Membranes made of composite polymer material are widely employed to separate gas mixtures in industrial processes. These membranes have better performance than membranes consisting of polymer alone. To understand the mechanism and therefore aid membrane design it is essential to explore the penetrant transport in the complex composites from the molecular level, but few researchers have done such research to our knowledge. Herein the penetrant transport in the composite Poly (4-methyl-2-pentyne) (PMP) and silica nanoparticle is being explored with molecular dynamics (MD) simulations. The structure of the PMP and amorphous silica nanoparticle composite was modeled and with the structure the variation of the cavity size distribution was established due to the existence of nanoparticles. The diffusivity of different penetrants, including H2, O2, Ar, CH4 and n-C4H10 was determined through least square fit of the data of mean square displacement at different times in the Fickian diffusive regime. The solubility coefficients and the permeability of different penetrants in PMP and the composite were calculated and the distribution of potential difference due to the penetrant insertion was analyzed in detail to find the reason of higher solubility in composite than pure PMP. Silica has different crystalline form. In faujasite silica, there are pores that are large enough to allow penetrants to pass through, while in cristobalite silica, the Si and O atoms are densely packed and there are no pores that penetrants can pass through. The transport properties of penetrants in the composite of PMP and nanoparticles of these two types of silica are therefore different. The molecular dynamics method was employed in the research to explore the transport of different penetrants in the composites of PMP and nanoparticles of two forms of silica, namely the cristobalite form and the faujasite form. The structures of the PMP and nanoparticle of cristobalite silica composite (PMPC) and the PMP and nanoparticle of faujasite silica composite (PMPF) were established and relaxed. With the relaxed structure, the cavity size change due to the insertion of both types of nanoparticle was analyzed. The diffusivity of different penetrants was determined through least square fit of the data of mean square displacement at different time in Fickian diffusive regime. The solubility coefficients and the permeability of different penetrants in PMPC and PMPF were calculated and compared. The parameters of "Ti" in the Lennard-Jones potential equation were estimated; MD simulation of penetrants transport in composite poly (4-methyl-2-pentyne) and TiO2 nanoparticles were done; the simulation results were compared with composite poly (4-methyl-2-pentyne) and silica nanoparticles. / Ph. D.

A porous silica –silica composite was processed with varying fiber diameters using the slurry moulding technique. The advantage of the process was that the density of the composite could be processed to the required levels. The reinforcements used were fibers obtained by leaching E-glass cloth, imported silica fibers with diameter <1.8µ and hollow silica fibers processed using sol-gel method. All the properties depend on the density of the composite. The compressive strength was measured in the perpendicular and parallel directions. Strength was high when the load axis was along the fiber direction. The composite with fine fibers (< 1.8 µ pure silica fibers) showed higher strength compared to the leached silica fibers. The thermal conductivity measurement on these composites showed an increase with temperature owing to the domination of radiation at high temperatures. As the vacuum level was approached, the thermal conductivity showed a decrease due to the absence of the convective part of the thermal transfer process. For use as a thermal protection system, it is important to measure the thermal response of these tiles in a simulated re-entry environment. Tests were done to measure this response for a given heat flux conditions at 38W/cm2 to 75W/cm2 and the backwall temperature was measured for various types of silica -silica composites. The role of impurities like sodium and B2O3 was also studied with respect to the conversion from amorphous to crystalline forms of SiO2. The severe increase in the coefficient of thermal expansion when SiO2 converted from amorphous to α– crystoballite was also measured. CSZP CSZP which belongs to the NZP family was processed using the co-precipitation technique. The influence of substituting the ‘P’ site with ‘Si’ atom was studied for its influence on thermal expansion – both at the bulk level by dilatometry and at the intrinsic level using high temperature XRD. For many anisotropic materials micro-cracking is a serious issue while cooling from the sintering temperature. It has been previously proved that this extent of micro-cracking depends on the particle size. Smaller the particle size is therefore preferred. One of the significant results obtained in this study was the successful use of microwaves to process crack free CSZP with fine grain size. CSZP with 95% density having a grain size as small as 1µ have been processed using microwave sintering. Dielectric property evaluation namely dielectric constant, dielectric loss and temperature coefficient of resonant frequency which are vital parameters required if this material is to be used as a candidate TPS have also been measured. The thermal conductivity of the sample was measured using Laser flash apparatus and was found to be 0.9 W/mk which provides an indication that this material can be used as a successful material for TPS. Finally a composite consisting of silica fiber with CSZP as matrix was processed and tested for heat flux. The low back wall temperature indicates that this material is a potential replacement for silica tile.

Marine diatoms are the dominant primary producers in coastal and shelf regions, and contribute to about 20% of the annual photosynthesis on Earth. Diatoms also exert a major control on the marine silicon (Si) cycle through the formation of biogenic silica (bSiO2). Continental shelves account for half of the total marine area in the Arctic, yet our knowledge of the cycling of Si for this critically climate-impacted region is limited. The overall objective of this thesis was to improve our understanding of marine bSiO2 dynamics and Si cycling in marine Arctic and Subarctic ecosystems using novel techniques. Phytoplankton and nutrient observations, including dissolved and particulate silica concentrations, are presented from a period of ten years within five biological ‘hotspots’ in the Bering and Chukchi Seas. The first measurements of bSiO2 production and dissolution rates are also presented from a period of four years at the same sites. Results from this work show that (i) although interannual variability is high, diatoms are responsible for most of the high primary productivity in the Bering and Chukchi Seas, (ii) bSiO2 is primarily re-dissolved within the euphotic zone rather than exported, and (iii) phytoplankton phenology and marine Si cycling are affected by short-term climatic changes in this region. We also present the first measurements of bSiO2 production rates along a transect from the Canadian Arctic Archipelago (CAA), through Baffin Bay and into the Labrador Sea. We show that diatoms are both abundant and productive throughout these regions in summer, despite widespread Si limitation in the low-nutrient surface waters. Finally, we also investigated the natural variations in the Si isotopic composition of silicic acid (30Si(OH)4). On a transect through the Bering and Chukchi Seas, Canada Basin and CAA, and finally to Baffin Bay and the Labrador Sea, we found that δ30Si(OH)4 signals reflect water mass composition, the dissolution of bSiO2 throughout the water column, and the biological utilization of Si in surface waters. Ultimately, this work provides insight into the processes controlling marine Si cycling within the Arctic and its links to the global marine Si cycle and other biogeochemical cycles. / Graduate / 2020-03-13

Thesis (MPH. (Occupational and Environmental Health))-- University of Limpopo, 2012 / Background: The objective of this study was to quantify personal time-weighted average respirable dust and silica exposure of workers at foundries in Gauteng and to rank the occupations in foundries according to the risk of exposure to silica quartz. Methods: A task-based risk assessment of 56 personal samples from two foundries was conducted. Personal exposure data was collected from workers’ breathing zones for the full working shift. All analyses of samples for silica dust were carried out in the CSIR Centre for Mining Innovation’s Laboratory, which has SANAS accreditation (ISO 17025) for both x-ray powder diffraction and particle size analysis methods. Results: The personal time-weighted average mean and median respirable silica dust concentration was 0.184 mg/m³ and 0.167 mg/m³ respectively. The maximum exposure concentration was 0.835 mg/m³ and minimum exposure was 0.010 mg/m³. The occupations within the foundries with the highest exposures were moulders, sand mixers, furnace operators and the lowest exposed occupations were grinders, closers, and casting operators. The majority of foundry workers (62%) in both foundries are exposed to respirable silica dust at above the South African occupational exposure level (OEL). Conclusion and recommendations: Foundry workers are over-exposed to respirable silica dust and are potentially at high risk of contracting silicosis and other occupational diseases associated with respirable silica dust. It is recommended that a dust control programme be implemented and a baseline study be conducted.

Nanoemulsions are templates that have the potential to fill the gap between micellar systems and latex particles in the preparation of porous materials. A nanoemulsion can also be used as a carrier for uploading the desired materials inside the pore formed after the removal of the template. In this research, oil-in-water (O/W) nanoemulsions were prepared by means of a low-energy method based on a phase inversion composition (PIC) technique, using two nonionic surfactants (Tween 80 and Span 80), which can be mixed in order to adjust the hydrophilic-lipophilic balance (HLB). The influence of a number of parameters on the tunability and stability of such nanoemulsions was also studied. The effect of the simultaneous intercrossing of multifactors on droplet size was explored using a process- mixture design, and the size of the nanoemulsion oil droplets was measured by means of dynamic light scattering (DLS). The nanoemulsions were combined with sol-gel method in order to prepare porous silica with a macroporosity in the 50 nm to 400 nm range. The results demonstrate that a precise synergy between the silica source and the nanoemulsions is essential for effective interactions and homogeneous structures. Depending on the nature of such interactions, a variety of materials were observed, from hollow particles to continuous gels. Changing the size of the oil droplet and the volume of the nanoemulsions produced silica with differing pore sizes and varying total pore volumes. The obtained hierarchical porous silica (HPS) were characterized using mercury porosimetry, small angle X-ray scattering (SAXS), nitrogen isotherms, Fourier transform infrared (FTIR) analysis, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The parallel use of the oil vesicles as containers for the further synthesis of metal oxide is a novel method of internally functionalizing the silica. When hydrophobic metal precursors are dissolved into the oil phase before the preparation of the nanoemulsion, they are confined within the globular cavities of the silica. The thermal treatment applied to the material to burn the organics then leads to the final formation of metal oxide nanoparticles, which are larger than the porosity of the silica matrix but entrapped within the large cavities, producing a "rattle-like" structure. This method was demonstrated through the synthesis of Fe2O3, Fe3O4, and Co3O4 nanoparticles, and the results showed that a rather large amount of metal oxide (up to a 60 wt.% of metal oxide in nanocomposites) be generated while still maintaining the nanometric size observed at lower concentrations. This method allows control of the type of metal oxide, the concentration of the metal oxide, and the pore size, which enables the creation of different types of nanocomposites. Metal oxide hierarchical porous silica (MHPS) nanocomposites were characterized based on nitrogen isotherms, TEM and SEM observations, FTIR analysis, X-ray diffraction (XRD), and Mossbauer spectroscopy. Magnetic measurements were also taken. This new method, using the new templating objects, is a perfect illustration of the concept of "integrative synthesis,??? whereby the combination of building units and reactional mechanisms leads to complex structures as a result of true synergy among the elements during the reaction. In this case, the size of the nanoemulsion and the total water volume both contribute to the generation of distinctive architectures. In addition, the reaction of the metal oxide precursors within the cavities limits the extension of the final crystal size, but the surrounding solid matrix plays a role as well by keeping the particles apart. The final factor is that the reactive materials cannot leak from the silica because of the rattle-like structure, but the reagents can reach those particles through the porosity of the silica framework.

Due to the wide application of silica based systems ranging from microelectronics to nuclear waste disposal, detailed knowledge of water-silica interactions plays an important role in understanding fundamental processes, such as glass corrosion and the long term reliability of devices. In this dissertation, atomistic computer simulation methods have been used to explore and identify the mechanisms of water-silica reactions and the detailed processes that control the properties of the water-silica interfaces due to their ability to provide atomic level details of the structure and reaction pathways. The main challenges of the amorphous nature of the silica based systems and nano-porosity of the structures were overcome by a combination of simulation methodologies based on classical molecular dynamics (MD) simulations with Reactive Force Field (ReaxFF) and density functional theory (DFT) based ab initio MD simulations. Through the development of nanoporous amorphous silica structure models, the interactions between water and the complex unhydroxylated internal surfaces identified the unusual stability of strained siloxane bonds in high energy ring structure defects, as well as the hydroxylation reaction kinetics, which suggests the difficulty in using DFT methods to simulate Si-O bond breakage with reasonable efficiency. Another important problem addressed is the development of silica gel structures and their interfaces, which is considered to control the long term residual dissolution rate in borosilicate glasses. Through application of the ReaxFF classical MD potential, silica gel structures which mimic the development of interfacial layers during silica dissolution were created A structural model, consisting of dense silica, silica gel, and bulk water, and the related interfaces was generated, to represent the dissolution gel structure. High temperature evolution of the silica-gel-water (SGW) structure was performed through classical MD simulation of the system, and growth of the gel into the water region occurred, as well as the formation of intermediate range structural features of dense silica. Additionally, hydroxylated silica monomers (SiO4H4) and longer polymerized silica chains were formed in the water region, indicating that glass dissolution is occurring, even at short time frames. The creation of the SGW model provides a framework for a method of identifying how interfacial structures which develop at glass-water interfaces can be incorporated into atomistic models for additional analysis of the dissolution of silicates in water.

No description available.

Typescript. / Digitized by Kansas Correctional Industries

Typescript (photocopy). / Digitized by Kansas Correctional Industries

Early intervention in cancer and other illnesses is highly desired. The evolution of the proteomics field has benefited the possibility of getting to this goal by allowing researchers to look at different biomarkers. However, the high complexity of biological samples and the low levels at which biomarkers are found in these fluids make the analyses even more complicated.Protein microarrays have arisen as alternatives to traditional methods to look at multiple protein levels simultaneously with the benefit of high specificity, low limits of detection and the requirement of small samples. In this work, a significant improvement in net signals obtained with fluorescent detection (using three-dimensional scaffolds based on silica colloidal crystals -SCC-) is presented in contrast to commercially available flat substrates.A novel approach to extract trace proteins in solution and more complex matrices by using sub-micrometer silica particles as support for antibodies in affinity capture experiments is presented. Bovine Serum Albumin, Ephrin-receptor A2, Alpha-fetoprotein, and Prostate Specific Antigen have been used as model proteins. Recoveries of 90% or more are obtained with this method and reusability of the particles was achieved. MALDI-MS detection was successfully performed with the protein extracts which opens up the opportunity of further analysis such as determining post-translational modifications which is relevant when dealing with biomarker candidates.Last we present the use of our substrates as alternatives to conventional targets in mass spectrometry (MS). Traditional Matrix-assisted Laser Desorption Ionization MS (MALDI-MS) of proteins presents the problem of adduct formation with clusters from the matrix used in the process. Those adducts can affect the accurate determination of the molecular weight for a given protein and when could potentially mask slight differences in molecular weight of very similar proteins in mixtures. We present the alternative of using SCC on silicon wafers as a target for MALDI-MS samples. Our peak widths are extremely narrow and approach the one of the isotopic envelops. At the same time, porosity of our material seems to prevent the formation of adducts, which enables the differentiation of proteins with small molecular weight differences like mutants or same proteins from different sources.