Gypsum (calcium sulphate dihydrate) is of great industrial importance with over 95,000 ktonnes being used in the world per annum. The greatest use of gypsum is in the production of plaster (calcium sulphate hemihydrate) for use as an interior finisher. Plaster is produced by the calcination (thermal decomposition) of gypsum. The most popular design is a continuous calciner where gypsum is fed continuously and is directly heated by hot air. There are a number of different phenomena occurring within a calciner, including heat transfer, mass transfer, particle and gas mixing, elutriation and the dehydration reaction itself. All these processes interact with each other. Although a lot of research has been carried out in these areas already, the literature has been found to contain significant discrepancies. This study contains experimental work which has been carried out in order to better understand the physical processes occurring within a gypsum calciner. The rate of dehydration of gypsum (35-67μm in diameter) has been studied in a fluidised bed reactor. Experiments were carried out at bed temperatures of 100 to 170°C. The fluidising gas was air with water vapour pressures of 0.001 to 0.30 atm. The dehydrations were under differential conditions. The results show that the dehydration under these conditions can be successfully modelled using the two dimensional Avrami-Er'ovev expression. A study of the fluidisation and elutriation properties of gypsum in batch vessels (cylindrical and conical) has been carried out. The mechanics of elutriation has been investigated and modelled for various freeboards, superficial gas velocities and air humidities. Tracer tests have also been carried out on a laboratory scale continuous conical kettle. Sodium carbonate was used as the inert tracer material. Runs were carried out at different air and gas flowrates and different bed temperatures. Residence time distributions were elucidated. Finally, the above experimental data and component models have been investigated for their applicability to producing a model of the laboratory scale gypsum calciner.

In Part I of this thesis an irradiated single crystal of dipotassium difluoromalonate monohydrate has been studied by Electron Spin Resonance. On X-irradiation the crystal yields CF(COO¯)2 radical with a highly anisotropic hyperfine tensor, characteristic of a (19)F nucleus. In addition, some other lines were also observed which were too weak to be analyzed. On γ-irradiation, the crystal yields mainly the same radical in addition to two types of CF(2)COO¯ radicals. In one type, the carboxyl group was found to be nearly coplanar with the CF(2) fragment while in the other, it was nearly perpendicular. A broad central line in each spectrum indicated also the possibility of the presence of CO(2)¯ radical. An unrestricted Hartree-Fock calculation, using the approximation of Intermediate Neglect of Differential Overlap was carried out on a number of fluorinated radicals to correlate the (19)F hyperfine tensors obtained in the present study with those obtained previously. The theory was used to calculate the theoretical hyperfine tensors for various radicals and was found to give a reasonably good agreement with the experimental results. On this basis the hyperfine tensor for CHFCOO¯ radical was predicted. The calculation also showed that one of the carboxyl groups in CF(COO¯)2 radicals is co-planar with the radical plane while the other makes an angle of 85°. In Part II, a crystal of zinc trifluoroacetate dihydrate, containing small amounts of Cu++ has been studied at 77°K and it was found that the Cu++ ion resides in an approximately tetragonal environment with the ground state consisting of mainly d(z2) orbital which is coupled to d(x2)-(y2) orbital, perhaps through vibronic interactions. Also a solution of copper trifluoroacetate in trifluoroacetic acid was studied at room temperature and at 77°K and the results were interpreted by assuming a tetragonal symmetry with the ground state being pure d(x2)-(y2). / Science, Faculty of / Chemistry, Department of / Graduate

The inflammatory response caused by the deposition of crystals of monosodium urate monohydrate (MSUM) and calcium pyrophosphate dihydrate (CPPD) in the synovial fluid of joints, results from the interaction of the crystals with neutrophils. Neutrophils (whose function in the body is to remove hazardous microorganisms and inflammatory debris) are activated by the binding of the crystals to the neutrophil cellular membrane, which leads to respiratory burst activity, engulfment of the crystals and release of proteolytic enzymes. Furthermore, we have found that crystals delay the normal “cell death program” or apoptosis, thus allowing for the accumulation of these cells, and extended inflammatory responses. Very little is known about the mechanisms of activation and delay of apoptosis, however, bcl-2 family proteins have been implicated in the control of neutrophil apoptosis. This study helps to define the role of several bcl-2 family proteins (both pro- and anti-apoptotic) by examining the differential expression of these proteins upon stimulation with crystals. Subsequent identification of signaling targets that function to regulate this process in response to crystals could lead to potential therapeutics for crystal-induced inflammatory diseases.

The inflammatory response caused by the deposition of crystals of monosodium urate monohydrate (MSUM) and calcium pyrophosphate dihydrate (CPPD) in the synovial fluid of joints, results from the interaction of the crystals with neutrophils. Neutrophils (whose function in the body is to remove hazardous microorganisms and inflammatory debris) are activated by the binding of the crystals to the neutrophil cellular membrane, which leads to respiratory burst activity, engulfment of the crystals and release of proteolytic enzymes. Furthermore, we have found that crystals delay the normal “cell death program” or apoptosis, thus allowing for the accumulation of these cells, and extended inflammatory responses. Very little is known about the mechanisms of activation and delay of apoptosis, however, bcl-2 family proteins have been implicated in the control of neutrophil apoptosis. This study helps to define the role of several bcl-2 family proteins (both pro- and anti-apoptotic) by examining the differential expression of these proteins upon stimulation with crystals. Subsequent identification of signaling targets that function to regulate this process in response to crystals could lead to potential therapeutics for crystal-induced inflammatory diseases.

The inflammatory response caused by the deposition of crystals of monosodium urate monohydrate (MSUM) and calcium pyrophosphate dihydrate (CPPD) in the synovial fluid of joints, results from the interaction of the crystals with neutrophils. Neutrophils (whose function in the body is to remove hazardous microorganisms and inflammatory debris) are activated by the binding of the crystals to the neutrophil cellular membrane, which leads to respiratory burst activity, engulfment of the crystals and release of proteolytic enzymes. Furthermore, we have found that crystals delay the normal “cell death program” or apoptosis, thus allowing for the accumulation of these cells, and extended inflammatory responses. Very little is known about the mechanisms of activation and delay of apoptosis, however, bcl-2 family proteins have been implicated in the control of neutrophil apoptosis. This study helps to define the role of several bcl-2 family proteins (both pro- and anti-apoptotic) by examining the differential expression of these proteins upon stimulation with crystals. Subsequent identification of signaling targets that function to regulate this process in response to crystals could lead to potential therapeutics for crystal-induced inflammatory diseases. / Medicine, Faculty of / Medicine, Department of / Experimental Medicine, Division of / Graduate

The energetics of cast calcium sulfate dihydrate-aluminium thermites was explored and its use as a potential metal-cutting tool was investigated. Thermite is a pyrotechnic composition that undergoes a highly exothermic reaction that burns relatively slowly. It is often used in cutting, welding and incendiary devices. Consolidation of thermite by casting was chosen to enable control of the burning front. The base case thermite comprised 60 wt-% calcium sulfate dihydrate oxidiser and 40 wt-% aluminium fuel. Addition of additives were considered for their effect on the cast thermite’s setting time, density, surface temperature, reaction products and burn rate. EKVI and FactSage thermodynamic simulations were used to determine optimum compositions for the various systems. The thermite powder compositions were sieved before mixing with water and casting in a mould. The casts were allowed to set for 3 days to form calcium sulfate dihydrate-aluminium compositions. The copper sulfate pentahydrate additive was found to significantly decrease the setting time of the casts. The heat of hydration of the base case was 59 ± 8 J g−1 . The compressive strength reached 2.9 ± 0.2 MPa, the open air burn rate was 12.0 ± 1.6 mm s −1 and a maximum surface temperature of 1370 ± 64 °C was recorded using a pyrometer. Bomb calorimetry indicated an energy output of 7.96 ± 1.07 MJ kg−1 , slightly lower than predicted by the EKVI simulation. The density of the castings was varied by either adding hollow sodium borosilicate glass spheres or by adding excess water. The glass spheres resulted in a burn rate that decreased nonlinearly with decreasing cast density. The excess water made no changes to the burning, except for increasing the burn rate of the copper sulfate pentahydrate-based thermite. Calcium sulfate in the casts was also dehydrated by thermal treatments at 155 °C and 200 °C. This resulted in significant increases in the burn rate due to the porosity created by the evaporation of the hydration waters. Castings that were thermally treated in an oven at 155 °C were successful in puncturing part of an aluminium block in confined burn tests. A hole with a diameter of ~13.6 mm and depth of ~7 mm was produced. It is recommended that the composition with copper sulfate pentahydrate be used as a binder in further tests. / Dissertation (MEng)--University of Pretoria, 2018. / Chemical Engineering / MEng / Unrestricted

No description available.

When proteins and DNA interact, arginine and lysine are the two amino acids most often in close contact with the DNA. In order to understand the radiation damage to DNA in vivo, which is always associated with protein, it is important to learn the radiation chemistry of arginine and lysine independently, and when complexed to DNA. This work studied X-irradiated single crystals of L-lysine monohydrochloride dihydrate (L-lysine·HCl·2H2O) and L-arginine monohydrochloride monohydrate (L-arginine·HCl·H2O) with EPR, ENDOR, EIE techniques and DFT calculations. In both crystal types irradiated at 66K, the carboxyl anion radical and the decarboxylation radical were detected. DFT calculations supported these assignments. Specifically, the calculations performed on the cluster models for the carboxyl anion radicals reproduced the proton transfers to the carboxyl group from the neighboring molecules through the hydrogen bonds. Moreover, computations supported the identification of one radical type as the guanidyl radical anion with an electron trapped by the guanidyl group. In addition, the radical formed by dehydrogenation of C5 was identified in the L-arginine·HCl·H2O crystals irradiated at 66K. For both crystal types, the deamination radicals and the dehydrogenation radicals were identified following irradiation at 298K. Different conformations of main-chain deamination radicals were detected at 66K and at 298K. In L-lysine·HCl·2H2O, these conformations are the result of the different rotation angles of the side chain. In L-arginine·HCl·H2O, one conformation at 66K has no O-H dipolar protons while the others have two O-H dipolar protons. In L-lysine·HCl·2H2O, two radicals with very similar sets of hyperfine couplings were identified as the result of dehydrogenation from C3 and C5. Two other radicals in low concentration detected only at 66K, were tentatively assigned as the radical dehydrogenated from C3 and the side-chain deamination radical. In L-argnine·HCl·H2O, the radicals from dehydrogenation at C5 and C2 also were identified. DFT calculations supported these assignments and reproduced conformations of these radicals.Finally, based on the radicals detected in the crystal irradated at 66K and at 298K, the annealing experiments from the irradiation at 66K, and the previous studies on the irradiated amino acids, the mechanisms of the irradiation damage on lysinie and arginine were proposed.

Magister Scientiae - MSc (Physics) / Zinc oxide (ZnO) is a wide and direct semiconductor with a wurtzite crystal structure. Its multifunctionality as the ideal candidate in applications such as blue-UV light emitting diodes, transparent conducting oxide, selective gas sensor and efficient catalyst support among others, has attracted a significant interest worldwide. Nano-scaled ZnO has been synthesized in a plethora of shapes. A rich variety of physical and chemical methodologies have been used in the synthesis of undoped or doped ZnO. However, such methods either necessitate relatively high vacuum infrastructures, elevated temperatures, or the use of toxic reagents. The "green chemistry" synthesis of metal oxide nanoparticles which is based on using natural plant extract as an effective 'reducing agent' of metal precursor, has been reported to be a cleaner and environment-friendly alternative to the physical and chemical methods. The thesis is based on the synthesis and the main physical properties of pure ZnO nanoparticles synthesized by a completely green chemistry process using the natural extract of Aspalathus Linearis to bio-reduce the zinc acetate precursor. The obtained ZnO nanopowdered samples were annealed at different temperatures from 300 °C to 600 °C. The samples were characterized using Scanning Electron Microscopy, Energy Dispersive Spectroscopy, Transmission Electron Microscopy, X-ray Diffraction, Differential Scanning Calorimetry, Thermogravimetric Analysis and Fourier Transform Infrared. Highly pure quasi-spherical ZnO nanoparticles with an average crystallite size of 24.6 nm (at 300 °C), 27.2 nm (at 400 °C), 27.6 nm (at 500 °C), and 28.5 nm (at 600 °C) were found. The results also showed that the average crystallite size increased with an increase in annealing temperature. It was successfully demonstrated that the natural plant extract of Aspalathus Linearis can be used in the bio-reduction of zinc acetate dihydrate to prepare highly pure ZnO nanoparticles.

Saccharides, a class of organic materials, are potential candidates for nonlinear optical applications. Ascorbic acid is a sugar acid and is classified as a monosaccharide. The molecule of ascorbic acid has two chiral centers and, therefore, four stereoisomers. Among them, two are naturally occurring compounds; L-ascorbic acid and D-isoascorbic acid. From these two acids various salts and other derivatives could be synthesized. In this thesis, four compounds of the ascorbic acid family were selected for detailed study based on their nonlinearity, chemical and physical stability and their crystallization characteristics. The thesis is organized into seven chapters. The first chapter covers the theoretical background of nonlinear optics, especially, second harmonic generation. Second chapter details the experimental techniques and methodology adopted. Chapter 3 discusses the crystal structure, growth, physical and nonlinear optical properties of Lithium Disoascorbate monohydrate (LDAM). Detailed analysis of refractive index measurements employing Brewsters angle method and determination of phase matching curves, effective nonlinear coefficient, walk off angle etc are given. In Chapter 4, investigations on Sodium D-isoascorbate monohydrate (NDAM) are presented. Detailed characterization of the crystals including thermal, optical, dielectric properties are carried out. Analyses of dielectric dispersion based on Cole-Cole equation are discussed. Comprehensive studies on laser damage of the crystals are discussed. Chapter 5 discusses the nonlinear optical properties of the monoclinic D-isoascorbic acid (DIA). Chapter 6 presents studies on the triclinic Lithium L-ascorbate dihydrate (LLA) crystals. The crystals exhibit intense non-collinear second harmonic rings as they possesses large birefringence coupled with high second order nonlinear coefficients. The SHG conversion efficiency of these crystals is 15 times that of KDP. In the final chapter, a comprehensive summary of the work carried out is presented along with scope for further investigations.