘n kern en skil morfologie. In beide gevalle was die RhB-akrilaat kleursel deeglik geintegreer in die matriks en sodoende was die migrasie van die kleursel heeltemal onderdruk. In albei gevalle het poli(AAm-ko-RhB) en kruisgebonde poli(AAm-ko-RhB) nanokleursels hoë hitte stabiliteit en hoë Tg waardes getoon. Die sintese van nanokleursels gebaseer op PAAm/RhB was sukselvol uit gevoer via inverse minie-emulsie polimerisasie. ‘n In situ inverse minie-emulsie polimerisasie met paraffin waks as die organiese fase was gebruik om soliede ink te produseer wat opgemaak is uit kruisgebonde PAAm/RhB nanokleursel. Die kruisgebonde poli(AAm-ko-RhB) soliede ink was voorberei deur die kruisgebonde PAAm/RhB nanokleursels (in suspensie met sikloheksaan) direk met die paraffin waks te meng by ‘n temperatuur hoër as die smeltpunt van die waks todat al die sikloheksaan verdamp het. Die soliede ink was verkry as ‘n homogene waksagtige materiaal met ‘n diep en helder kleur wat ‘n aanduiding was dat die nanokleursels goed versprei was in die waks. DSC termogramme het bewys dat die ink slegs een skerp smelt punt oorgang het wat beteken dat die materiaal geskik is om te gebruik in ink-smelt drukkers.

This work was concerned with the determination of mass transfer and kinetic parameters of ozone reactions with four organic compounds from different families, namely reactive dye RO16, triclocarban, naphthalene and methanol. In order to understand the mechanisms of ozone reactions with the organic pollutants, a radical scavenger (t-butanol) was used and the pH was varied from 2 to 9. Ozone solubility (CAL*) is an important parameter that affects both mass transfer rates and chemical reaction kinetics. In order to determine accurate values of the CAL* in the current work, a set of experiments were devised and a correlation between CAL* and the gas phase ozone concentration of the form CAL*(mol/L) = 0.0456 CO3 (g/m3 NTP) was obtained at 20°C. This work has also revealed that t-butanol did not only inhibit hydroxyl radical reactions but also increased mass transfer due to it increasing the specific surface area (aL). Values of the aL were determined to be 2.7 and 3.5 m2/m3 in the absence and presence of t-butanol respectively. It was noticed that the volumetric mass transfer coefficient (kLa) has increased following the addition of t-butanol. Ozone decomposition was studied at pH values of 2 to 9 in a 500 mL reactor initially saturated with ozone. Ozone decomposition was found to follow a second order reaction at pH values less than 7 whilst it was first order at pH 9. When the t-butanol was added, the decomposition of ozone progressed at a lower reaction order of 1.5 for pH values less than 7 and at the same order without t-butanol at pH 9. Ozone decomposition was found significant at high pHs due to high hydroxide ion concentration, which promotes ozone decomposition at high pHs. The reaction rate constant (k) of RO16 ozonation in the absence of t-butanol was determined. The result suggests that RO16 degradation occurs solely by molecular ozone and indirect reactions by radicals are insignificant. The chemical reaction of triclocarban with ozone was found to follow second order reaction kinetics. The degradation of naphthalene using the liquid/gas-ozone (LGO) system was studied. This result showed that hydroxyl radicals seemed to have limited effect on naphthalene degradation which was also observed when a radical scavenger (t-butanol) was used. Reaction rate constants were calculated and were found around 100 times higher than values reported in the literature due to differences in experimental conditions. From the results of the experimental investigation on the degradation of methanol by ozone it was found that the rate constant (k) of the degradation reaction increased at pH 9. The reaction stoichiometry was found to have a value of 1 mol/mol. The two steps of the liquid/solid-ozone (LSO) system were studied on beds of silica gel and a zeolitic material (D915) and the ozone adsorption process was modeled and found that particle rate controls ozone adsorption step but liquid rate controls the water treatment step. Ozone desorption with pure deionised water was studied. The water flow rate was found to accelerate the desorption rates but pH was found to decrease the desorption rates. In contrast, the effect of pH was insignificant in the presence of t-butanol. Determination of the adsorption isotherms for RO16, naphthalene and methanol revealed that RO16 did not exhibit adsorption on silica gel, but both naphthalene and methanol showed adsorption on D915 described by Langmuir model.

The molecular identity of the green emission of polyfluorene is investigated in the view point of the molecular interactions between modeled segments. The semi-empirical quantum methods, ZINDO/S and AM1 (AM1-CIS), are used in combination to provide reasonable explanations for experimental spectroscopic properties of monodisperse fluorene oligomers and fluorene oligomers with a central keto defect in dilute solutions. Applying the same method, the molecular interactions between model segments are found to exist and are significant. However, the spectroscopic property change from the molecular interactions is negligible. In addition, the effects of mechanical stress and multi-defects on fluorene oligomers are investigated. On the other hand, the redox mechanisms proposed for the oxidation of an amphiphilic cyanine (C8S3) J-aggregates immobilized at ITO electrode and the subsequent dehydrogenated dimmer formation during cyclic voltammetry based on analysis of absorption spectra during the process are verified with the combined semi-empirical quantum methods similar to the previous methods. The absorption spectra assigned by experiment for electrochemical species involved in the proposed mechanism show reasonable match to the theoretically estimated absorption energies of the corresponding simplified model systems. In addition, the standard reduction potentials of the fairly large molecules, C8S3 monomer and its dehydrogenated dimer, are pursued with quantum mechanical calculations. The free energy difference between the oxidized and reduced states of the target systems is decomposed to electronic energy, solvation energy and temperature-dependent free energies terms. Based on AM1 ground state geometries and with the corresponding temperature dependent free energies, the electronic energies and the solvation energies are each evaluated by two different methods. The electronic energies are calculated with AM1 method and DFT calculation and, also, the solvation energies are obtained based on the atomic partial charges from AM1 and DFT wavefunctions with continuum dielectric solvent approximation. The four calculation schemes from the combinations of the electronic and solvation energy estimation methods are tested with the redox compounds with various molecular weights and the estimations are compared with the corresponding experimental redox potentials. The relative redox potentials between two different redox systems are found to be reasonably estimated with the four calculation schemes. / text

Liquid crystals are traditionally aligned via a rubbed substrate. The rubbing creates anisotropic defects and strain in the material which provide an energetically favorable orientation for the liquid crystal (LC). This is a well-developed technology that is used in virtually all liquid crystal displays (LCDs). However, it is only capable of uniform alignment on a large planar substrate. This work utilizes a new class of photoalignment materials (PM) that replace the traditional buffing technique. PMs allow for patterned LC alignment using polarized photo-lithography. Further, instead of using a nematic liquid crystal, a UV curable liquid crystal polymer (LCP) is coated on this patterned alignment material. This generates a cured, aligned, and patterned thin film that has retardance and diattenuation if a dichroic dye is incorporated in the LCP. Using these materials and methods, retarders, polarizers, and polarized fluorescent sources are fabricated with dimensions as small as a few microns. In addition to exploring the material and processing properties of the PM and LCP system, arrays of micropolarizer are fabricated for the construction of a prototype polarization camera, termed an imaging polarimeter. An imaging polarimeter is a device that measures not only the intensity but also the polarization state of a light field. My imaging polarimeter design incorporates a patterned LCP polarizer focal plane array (FPA) that is aligned and mounted to a charge-couple-device (CCD) image sensor. A polarizer FPA allows an individual pixel on a CCD sensor to detect a unique polarization state, such as a specific linear polarization orientation or right or left handed circular polarization. Neighboring pixels are designed to detect different states and each cluster can then estimate the incident polarization state. Results of a linear LCP polarimeter operating in the visible spectrum are presented.

The concern of this dissertation is the understanding and improvement of a class of lasers that is responsible for some of the shortest optical pulses available today. In particular, we seek ways to produce from synchronously pumped mode-locked dye laser systems, shorter pulses of higher intensity with improved pulse-to-pulse consistency. Specific topics.that are discussed herein include the study of the role of the pump pulse in synchronously pumped mode-locked lasers, the study of the pulse shaping and shortening due to an intracavity saturable absorber, and the study of a fundamental pulse train instability associated with these lasers.