<p>Admixtures like reactants and byproducts are solublenon-crystallizing compounds that can be present in industrialsolutions and affect crystallization of the main substance.This thesis provides experimental and molecular modellingresults on the influence of admixtures on crystal nucleation ofvanillin (VAN). Seven admixtures: acetovanillone (AVA),ethylvanillin (EVA), guaiacol (GUA), guaethol (GUE), 4-hydroxy-acetophenone (HAP), 4-hydroxy-benzaldehyde (HBA), andvanillic acid (VAC) have been used in this study. Classicalnucleation theory is used as the basis to establish arelationship between experimental induction time andsupersaturation, nucleation temperature, and interfacialenergy. A novel multicell device is designed, constructed, andused to increase the experimental efficiency in thedetermination of induction times by using 15 nucleation cellsof small volumes simultaneously. In spite of the largevariation observed in the experiments, the solid-liquidinterfacial energy for each VAN-admixture system can beestimated with an acceptable statistical confidence. At 1 mole% admixture concentration, the interfacial energy is increasedin the presence of GUA, GUE, and HBA, while it becomes lower inthe presence of the other admixtures. As the admixtureconcentration increases from 1 to 10 mole %, the interfacialenergy also increases. The interfacial energies obtained are inthe range 7-10 mJ m^-2. Influence of admixtures on metastable zone widthand crystal aspect ratio of VAN is also presented. Theexperimental results show that the admixtures studied arepotential modifiers of the nucleation of VAN. Molecularmodelling by the program Cerius2 is used to identify the likelycrystal growth faces. Two approaches, the surface adsorptionand the lattice integration method, are applied to estimatequantitatively the admixture-crystal interaction energy on thedominating crystal faces of VAN,<i>i.e</i>., {0 0 1} and {1 0 0}. However, a simple and clearcorrelation between the experimental values of interfacialenergy and the calculated interaction energies cannot beidentified. A qualitative structural analysis reveals a certainrelationship between the molecular structure of admixtures andtheir effect on nucleation. The determination of the influenceof admixtures on nucleation is still a challenge. However, themolecular and crystal structural approach used in this thesiscan lead to an improved fundamental understanding ofcrystallization processes. Keywords: Crystallization,nucleation, vanillin, admixtures, additives, impurities,induction time, interfacial energy, molecular modelling,interaction energy.</p>

Cadmium Telluride (CdTe) is a leading thin film photovoltaic (PV) material due to its near ideal bandgap of 1.45 eV and its high optical absorption coefficient. The typical CdTe thin film solar cell is of the superstrate configuration where a window layer (CdS), the absorber (CdTe) and a back contact are deposited onto glass coated with a transparent electrode. Substrate CdTe solar cells where the above listed films are deposited in reverse are not common. In this study substrate CdTe solar cells are fabricated on flexible foils. The properties of the Molybdenum back contact, Zinc Telluride (ZnTe) interlayer and CdTe absorber on the flexible foils were studied and characterized using X-Ray Diffraction (XRD), and Scanning Electron Microscopy (SEM). Substrate curvature and film flaking was observed during the fabrication as a result of differences in thermal expansion coefficients between the substrate and the deposited films, and also due to impurity diffusion from the foil into the film stack. In order to overcome this problem diffusion barriers where used to eliminate contamination. Silicon dioxide (SiO2), silicon nitride (Si3N4) and molybdenum nitride (MoxNy) were used as such barriers. Electrical characterization of completed devices was carried out by Current-Voltage (J-V), Capacitance-Voltage (C-V) and Spectral Response (SR) measurements. Roll-over was observed in the first quadrant of J-V curves indicating the existence of a back barrier due to a Schottky back contact. The formation of non-rectifying contact to p-CdTe thin-film is one of the major and critical challenges associated with the fabrication of efficient and stable solar cells. Several materials (ZnTe, Cu, Cu2Te, and Te) were studied as potential candidates for the formation of an effective back contact.

Since materials properties are determined by the interactions between the constituent atoms, an accurate description of the inter-atomic interactions is crucial to characterize and control material properties. Particularly, a quantitative understanding of the formation and nature of defects and impurities becomes increasingly important in the era of nanotechnology, as the imperfections largely influence many properties of nanoscale materials. Indeed, due to its technological importance and scientific interest, there have been significant efforts to better understand their behavior in semiconductors and oxides, and their interfaces, yet many fundamental aspects are still ambiguous due largely to the difficulty of direct characterization. Hence, our study has focused on developing a better understanding of atomic-scale defects and impurities using first principles quantum mechanical calculations. In addition, based on the improved understanding, we have attempted to address some engineering problems encountered in the current technology. The first part of this thesis focuses on mechanisms underlying the transient enhanced diffusion of arsenic (As) during post-implantation annealing by examining the interaction of As with vacancies in silicon. In the second part, we address some fundamental features related to plasma-assisted nitridation of silicon dioxide; this study shows that oxygen vacancy related defects play an important role in (experimentally observed) peculiar nitridation at the Si/SiO2 interface during post O2 annealing. In the third part, we examine the interaction between vacancies and dopants in sp2–bonded carbon such as graphene and nanotube, specifically the formation and dynamics of boron-vacancy complexes and their influence on the electrical properties of host materials. In the fourth part, we study the interfacial interaction between amorphous silica (a-SiO2) and graphene in the presence of surface defects in a-SiO2; this study shows possible modifications in the electronic structure of graphene upon the surface defect assisted chemical binding onto the a-SiO2 surface. In the last part, we examine the structural and electronic properties of bismuth vanadate (BiVO4) which is a promising photocatalyst for water splitting to produce hydrogen; this study successfully explains the underlying mechanism of the interesting photocatalytic performance of BiVO4 that has been experimentally found to strongly depend on structural phase and doping. / text

Introduction Copper-64 is an emerging radionuclide with applications in PET molecular imaging and/or internal therapy and it is typically produced by proton irradiation of isotopically enriched 64Ni electrodeposited on a suitable backing substrate. We recently reported a simple and efficient method for the preparation of nickel targets from electrolytic solutions of nickel chloride and boric acid [1]. Herein we report our recent research work on the analysis of metallic impurities in the copper-fraction of the radiochemical separation process. Material and Methods Nickel targets were prepared and processed as previously reported [1]. Briefly, the bath solution was composed of a mixture of natural NiCl2. 6H2O (135 mg/ml) and H3BO3 (15 mg/ml) and Ni was electrodeposited using a gold disk as cathode and a platinum wire as anode. The plating process was carried out at room temperature using 2 ml of bath solution (pH = 3.7) and a constant current density of 60 mA/cm2 for 1 hour. The unirradiated Ni targets were dissolved in 1–2 ml of concentrated (10M) HCl at 90 oC. After complete dissolution of the Ni layer, water was added to dilute the acid to 6M, and the solution was transferred onto a chromatographic column containing AG 1-X8 resin equilibrated with 6M HCl. The Ni , Co and Cu isotopes were separated by using the well-known chromatography of the chloro-complexes. The sample-fractions containing the Cu isotopes (15 ml, 0.1M HCl) were collected in plastic centrifuge tubes previously soaked in 1M HNO3 and rinsed with Milli-Q water (18 MΩ cm). Impurities of B, Co, Ni, Cu and Zn in these samples were determined by inductively coupled plasma-mass spectroscopy (ICP-MS) at the Department of Geosciences (Laboratory of Isotopic Studies) of the National University. Results and Conclusions The mass of Ni deposited in 1 h was 25.0 ± 1.0 mg (n = 3) and the current efficiency was > 75 % in all cases. The pH of the electrolytic solution tended to decrease along the electrodeposition process (3.71.6). The results of ICP-MS analysis of the Cu-fractions from the cold chromatography separation runs are shown in FIG. 1. We were particularly interested in the boron impurities as H3BO3 is used as buffer for electrodeposition of the Ni targets. Except for the Ni impurities that were deter-mined to be in the range of ppm (mg/l), all other analyzed metallic impurities were found to be in the range of ppb (µg/l), including boron. The Co, Ni, Cu and Zn impurities determined in the Cu-fraction in this work using Ni targets electrode-posited from a NiCl2 acidic solution, are in the same order of magnitude compared with that obtained when using targets prepared from an alkaline solution [2], with the advantage of the simplicity of the electrodeposition method from NiCl2 solutions, as the target material is already recovered in the chemical form of NiCl2, enabling a simpler, one step process to prepare a new plating solution when using enriched 64Ni target material for the production of 64Cu.

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Computational quantum mechanics in the frame work of density functional theory (DFT) was used to investigate the effect of chemical impurities on high field conduction in polyethylene (PE). The impurity states in the band gap caused by common chemical impurities were characterized in terms of their “depth”, i.e. energy relative to their relevant band edge (valence band or conduction band), and in terms of the extent to which their wavefunctions were localized to a single polymer chain or extended across chains. It was found that impurity states can affect high field phenomena by providing “traps” for carriers, the depths of which were computed from first principle in agreement with estimates in literature. Since the square of the wavefunction is proportional to the spatial electron probability density, transfer of charge between chains requires wavefunctions which are extended across chains. Impurity states which are extended between chains can facilitate the inherently limited interchain charge transfer in PE, as the DFT study of iodine doped PE revealed. The introduction of iodine into PE increases conductivity by several orders of magnitude, increases hole mobility to a much greater extent than electron mobility, and decreases the activation energy of conduction from about 1 eV to about 0.8 eV. These characteristics were explained in terms of the impurity states introduced by iodine and wavefunctions of those states. Understanding the effect of iodine on conduction in PE provided a basis for understanding the effect of common chemical impurities on conduction therein. In particular, carbonyl and vinyl impurities create states which should promote hole mobility in a manner very similar to that caused by iodine. It was demonstrated that in the context of high field conduction in PE, besides the traditional focus on the depth of impurity states, it is important to study the spatial features of the states wavefunctions which are neither discussed nor accounted for in present models.

Computational quantum mechanics in the frame work of density functional theory (DFT) was used to investigate the effect of chemical impurities on high field conduction in polyethylene (PE). The impurity states in the band gap caused by common chemical impurities were characterized in terms of their “depth”, i.e. energy relative to their relevant band edge (valence band or conduction band), and in terms of the extent to which their wavefunctions were localized to a single polymer chain or extended across chains. It was found that impurity states can affect high field phenomena by providing “traps” for carriers, the depths of which were computed from first principle in agreement with estimates in literature. Since the square of the wavefunction is proportional to the spatial electron probability density, transfer of charge between chains requires wavefunctions which are extended across chains. Impurity states which are extended between chains can facilitate the inherently limited interchain charge transfer in PE, as the DFT study of iodine doped PE revealed. The introduction of iodine into PE increases conductivity by several orders of magnitude, increases hole mobility to a much greater extent than electron mobility, and decreases the activation energy of conduction from about 1 eV to about 0.8 eV. These characteristics were explained in terms of the impurity states introduced by iodine and wavefunctions of those states. Understanding the effect of iodine on conduction in PE provided a basis for understanding the effect of common chemical impurities on conduction therein. In particular, carbonyl and vinyl impurities create states which should promote hole mobility in a manner very similar to that caused by iodine. It was demonstrated that in the context of high field conduction in PE, besides the traditional focus on the depth of impurity states, it is important to study the spatial features of the states wavefunctions which are neither discussed nor accounted for in present models.

Polyvinyl alcohol (PVA) desize effluent is a high COD contributor to towel manufacturing plant's Primary Oxygenation Treatment of Water operation, and being non-biodegradable, is a threat to the environment. When all-PVA/wax size is used in weaving, significant incentives exist to recover the synthetic polymer material from the desize wash water stream and reuse it. A new technology that would eliminate the disadvantages of the current Reverse Osmosis Ultrafiltration (UF) PVA recovery process is Vacuum Flash Evaporation (VFE). This research adapts the VFE process to the recovery and reuse of all-PVA size emanating from towel manufacturing, and compares the economics of its implementation in a model plant to current plant systems that use PVA/starch blend sizes with no materials/water recovery. After bench scale research optimized the VFE PVA recovery process from the desize effluent and determined the mass of virgin PVA that was required to be added to the final, recycled PVA size formulations. The physical changes in the recycled size film and yarn composite properties from those of the initial (conventional) slashing were determined using a number of characterization techniques, including DSC, TGA, SEM, tensile testing, viscometry, number of abrasion cycles to first yarn breaks, microscopy and contact angle measurements. Cotton chemical impurities extracted from the yarns during desizing played an important role in the recovered PVA film physical properties. The recovered PVA improved the slashed yarn weave ability. Along with recovered PVA, pure hot water was recovered from the VFE. Virgin wax adds to the final, recycled size formulations were determined to be unnecessary, as the impurities extracted into the desize effluent stream performed the same functions in the size as the wax. Using the bench results, the overall VFE process was optimized and demonstrated to be technically viable through six cycles, proof-of-concept trials conducted on a Webtex Continuous Pilot Slasher. Based on the pilot scale trials, comparative economics were developed. Incorporation of the VFE technology for PVA size recovery and recycling resulted in ~$3.2M/year in savings over the conventional PVA/starch/wax process, yielding a raw ROI of less than one year based on a $3M turnkey capital investment.

Produced water presents economical and environmental challenges to oil producers. Downhole separation technology is able to separate oil or gas from produced fluid in downhole environment and injects waste water into deeper formations, thus saving energy and reducing waste emission. More than 120 downhole separation systems have been installed worldwide, but only about 60% of the installations achieved success. Most of the failures were due to the injectivity decline under the invasion of impurities in the injected water, such as suspended particles and oil droplets. A reliable model is needed to predict the reaction of reservoir permeability under the invasion of such impurities and serves as a tool to screen appropriate formations for downhole separator installations. / Previous experimental studies on particle-induced permeability damage reveal that high particle concentration, low fluid velocity, large particle size lead to more severe damage. The damage mechanisms are attributed to surface interception, bridging and size exclusion of particles in porous media. While for droplets, the resultant permeability decline is mostly due to surface interception. Empirical correlations with key parameters determined by core flooding data are widely applied to the simulation of permeability decline under invasion of particles and droplets. These correlations are developed based on characteristics of certain rocks and fluids, thus their applications are very restricted. / A more scientific method is to model the flow and capture of particulates at pore level. Reservoir rocks are porous media composed of pores of various sizes. Pore network models employ certain assumptions to imitate real porous media, and have been proved realistic in simulating fluid flow in porous media. In this study, a 2-dimensional square network model is used to simulate capture of particles and droplets in porous media. Pore bodies are represented by globes and pore throats are imitated with capillary tubes. The flow rates in the network are obtained by simultaneously solving mass balance equations at each pore body. The network model is tuned to match the porosity and permeability of a certain rock and serves as the infrastructure where the capture process takes place. / Particles are categorized as Brownian and non-Brownian particles according to size. For Brownian particles, diffusion is dominant and Fick’s law is applied to each pore inside the network to obtain deposition rate. For non-Brownian particles, their trajectories are mainly governed by gravity and drag force acting on them. Besides, the size of each particle is compared with the size of the pore where it is captured to determine the damage mechanism. For particles much smaller than the pore size, surface deposition is dominant and the permeability decline is gradual. For particles with sizes comparable to pore size, bridging and clogging are dominant and the permeability decline is much more severe. / Unlike particles, droplets can not be captured on top of each other. Accordingly, a captureequilibrium theory is proposed. Once the pore surface is covered by droplets, equilibrium is reached and droplets flow freely through porous media without being captured. The simulation on capture of oil droplets reveals that the surface wettability has significant influence on the resultant permeability damage. Most natural reservoirs are neutrally or oil wet. It is thus recommended to apply these surface conditions to future simulations. / The proposed model is validated with test data and reasonably good agreements are obtained. This new mechanistic model provides more insights into the capture process and greatly reduces the dependence on core flooding data.