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In June 1994, a 150-m-long secondary road pavement section was built as part of the realignment of route 616 and 757 in Bedford County, Virginia to evaluate the performance of geosynthetically stabilized flexible pavements. The California Bearing Ratio (CBR) of the subgrade after construction was approximately 8%. The pavement section is was divided into nine individual sections, each approximately 15 m long. Sections one through three have a 100-mm-thick limestone base course (VDOT 21-B), sections four through six have a 150-mm-thick base course, and sections seven through nine have a 200-mm-thick base course. Three sections were stabilized with geotextiles and three with geogrids at the base course-subgrade interface. The remaining three sections were kept as control sections. One of each stabilization category was included in each base course thickness group. The hot-mix asphalt (HMA), SM-2A, wearing surface thickness was 78-90 mm. The outside wheel path of the inner lane was instrumented with strain gages, pressure cells, piezoelectric sensors, thermocouples, and moisture sensors. Section performances based on the instrumentation response to control and normal vehicular loading indicated that geosynthetic stabilization provided significant improvement in pavement performance. Generally, the measured pressure at the base course-subgrade interface for the geotextile-stabilized sections was lower than the geogrid-stabilized and control sections, within a specific base course thickness group. This finding agreed with other measurements, such as rut depth, ground penetration radar survey, and falling weight deflectometer survey. The control section (100-mm-thick base course) exhibited rutting that was more severe than the geosynthetically stabilized sections. Falling weight deflectometer back-calculation revealed consistently weaker subgrade strength for the geogrid-stabilized and control sections than for the geotextile-stabilized sections over the three year evaluation period. To quantitatively assess the extent of contamination, excavation of the first three sections in October 1997 revealed that fines present in the base course were significantly greater in the control and geogrid-stabilized section than in the geotextile-stabilized section. These findings led to the conclusion that the subgrade fine movement into the base layer when a separator is absent jeopardizes its strength. Further analysis of the field data showed that geotextile-stabilization may increase the service life of flexible secondary road pavements by 1.5 to 2 times. Finally, a new mechanistic-empirical flexible pavement design method for pavements with and without geosynthetics has been developed. Elasto-viscoelastic material characterization is used to characterize the HMA layer. The field results from Bedford County, Virginia project have been used to calibrate and validate the final developed design procedure. The concept of transition layer formed at the interface of base course and subgrade is also incorporated into the design approach. Powerful axisymmetric linear elastic analysis is used to solve the system of equations for mechanical and thermal loading on the pavement structure. Elasto-viscoelastic correspondence principle (EVCP) and Boltzman superposition integral (BSI) are used to convert the elastic solution to its viscoelastic counterpart and also to introduce the dynamic nature of vehicular loading. Pseudo-elastoplasticity is introduced into the problem by determining the extent of plastic strain using laboratory experimentation results and estimating the failure mechanisms, based on accumulated strains as opposed to the total strain (recoverable and non-recoverable). The pavement design approach presented in this dissertation is a hybrid of already existing techniques, as well as new techniques developed to address the visco-plastic nature of HMA. / Ph. D.

Freeze concentration is a thermal separation process that is used to purify aqueous solutions. One application of recent interest is seawater desalination. For freeze concentration to be an effective desalination method, a high ice growth rate and product purity must be achieved with energy usage comparable to that of competing technologies. The purpose of this thesis is to develop a coupled heat and mass transfer model to predict the growth rate and purity of the solid phase for ice grown about a horizontal, immersed tube. By simultaneously solving the heat and mass transfer problems, this model improves upon previous attempts found in the literature. In addition, an experimental apparatus was constructed and a series of ten experiments was run, considering a range of cooling rates, process times, and saltwater concentrations. Average ice growth velocities ranged from 3.1-13.1 mm/h and the observed partition coefficient ranged from 0.42-0.71. The model was calibrated using experimental data, and the coefficients of variation for the fitted model's prediction of ice mass and capture concentration were 15.4% and 7.6% respectively. Based on insights from modeling and experimentation, a series of suggestions are made regarding future modeling and process design. / Master of Science / Freeze concentration is a thermal process that is used to purify a liquid containing dissolved solids. One application of recent interest is seawater desalination. For freeze concentration to effectively purify seawater, a high ice growth rate and product purity must be achieved with energy usage comparable to that of competing technologies. The purpose of this thesis is to develop a coupled heat and mass transfer model to predict the growth rate and purity of the solid phase for ice grown about a horizontal, immersed tube. By simultaneously solving the heat and mass transfer problems, this model improves upon previous attempts found in the literature. In addition, an experimental apparatus was constructed and a series of ten experiments was run, considering a range of cooling rates, process times, and saltwater concentrations. Average ice growth velocities ranged from 3.1-13.1 mm/h and the salinity of the ice ranged from 0.42-0.71% of the original concentration. Based on insights from modeling and experimentation, a series of suggestions are made regarding future modeling and process design.

The ultimate threshold state of a human life is the time preceding death. Hospice care provides a gateway environment for many people for their transition to the other side. Societies throughout history have had rituals and traditions to support the dying and their loved ones, but for modern society, few of these rituals remain. Death has become a topic to avoid "no one wants to look at it or speak about it. This taboo treatment of death often results in the isolation of people at the end of their lives. It also has a major impact on those who are losing their loved ones, as well as the caregivers that deal with death on a daily basis. Through the lens of hospice, this thesis will explore spaces of transition in architecture - the idea of thresholds, both physical and emotional. It seeks to develop a design that considers all of its users and their experience of death and dying. / Master of Architecture

Submitted in fulfilment of the requirements of the Masters Degree in Technology: Chemistry, Durban University of Technology, 2012. / The thesis involves a study of the thermodynamics of ternary liquid mixtures involving carboxylic acids with sulfolane, hydrocarbons and acetonitrile. Carboxylic acids are an important group of polar compounds with many industrial and commercial uses and applications. In South Africa, these carboxylic acids together with many other oxygenates and hydrocarbons are manufactured by SASOL using the Fischer–Tropsch process. The separation of these acids from hydrocarbons is a commercially viable option, and is an important reason for this study. This work focuses on the use of sulfolane in effecting separation by solvent extraction and not by the more common and energy intensive method of distillation. Sulfolane was chosen because of its high polarity and good solvent extraction properties. The first part of this study involves the determination of excess molar volumes (VmE) of binary mixtures of sulfolane (1) + carboxylic acids (2) at different temperatures of 303.15 K and 308.15 K, where carboxylic acids refer to acetic acid, propanoic acid, butanoic acid, 2-methylpropanoic acid, pentanoic acid and 3-methylbutanoic acid respectively. The densities of the binary systems of sulfolane (1) + carboxylic acids (2) were measured at T = 303.15 K and 308.15 K. The excess molar volumes were calculated from the experimental densities at each temperature. The VmE were negative for the entire mole fractions for all the binary systems. It was found that the VmE in the systems studied increase with an increase in temperature, and also VmE decreases with an increase in the carbon chain length of the carboxylic acid. The VmE data results were correlated using Redlich-Kister equation. Abstract ii The second part was the study of the binodal or solubility curves and tie line data for the ternary systems of [sulfolane (1) + carboxylic acids (2) + hydrocarbons (3)] and [acetonitrile (1) + carboxylic acids (2) + hydrocarbon (3)]. Hydrocarbons refer to pentane, hexane, dodecane and hexadecane. The binodal curve experimental data was determined by the cloud point technique. Liquid-liquid equilibrium (LLE) phase diagrams were constructed using the mole fractions and refractive indices (nD). Tie line data were obtained for the sulfolane-rich and hydrocarbon-rich phases as well as the acetonitrile-rich and hydrocarbon-rich phases respectively. The tie lines in both cases were skewed towards the hydrocarbon-rich phases indicating that relative mutual solubility of carboxylic acids is higher in the hydrocarbon-rich phase than in the solvent-rich phase. Selectivity values were calculated from the tie-lines to determine the extraction capabilities of solvents sulfolane and acetonitrile. Selectivity values in all cases were greater than one, meaning that both sulfolane and acetonitrile can be used to separate carboxylic acids from hydrocarbons. Binodal curve data were correlated by the Hlavatý, beta (𝛽) and log𝛾 equations; average standard deviation error for Hlavatý was 0.012, for beta (𝛽), 0.023 and for log𝛾, 0.021. The NRTL and UNIQUAC models were used to correlate the experimental tie-lines. The calculated values based on the NRTL equation were found to be better than those based on UNIQUAC equation; the average root-mean square deviation, (rmsd), between the phase composition obtained from experiment and that from calculation was 0.061 for the NRTL model, as compared to 0.358 for UNIQUAC model for the ternary systems involving sulfolane. For ternary systems of acetonitrile, the NRTL equation was better than the UNIQUAC with the rsmd of 0.003 and 0.287for UNIQUAC equation. / DUT Postgraduate Development and Support Directorate (PGDS)

Submitted in fulfilment of the academic requirements for the Masters Degree in Technology: Chemistry, Durban University of Technology, 2012. / In this work, the thermodynamics of ternary liquid mixtures involving carboxylic acids with sulfolane, hydrocarbons including cycloalkane, and alcohols are presented. In South Africa, Sasol is one of the leading companies that produce synthesis gas from low grade coal. Carboxylic acids together with many other oxygenate and hydrocarbons are produced by Sasol using the Fischer-Tropsch process. Carboxylic acids class is one of the important classes of compounds with great number of industrial uses and applications. The efficient separation of carboxylic acids from hydrocarbons and alcohols from hydrocarbons is of economic importance in the chemical industry, and many solvents have been tried and tested to improve such recovery. This work focussed on the use of the polar solvent sulfolane in the effective separation by solvent extraction and not by more common energy intensive method of distillation. The first part of the experimental work focussed on ternary liquid-liquid equilibria of mixtures of [sulfolane (1) + carboxylic acid (2) + heptane (3) or cyclohexane or dodecane] at T = 303.15 K, [sulfolane (1) + alcohol (2) + heptane (3)] at T = 303.15 K. Carboxylic acid refers to acetic acid, propanoic acid, butanoic acid, 2-methylpropanoic acid, pentanoic acid and 3-methylbutanoic acid. Alcohol refers to methanol, ethanol, 1- propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and 2-methyl-2-propanol. Ternary liquid- liquid equilibrium data are essential for the design and selection of solvents used from liquid- liquid extraction process. Abstract vi The separation of carboxylic acids from hydrocarbons and the alcohols from hydrocarbons is commercially lucrative consideration and is an important reason of this study. The separation of carboxylic acids or alcohols from hydrocarbons by extraction with sulfolane was found to be feasible as all selectivity values obtained are greater than 1. The modified Hlavatý, beta (β) and log equations were fitted to the experimental binodal data measured in this work. Hlavatý gave the best overall fit as compared to beta ( ) and log function. The NRTL (Non-Random, Two Liquid) and UNIQUAC Universal Quasichemical) model were used to correlate the experimental tie-lines and calculate the phase compositions of the ternary systems. The correlation work served three purposes:  to summarise experimental data  to test theories of liquid mixtures  prediction of related thermodynamics properties. The final part of the study was devoted to the determination of the excess molar volumes of mixtures of [sulfolane (1) + alcohol (2)] at T = 298.15 K, T = 303.15 K and T = 309.15 K. Density was used to determine the excess molar volumes of the mixtures of [sulfolane (1) + alcohols (2)]. Alcohol refers to methanol, ethanol, 1- propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol. The work was done to investigate the effect of temperature on excess molar volumes of binary mixtures of alcohols and sulfolane, as well as to get some idea of interactions involved between an alcohol and sulfolane. The excess molar volume data for each binary mixture was fitted in the Redlich–Kister equation to correlate the composition dependence of the excess property. / National Research Foundation

Submitted in fulfilment of the academic requirements for the Masters Degree in Technology: Chemistry, Durban University of Technology, 2012. / National Research Foundation

Zeolites are a well-known class of crystalline oxide materials with tunable compositions and nanoporous structures, and have been used extensively in catalysis, adsorption, and ion exchange. The zeolite MFI is one of the well-studied zeolites because it has a pore size and structure suitable for separation or chemical conversion of many industrially important molecules. Modification of zeolite structures with organic groups offers a potential new way to change their properties of zeolites, beyond the manipulation of the zeolite framework structure and composition. The main goals of this thesis research are to study the organic-modification of the MFI pore structure, and to assess the effects of such modification on the adsorption and transport properties of zeolite MFI sorbents and membranes. In this work, the internal pore structure of MFI zeolite particles and membranes has been modified by direct covalent condensation or chemical complexation of different organic molecules with the silanol defect sites existing in the MFI structure. The organic molecules used for pore modification are 1-butanol, 1-hexanol, 3-amino-1-propanol, 1-propaneamine, 1,3-diaminopropane, 2-[(2-aminoethyl)amino]ethanol, and benzenemethanol. TGA/DSC and 13C/29Si NMR characterizations indicated that the functional groups were chemically bound to the zeolite framework, and that the loading was commensurate with the concentration of internal silanol defects. Gas adsorption isotherms of CO2, CH4, and N2 on the modified zeolite materials show a range of properties different from that of the bare MFI zeolite. The MFI/3-amino-1-propanol, MFI/2-[(2-aminoethyl)amino]ethanol, and MFI/benzenemethanol materials showed the largest differences from bare MFI. These properties were qualitatively explained by the known affinity of amino- and hydroxyl groups for CO2, and of the phenyl group for CH4. The combined influence of adsorption and diffusion changes due to modification can be studied by measuring permeation of different gases on modified MFI membranes. To study these effects, I synthesized MFI membranes with [h0h] out-of-plane orientation on α-alumina supports. The membranes were modified by the same procedures as used for MFI particles and with 1-butanol, 3-amino-1-propanol, 2-[(2-aminoethyl)amino]ethanol, and benzenemethanol. The existence of functional groups in the pores of the zeolite was confirmed by PA-FTIR measurements. Permeation measurements of H2, N2, CO2, CH4, and SF6, were performed at room temperature before and after modification. Permeation of n-butane, and i-butane were measured before and after modification with 1-butanol. For all of the studied gases, gas permeances decreased by 1-2 orders of magnitude compared to bare MFI membranes for modified membranes. This is a strong indication that the organic species in the MFI framework are interacting with or blocking the gas molecule transport through the MFI pores. A detailed fundamental study of the CO2 adsorption mechanism in modified zeolites is necessary to gain a better understating of the adsorption and permeation behavior of such materials. Towards this end, an in situ FTIR study was performe.For the organic molecules with only one functional group (1-butanol, benzenemethanol, and 1-propaneamine), physical adsorption was found - as intuitively expected - to be the only observed mode of attachment of CO2 to the modified zeolite material. Even in the case of MFI modified with 1,3-diaminopropane, only physical adsorption is seen. This is explained by the isolated nature of the amine groups in the material, due to which only a single amine group can interact with a CO2 molecule. On the other hand, chemisorbed CO2 species are clearly observed on bare MFI, and on MFI modified with 3-amino-1-propanol or 2-[(2-aminoethyl)amino]ethanol. Specifically, these are carbonate-like species that arise from the chemisorption of CO2 to the silanol group in bare MFI and the alcohol groups of the modifying molecule. The possibility of significant contributions from external surface silanol groups in adsorbing CO2 chemisorbed species was ruled out by a comparative examination of the FTIR spectra of 10 μm and 900 nm MFI particles modified with 2-[(2-aminoethyl)amino]ethanol.

The major innovation of this work is an establishment of a novel chiral separation process using preferential crystallization coupled with a membrane barrier. This hybrid process was proved to be promising from a significant increase in product yield and purity compared to existing chiral separation processes. This work sets up a process design platform to extend the use of this hybrid process to a separation of other mixtures. This novel process especially is a promising alternative for chiral separation of pharmaceutical compounds which include more than fifty percent of approved drugs world-wide. A better performance chiral separation technique contributes to cut the operating cost and to reduce the price of chiral drugs.

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