La connaissance d’un système gaz/solide requiert l’analyse de l’adsorption, du premier stade jusqu’à saturation. C’est la motivation de l’analyse des surfaces sous vide. L’approche des surfaces divisées est souvent tronquée. Pratiquée à des pressions suffisamment élevées pour être compatible avec un temps de réaction raisonnable, elle ne permet pas l'analyse de la surface nue à la monocouche. L’objectif du présent travail a été d’établir une continuité d’observation par FTIR, de l’UHV à la pression ambiante, de poudres de MgO, ZnO et ZnxMg1-xO exposées à l’eau ou à l’hydrogène. Il a été montré que les fumées de ZnO se comparent à des cristaux présentant les faces (0001), (0001̅), (101̅0), (112̅0), avec un rapport non-polaire/polaire de 75/25. Par FTIR combinée à la photoémission et à la désorption thermique, trois étapes de l’hydroxylation des fumées de MgO ont été identifiées : défauts ponctuels (10-8 mbar), marches (10-6 mbar) puis terrasses (> 10-5 mbar), avec une restructuration qui prouve que l’eau change la structure de surface de MgO. La représentation commune de la surface de MgO par une suite de facettes (100) est mise en cause. Aux faibles teneurs en zinc, l’oxyde mixte ZnxMg1-xO est formé de cristallites cubiques de même structure que MgO. Le zinc en substitution tend à ségréger vers les sites de basse coordinence où il affecte les propriétés d’adsorption d’eau et d’hydrogène. Par ailleurs, le mélange ZnO-MgO obtenu par combustion d’alliage ZnMg offre une possibilité d’application grâce aux propriétés bactéricides de ZnO et de faible toxicité de MgO. L’ensemble des résultats montre la pertinence de l’étude des poudres pratiquée dans les conditions de l’UHV. / The analysis of adsorption from the first stage to saturation is necessary to understand gas/solid interactions. This is the motivation for surface analysis under vacuum. The common approach of dispersed materials surfaces is incomplete since working pressures, that are high enough to achieve reasonable reaction times, do not allow studies of powder surfaces from bare to fully covered. The aim of the present work is to examine the successive changes of ZnO, MgO and ZnxMg1-xO nanopowders upon exposure to water or hydrogen from UHV to the ambient by FTIR. It is shown that ZnO smokes behave in a same way as a collection of single crystals which exhibit (0001), (0001̅), (101̅0) and (112̅0) faces with a non-polar/polar ratio of 75/25. Combining FTIR with XPS and TPD techniques, three stages of hydroxylation were identified on MgO smokes: point defects (10-8 mbar), steps (10-6 mbar) then terraces (> 10-5 mbar). Results indicate a reorganisation of surface structure showing that water adsorption on MgO(100) is an irreversible process. The common model of MgO as a series of (100) facets is questioned. At low concentrations of zinc, the mixed oxide ZnxMg1-xO consists of crystals with similar structure as MgO. A segregation of Zn2+ toward low coordinated surface sites is suggested to explain the changes in reactivity of the ZnxMg1-xO with respect to water and hydrogen at low coverages. Furthermore, the mixture ZnO-MgO produced by combustion of ZnMg alloy combines the antibacterial properties of ZnO and the biocompatibility of MgO, interesting for potential applications. The overall results demonstrate the relevance of the study of powders in ultra-high vacuum conditions.

Cette thèse porte sur la croissance de films minces d’oxydes de zinc/fer (ZnxFe1-xO1+δ par ablation laser pulsée (PLD) et sur la possibilité de contrôler leurs propriétés structurales et physico-chimiques en variant les conditions d’élaboration : pression d’oxygène et température de croissance, proportions respectives de zinc/fer. Pour de fortes valeurs de x (x > 65%), les films sont monophasés de structure wurtzite type ZnO (films Fe:ZnO), avec une transparence optique dans la gamme UV-visible de 80% mais sans propriété ferromagnétique ; en fonction de leur teneur en fer (1-x), ils évoluent de très bons conducteurs électriques à quasi-isolants. Pour de faibles valeurs de x (x < 15%), les films sont également monophasés de structure spinelle type Fe3O4 (films Zn:Fe3O4). Ils présentent de très bonnes propriétés ferromagnétiques dès la température ambiante ainsi qu’une bonne conductivité électrique, les effets de localisation des porteurs de charge se manifestant en dessous de la température de Verwey. Le nombre de parois d’antiphase peut être diminué par une croissance en deux étapes, comme l’atteste les mesures de magnétorésistance. Aux taux intermédiaires de zinc (15% < x < 65%), les films sont nano-composites. Dans le cas d’une coexistence des phases Fe:ZnO et Zn:Fe3O4, la bonne conductivité de Zn:Fe3O4 jointe à la multiplicité des variantes épitaxiales et donc des interfaces fournit un matériau adapté à la thermoélectricité. Dans le cas d’une coexistence de la phase ferrromagnétique Zn:Fe3O4 avec la phase Zn:FeO antiferromagnétique de type sel gemme, un fort couplage d’échange ainsi qu’une anisotropie magnétique perpendiculaire élevée sont mis en évidence. / This thesis deals with the growth of thin films of zinc/iron oxides (ZnxFe1-xO1+δ) by pulsed laser deposition (PLD) and the possibility of controlling their structural and physicochemical properties by varying the elaboration conditions: oxygen pressure and growth temperature, respective proportions of zinc/iron. For high values of x (x> 65%), the films are single-phase with a ZnO-type wurtzite structure (Fe:ZnO films), with 80% optical transparency in the UV-visible range but without ferromagnetic properties; depending on their iron (1-x) content, they evolve from very good electrical conductors to near-insulators. For small values of x (x <15%), the films are also single-phase with a Fe3O4-type spinel structure (Zn:Fe3O4 films). They exhibit very good ferromagnetic properties at ambient temperature as well as good electrical conductivity, the localization effects of charge carriers occurring below the Verwey temperature. The number of antiphase walls can be decreased by a two-step growth, as evidenced by magnetoresistance measurements. At intermediate zinc rates (15% <x <65%), the films are nano-composites. In the case of a coexistence of the Fe:ZnO and Zn:Fe3O4 phases, the good conductivity of Zn:Fe3O4 combined with the multiplicity of epitaxial variants and thus of the interfaces provides a material suitable for thermoelectricity. In the case of a coexistence of the ferrromagnetic Zn:Fe3O4 phase with the Zn:FeO antiferromagnetic rocksalt phase, strong exchange coupling as well as high perpendicular magnetic anisotropy are demonstrated.

With the proliferation of industries world-wide, there is a growing need and interest in sensing and monitoring environmental pollutants and monitoring the concentration of chemicals/gases in industrial process control. There is also an increasing demand for chemical sensors in other applications such as home security, breath analysis and food processing. Design and development of metal-oxide based gas sensor system is reported in this thesis. The system consists of three components viz. micro heater(which aids inheating the sensor film to required temperatures), CMOS ASIC (the sensor interface circuit) and the thin film transducer(a semiconducting metal oxide thin film whose resistance changes with the concentration of the target gas). Microheaters were realized through PolyMUMPs process. Thermal characterization of surface-micromachined microheaters is carried out from their dynamic response to electrothermal excitations. An electrical equivalent circuit model is developed for the thermo-mechanical system. The mechanical parameters are extracted from the frequency response obtained using a Laser Doppler Vibrometer. The resonant frequencies of the microheaters are measured and compared with FEM simulations. The thermal time constants are obtained from the electrical equivalent model by fitting the model response to the measured frequency response. Microheaters with an active area of140m × 140m have been realized on two different layers(poly-1 andpoly-2) with two different air-gaps (2m and 2.75m). The effective time constants, combining thermal and mechanical responses, are intherangeof0.13msto0.22msforheatersonpoly-1,and1.9s to0.15ms for microheaters on poly-2 layer. The thermal time constants of the best microheaters are in the range of a few s, thus making them suitable for sensor applications that need faster thermal response. The mechanical deformation of the microheaters subjected to an electrothermal excitation, due to thermal stress, is also analyzed using lensless in-line digital holographic microscopy (DHM). The numerically reconstructed holographic images of the micro-heaters clearly indicate the regions under high stress. Double exposure method has been used to obtain the quantitative measurements of the deformations, from the phase analysis of the hologram fringes. The measured deformations correlate well with the theoretical values predicted by a thermo-mechanical analytical model. The results show that lensless in-line DHM with Fourier analysis is an effective method for evaluating the thermo-mechanical characteristics of MEMS components. A sensor interface circuit comprising a resistance-to-time period converter as the front-end circuit and a proportional temperature controller to control the microheater temperature is designed and realized in 130nm UMC CMOS technology. The impact of biasing the transistors in subthreshold versus saturation conditions on analog circuit performance is systematically analyzed. A cascode current mirror, designed in 130nm CMOS technology, is biased in subthreshold and saturation regions and its performance has been analyzed through rigorous analytical modeling. The analytical results have been validated with SPICE simulations. It is demonstrated that the subthreshold operation provides better performance in terms of linearity, power, area, output impedance and tolerance to temperature variation, making it a preferable option for applications such as signal conditioning circuitry for environmental sensors. On the other hand, biasing the circuit in saturation is preferable for applications like transceivers and data converters where high bandwidth, SNR and low sensitivity to process variations are the key requirements. Based on this analysis, a sensor interface circuit has been prototyped for resistance measurement on 130nm CMOS technology, using subthreshold cascode current mirrors as the key building blocks. This current mirror results in 14X lower power compared to above-threshold operation. The interface circuit spans 5 orders of magnitude of resistance, and consumes an ultra low power of 326W. A proportional temperature controller with an integrated on-chip power MOSFET is also realized on the same chip for heating and temperature control of microheaters. The microheater is reused as temperature sensor. The entire circuit works with 1.2V supply, except the power MOSFET and the heater driver circuit, which operate with 3.3V supply. ZnO, a semiconducting metal-oxide, is used as the sensing material. Thin films of ZnO are spin-coated over insulating substrates using sol-gel processing technique. Gold pads deposited over the sensing film act as electrodes. The sensor film is characterized at different temperatures for its sensitivity to ethanol. A peak response of 14% change in resistance is observed for 5ppm ethanol, at a working temperature of 275◦C.

Currently available solid lubricants only perform well under a limited range of environmental conditions. Unlike them, oxides are thermodynamically stable and relatively inert over a broad range of temperatures and environments. However, conventional oxides are brittle at normal temperatures; exhibiting significant plasticity only at high temperatures (>0.5Tmelting). This prevents oxides' use in tribological applications at low temperatures. If oxides can be made lubricious at low temperatures, they would be excellent solid lubricants for a wide range of conditions. Atomic layer deposition (ALD) is a growth technique capable of depositing highly uniform and conformal films in challenging applications that have buried surfaces and high-aspect-ratio features such as microelectromechanical (MEMS) devices where the need for robust solid lubricants is sometimes necessary. This dissertation investigates the surface and subsurface characteristics of ALD-grown ZnO/Al2O3 nanolaminates and ZrO2 monofilms before and after sliding at room temperature. Significant enhancement in friction and wear performance was observed for some films. HRSEM/FIB, HRTEM and ancillary techniques (i.e. SAED, EELS) were used to determine the mechanisms responsible for this enhancement. Contributory characteristics and energy dissipation modes were identified that promote low-temperature lubricity in both material systems.

This thesis deals with the study of growth of zinc oxide crystals from supersaturated solutions using a scanning electron microscope and XRD methods. The work is divided into a theoretical and an experimental part. The theoretical part analyses issues related to the principle of operation of electrochemical cells with an emphasis on Ni-Zn batteries and phenomena limiting the life and efficiency of Ni-Zn batteries with a focus on phenomena that affect precipitation processes of zinc oxide crystals. It also analyses and compares the appropriateness of the methods that have been used to study the growth of the prepared zinc oxide crystals. The experimental part describes the preparation of a supersaturated solution, the process of each analysis and its evaluation. The results of each method are compared with the theoretical assumptions and among themselves. The experimental part also contains a chapter dealing with the design of in situ X-ray diffraction analysis methods of the obtained zinc oxide crystals.

Solid state lighting is a new environmentally friendly light source. So far, light emitting diodes (LEDs) and organic LEDs (OLEDs) have been presented as candidates with potentially high efficiency. Recent advances of OLEDs in device architecture, light-out coupling, and materials have ensured high efficiency, exceeding that of incandescent light bulbs. In contrast to conventional point source LEDs, OLEDs distribute light throughout the surface area and are not restricted by their size. Additionally, OLEDs are expected to reach sufficient stability in the near future. The remaining challenge for OLEDs is their cost. New OLED technologies provide cost effective manufacturing methods which could be presented for transparent electrode materials because indium tin oxide (ITO), a widely used material as a transparent electrode for OLEDs, is less than optimal due to its high element price. In this work, alternative transparent electrodes for OLEDs as a replacement of ITO were studied. First, Al doped ZnO (ZnO:Al) which is composed of abundant materials was investigated with DC magnetron sputtering under a wide range of experimental conditions. The optimised ZnO:Al received comparable performance with conventional ITO films, low sheet resistance of 22.8 Ω/sq as well as a high transparency of 93.1 % (average value in the visible range). Various type of p-i-n OLEDs were employed on the structured ZnO:Al using photolithography. Green OLEDs with double emission layers have been archived stable efficiencies even at higher luminance. Also, OLEDs using two fluorescent colour system on ZnO:Al anode showed a purely white emission. It has been found that the OLEDs on ZnO:Al anode has comparable or better device efficiencies and operational lifetime compared to OLEDs on conventional ITO anode. As another alternative electrode, the conductive polymer Baytron®PH510 (PEDOT:PSS) was investigated. Due to a relatively high sheet resistance of PEDOT:PSS, metal grid was designed for large size OLEDs. White OLEDs on PEDOT anode with a size of 5 × 5 cm2 have achieved more than 10 lm/W of power efficiency using a scattering foil. Furthermore, up-scaled devices on 10 × 10 cm2 were also demonstrated. These results showed ZnO:Al and PEDOT are suitable for OLEDs as anode and have high potential as alternative transparent electrode materials.

Zincor, a refinery in South Africa, uses the conventional roast-leachelectrowinning process to produce zinc metal. The roasting process of ZnS concentrate makes use of four Lurgi fluidized bed roasters to produce calcine (contains ZnO and ZnFe2O4 as zinc products) and SO2 gas. The roasting plant consists of two 18 m2 and two 35 m2 cross sectional area roasters. Prior to 1996, Zincor utilized air as the only oxidant and fluidizing medium in its roasters. The maximum dry feed rates that the roasters could process were 6.5 t/d.m2. In an attempt to increase production, oxygen enrichment was first trialled and then introduced into the fluidizing air. The ability of oxygen enrichment to increase the rate of the ZnS oxidation reaction allowed higher feed rates to the roasters. This was successful and oxygen enrichment was permanently implemented. That enabled dry feed rates to be maintained at 7.0 t/d.m2 and 7.3 t/d.m2 for the small and big roasters respectively. Oxygen enrichment up to 26% in the fluidizing air is utilized. Due to the highly competitive nature of the zinc industry, innovative processing techniques are necessary to be competitive. The aim of this study is to determine whether oxygen enriched air can be reduced by introducing micro-pelletized concentrate into the roaster feed blend, whilst maintaining current roaster feed rates and calcine quality. This study was executed in four parts. Firstly, the role entrainment played in influencing average particle residence time. Secondly, a study of production methods for stable micro-pellets. Thirdly, a study of the influence of oxygen enrichment and particle size on the roasting of micropellets. The fourth part of the study was introduction of micro-pellets into the Zincor roasters to determine whether oxygen enrichment could be reduced. The particle size distribution of a blend of feed concentrate to the roasters is 50% passing approximately 48 μm. This leads to entrainment values between 87% and 91%. The micro-pelletization process reduces the –500 μm fraction from 87% to 10%, which degrades to 30% during roasting. This requires that approximately 48% of the concentrate needs to be micro-pelletized to restore the 70% designed entrainment target. It was determined that entrained particles spend on average 0.46 hr to 2.44 hr in the bed compared to particles in the overflow that have residence times between 3.93 and 4.00 hr. The calculated times for entrainable particles are somewhat higher and for the bed overflow lower compared to the values measured by Spira, 1970. The required reaction time for micropellets was found to be far below their residence time inside a Zincor roaster. With a load of 20% micro-pellets introduced into the feed concentrate, the oxygen enrichment could be reduced by 60%. The quality of the calcine produced was maintained above the target of 98.8% ZnS to ZnO conversion. The results of this study have shown that the use of micro-pelletization of concentrate at Zincor reduces entrainment of particles successfully. Manipulation of entrainment through micro-pelletization can be used successfully to reduce oxygen enrichment, whilst improving production and maintaining quality at Zincor. Copyright / Dissertation (MEng)--University of Pretoria, 2009. / Materials Science and Metallurgical Engineering / unrestricted

M.Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / Phenol, 2-chlorophenol (2-CP) is used in the manufacture of several chemical compounds including other chlorophenols, dyes, dentifrice and pesticides. The usage of these chemicals results in the discharge of 2-CP that is harmful to most biota in the environment. Therefore there is need to remove or degrade 2-CP from the environment, especially in water. This research focused on the synthesis, characterization and application of Ag doped semiconductor (TiO2, ZnO, and ZnS) nanoparticles for the removal of 2-CP from water. Sol-gel and co-precipitation methods were used to synthesize the nanoparticles with different Ag contents (1%, 3% and 5%). Silver metal was used as a doping agent due to its antibacterial activity and ability to improve the photocatalytic activity of the semiconductors for 2-CPdegradation under UV irradiation. Characterization techniques such as X-ray diffraction (XRD), Fourier transform infrared (FTIR), Ultra-violet visible spectroscopy (UV-Vis) and photoluminescence spectra (PL) were used to characterize the structural, optical and physical properties of the nanoparticles, while Transmission electron microscopy (TEM) was used to characterize the surface of the nanoparticles. The XRD results confirmed the formation of anatase, wurtzite and blend phases of TiO2, ZnO and ZnS nanoparticles, respectively. The band gaps of the synthesized nanoparticles were 3.42 eV, 3.23 eV and 3.12 eV for TiO2, ZnO and ZnS nanoparticles respectively. The TEM images showed that all synthesized nanoparticles were uniform in shape. Photocatalytic degradation of 2-CP under UV irradiation confirmed that the semiconductor’s photocatalytic activities improved with the addition of Ag ions. The best removal percentage was obtained at doped Ag percentages of 5, 1 and 5 % using TiO2, ZnO and ZnS, respectively. In addition, the effects of various parameters affecting the photocatalytic degradation such as pH, initial concentrations of 2-CP and amount of catalyst (Ag doped TiO2, ZnO and ZnS, respectively) loading were examined and optimized. At the different initial concentrations of 2-CP, namely, 8, 20 and 50 ppm, the highest degradation efficiency was obtained at pH of 10.5 and 5 mg of catalyst dosage. However a decrease in initial concentration of 2-CP showed an increase in the photocatalytic efficiency. The degradation percentage of 2-CP obtained with Ag doped TiO2; ZnO and ZnS nanoparticles were 74.74, 57.8 and 45.49 %, respectively. Doping of these materials with Ag enhanced their photocatalytic activity; thus, they have the potential of degrading phenolic compounds, especially 2-chlorophenol, in water.

Un-doped, Tb3+ as well as Yb3+ doped ZnO nanocrystals with different concentrations of RE3+ (Tb3+, Yb3+) ions were successfully synthesized via sol-gel method to produce rare earth activated zinc oxide nanophosphors. The phosphor powders were produced by drying the precursor gels at 200˚C in ambient air. Based on the X-ray diffraction results, it was found that the pure and RE3+ doped ZnO nanophosphors were highly polycrystalline in nature regardless of the incorporation of Tb3+ or Yb3+ ions. Moreover, the diffraction patterns were all indexed to the ZnO Hexagonal wurtzite structure and belong to P63mc symmetry group. The Raman spectroscopy confirmed the wurtzitic structure of the prepared samples. Elemental mapping conducted on the as prepared samples using Scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometer (EDX) revealed homogeneous distribution of Zn, O, and RE3+ ions. The high resolution transmission electron microscope (HR-TEM) analyses indicated that the un-doped and RE3+ doped samples were composed of hexagonal homogeneously dispersed particles of high crystallinity with an average size ranging from 4 to 7 nm in diameter, which was in agreement with X-ray diffraction (XRD) analyses. ZnO:Tb3+ PL study showed that among different Tb3+ concentrations, 0.5 mol% Tb3+ doped ZnO nanoparticles showed clear emission from the dopant originating from the 4f-4f intra-ionic transitions of Tb3+ while the broad defects emission was dominating in the 0.15 and 1 mol% Tb3+doped ZnO. Optical band-gap was extrapolated from the Ultraviolet Visible spectroscopy (UV-Vis) absorption spectra using TAUC‟s method and the widening of the optical band-gap for the doped samples as compared to the un-doped sample was observed. The PL study of ZnO:Yb3+ samples was studied using a 325 nm He-Cd laser line. It was observed that the ZnO exciton peak was enhanced as Yb3+ions were incorporated in ZnO matrix. Furthermore, UV-VIS absorption spectroscopic study revealed the widening of the band-gap in Tb3+ doped ZnO and a narrowing in the case of Yb3+ doped ZnO system. X-ray photoelectron spectroscopy demonstrated that the dopant was present in the doped samples and the result was found to be consistent with PL data from which an energy transfer was evidenced. Energy transfer mechanism was evidenced between RE3+ and ZnO nanocrystals and was discussed in detail. / Physics / M.Sc. (Physics)

This thesis builds around the idea of a biofuel production process that is comprised of biomass production, biomass gasification, gas cleaning, and fuel production. In this work, we specifically looked into H2S removal as a part of cleaning the producer gas and flocculation of microalgae which is involved in the harvesting of microalgae after biomass production. One of the impurities to remove from the producer gas is hydrogen sulfide which can be removed by using a packed bed of zinc oxide. Despite the regular use, it was only recently shown that during reaction with H2S, nano-size particles of ZnO exhibit void formation and outward growth. In this work, a micro-scale model was introduced to describe the void formation and outward growth. On the macro-scale, the simulations captured pore clogging of pellets due to the outward growth. The pore clogging prevents the full conversion of pellets and consequently leads to shorter breakthrough times of beds. The second problem investigated here deals with the flocculation of microalgae. Microalgae is produced in relatively low concentrations in the incubator liquid medium and during the harvesting, the concentration is increased to an acceptable level. The harvesting process includes a flocculation followed by a filtration or centrifuge unit. During flocculation, microalgae are stimulated to aggregate and form clusters. The experiments showed that the mean size of clusters formed during flocculation increases with time to a maximum and then starts decreasing, resulting in an overshoot in the mean size profile. The size of clusters influence the efficiency of the afterward filtration or centrifuge, thus it is of interest to carefully track the size evolution of clusters, making the studying of overshoot a crucial research topic. In this work, the possible mechanisms behind this overshoot were investigated. / <p>QC 20170330</p>