3. Electronic Theses and Dissertations (ETDs) - All submissions
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Item Evaluation of metal nanocomposite polymer inclusion membranes (PIMs) for trace heavy metal extraction in natural waters(2020) Maiphetlho, KgomotsoThe shortcomings of the conventional membranes in water applications such as low stability and the hydrophobic nature reduces the membrane productivity and lifespan. These result in expensive procedures that hinder membrane science technology. Hence, recent investigations have resulted in the synthesis of nanocomposite membranes as an alternative. In this work, silver nanocomposite polymer inclusion membranes (PIMs) were synthesized to evaluate the extraction of trace metal ions in natural waters. To characterise the PIMs, scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDX), contact angle measurements and water uptake measurements were used. The contact angle and the water uptake measurements highlighted that the introduction of the silver nanoparticles (Ag NPs) into the membrane, modified the membrane hydrophobic/hydrophilic character. The evaluation of the synthesized PIMs demonstrated that the PIMs containing Ag NPs exhibit better extraction capacity as opposed to the bare PIMs and the PIM with (40 w.t% D2EHPA, 10 w.t% Ag NPs and 50 w.t% PVC) has the optimum composition. It was then used to optimise the parameters that are important for the extraction of trace metal ions and those were sample pH 5, 1 M HNO3 of the receiving solution and 120 hrs for the extraction time. The selectivity of the nanocomposite PIM was investigated and it was found that its affinity towards a range of divalent cations (Co2+, Ni2+, Cu2+, and Cd2+) in synthetic water solutions, based on the percentage recovery factor of the extracted metal ions, follow the order; Cd 2+ (94) > Cu2+ (87) > Ni2+ (78) > Co2+ (67), where the numerical data in the brackets correspond to the percentage recovery factor of metal ion extracted from the source solution, respectively. This order can be explained by the Hard and Soft Acids and Bases Theory and the hydration energy of the metal cations. However, the stability of the PIM was still compromised during repeated cycle operations despite an improvement of hydrophilicity with introduction of Ag NPs, this was indicated by an appreciable leaching of the carrier (D2EHPA) and Ag NPs in a 4:1 ratio (identical to the ratio of these components in the original membrane). This silver nanocomposite PIM was tested in dam water. No matrix effect was observed on metal ion transport efficiency in such waters. The obtained transport efficiencies for the metal ions were Cd2+ (88), Cu2+ (80) , Ni2+ (62) , Co2+ (70) and Fe2+ (37) respectively. The newly synthesized PIM could be used for future extraction of the target metals in water systems. The designed PIM system has also the potential to be used as passive sampler for in situ extraction of the target metals in water systems. However, further studies are needed to improve the stability of both the carrier and nanoparticles in the membraneItem Optimum design parameters and mechanical properties of polymeric nanocomposites using NSGA-II optimization method(2018) Rabothata, Mahlatse SolomonThe aim of this work was to develop a method for optimizing both design parameters and mechanical properties of polymer based nanocomposites using numerical multi-objective optimization (MOO) methods. The main objective was to simultaneously maximize the elastic modulus and the tensile strength of nanocomposites. The rationale behind focusing on these particular properties is that they play a significant role in designing of materials for structural applications. Ji and Zare models of determining the elastic modulus and tensile strengths of polymeric nanocomposite materials were respectively used for the formation of the objective functions for numerical optimization. The design variables (i.e major factors affecting the given mechanical properties) were identified as the diameter of nanofillers, thickness of the interphase region, nanofillers loading as weight fraction, elastic modulus of the interphase, interfacial shear stress and the orientation factor of the nanofillers. The Fast Non-dominated Sorting Genetic Algorithm (NSGA-II) approach in MATLAB was used to maximize the objective functions by obtaining the optimum solutions of the given design variables. The optimization model was able to successfully find optimum solutions of the design variables. Furthermore, the overall optimization results were found to be in good agreement with the available experimental results from literature. The proposed optimization model was found to be significantly accurate in finding the optimum values of the design variables for improving the mechanical properties of nanocomposites. The optimum values of the design variables were determined to be 2.12 – 2.96 nm for the thickness of the interphase, 5.41 – 7.01 nm for the diameter of the nanofillers, 2.95 – 4.69 wt.% for the nanofillers loading, and 1 for the nanofillers orientation factor. In addition, the results further showed that nano-reinforcements such as multi-wall car-bonnanotubes(MWCNTs)yields high elastic modulus of the interphase and interfacial shear stress.Item Synthesis and performance evaluation of Nanocomposite SAPO-34/ceramic membranes for CO₂/N₂ mixture separation(2017) Kgaphola, Kedibone LawrenceGlobal warming, resulting from emission of greenhouse gases (GHGs), is the cause of drastic climate changes that threatens the economy and living conditions on the planet. Currently, recovery and mitigation of these greenhouse gases remains a technological and scientific challenge. Various recovery processes for the mitigation of GHGs have been reported including among others carbon capture and storage (CCS). The most mature and applied technology in CCS process involves the absorption of carbon dioxide on amine based solvents. However, studies have shown that this process has several drawbacks that include low stability and high energy required to strip off the absorbed CO2 and regenerate the solvent. This presents an opportunity for the development of new materials for CO2 capture such as zeolite membranes. Previous studies have shown that the separation of CO2 can be achieved with high selectivity at low temperatures using thin-film SAPO-34 membranes (thin layers on supports). This is because CO2 adsorbs strongly on the membranes compared to other gases found in flue gas. In the thin-film membranes supported on ceramic or sintered stainless steel, thermal expansion mismatch may occur at higher operating temperatures resulting in loss of membrane selectivity due to the formation of cracks. A new method is required to overcome the aforementioned problems, thereby enhancing the separation application of the membranes at higher temperatures. The effective separation and capture of CO2 from the coal-fired power plant flue gas is an essential part in the CCS process (Figueroa et al., 2016; Yang et al., 2008). Currently, the capture stage is a huge contributor to the overall cost of CCS (Yang et al., 2008). This is due to the high-energy intensity and inefficient thermal processes applied in the separation and capture in various industrial applications (Yang et al., 2008). This work presents the use of nanocomposite SAPO-34 zeolite membranes synthesized via the pore-plugging hydrothermal method for the separation of CO2 during post-combustion CO2 capture. The SAPO-34 membranes used were supported on asymmetric α-alumina as membrane supports. The membranes were characterized with a combination of dynamic and static physicochemical techniques such as Basic Desorption Quality Test (BDQT), X-ray diffraction (XRD) spectroscopy, Scanning Electron Microscopy (SEM), Fourier Transform Infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). The characteristic peaks at 2θ = 21°, 26°, and 32° on the XRD pattern confirmed the presence of SAPO-34 with a rhombohedral crystalline structure. The SEM images showed the formation of the cubic crystalline which were consistent with the reported morphology of SAPO-34. FTIR spectra showed the presence of the essential double-6 membered rings (D6R) and TO4 structural groups in surface chemistry of crystalline materials further confirming the presence SAPO-34. The TGA confirmed that the membranes possessed high thermal stability. To assess the feasibility of the synthesis process, the nanocomposite zeolites were grown within the tubular supports. The SEM images of the cross-section of the membrane confirmed the presence of the zeolites within the pores of the support confirming the fabrication of nanocomposite membranes by the pore-plugging synthesis method. The permeation tests used a dead-end filtration mode to measure the single gas permeance and the ideal selectivity of CO2 and N2 were calculated. The BDQT was essential in the study of the quality of the as-synthesized nanocomposite membranes. The quality of the membranes increased with an increase in the synthesis layers of the membranes. However, with an increase in synthesis layers, the membrane thickness also increases. The membrane thickness affected the gas permeance for CO2 and N2 significantly. The permeance of the N2 gas decreased from 10.73 x10-7 mol.s-1.m2Pa-1 after the first synthesis to 0.31 x10-7 mol.s-1.m2Pa-1 after seven synthesis layers. Alternatively, the more adsorbing gas CO2 decreased from 12.85 x10-7 mol.s-1.m2Pa-1 to 2.44 x10-7 mol.s-1.m2Pa-1. The performance of these zeolite membranes depends significantly on the operating conditions. Hence, we studied extensively the influence of the various operating conditions such as temperature, feed pressure and feed flowrate in this work. Results indicated that the membrane separation performance in this study is largely dependent on the temperature. In addition, the ideal selectivity decreased significantly with an increase in temperature. High temperatures results in less adsorption of the highly adsorbing CO2 gas, the permeance reduces significantly, while the permeance of the less adsorbing N2 increased slightly. The feed flow rate has less effect on the adsorbing gas while the non-absorbing gas increased resulting in a decrease in the ideal selectivity as well. The nanocomposite membranes in this study have a low flux compared to their thin film counterparts. An increase in feed pressure significantly increased the flux significantly as well as the ideal selectivity. Maxwell-Stefan model simulation was done in this study to describe the permeance of pure CO2 single gas permeance as a function of temperature. This model considered explicitly the adsorption-diffusion mechanism, which is the transport phenomenon, involved in the transport of CO2 through the zeolite membrane. The description of the support material was included in the model as well. However, the model was only applied to the CO2 gas permeation well within the experimental data. We then compared the model was with the experimental results and a good correlation was observed. In conclusion, SAPO-34 nanocomposite zeolite membranes were obtained at low temperatures (150 °C) with a short synthesis time (6 h). In addition, the high thermal stability of the as-synthesized SAPO-34 membranes makes them ideal for high temperature CO2 separation such as the intended post-combustion carbon capture. The BDQT revealed that the quality of the membranes was related to the thickness of the membranes. Therefore, better membrane quality was obtained with relatively thicker membranes. The separation performance evaluation was conducted on the membrane with the greatest quality. Our findings demonstrate that the performance of the membranes depends extensively on the operating conditions.Item Developing electrical tree resistant epoxy nanodielectrics with improved thermal properties(2017) Hank, Andrew MarvinTwo of the main contributors to high voltage insulation failure are thermal and electrical stresses. The failures may be mitigated by using nanodielectrics. The enhanced effect of nanoparticles in nanodielectrics is attributed to an interaction zone/interphase around each individual nanoparticle between the nanoparticle and host polymer. However, particle clumping or agglomerates are a major challenge in nanodielectric technology. In this work mitigation of the clumping challenges was explored through Rheology in determining optimal particle loading levels. The nanodielectrics studies were Boron Nitride and Carbon Nanospheres in Araldite Epoxy. The rheology results indicated an optimal loading level of 1.09 vol % to 1.35 vol% for Boron Nitride in Epoxy and 0.33 vol% for Carbon Nanospheres in Epoxy. Microscopy, dielectric spectroscopy, electrical tree characterisation, thermal expansion and laser flash analysis were used to validate the efficacy of the rheology results. The results indicated improved properties of the resultant dielectric such as; increased mechanical stiffness, increased electrical resistance and the percolation threshold, partial discharge suppression and increased thermal conductivity at the glass transition temperature. This study has established a rheology-based technique incorporated in the manufacturing process to determine the optimal filler loading of C/Epoxy and BN/Epoxy nanodielectrics. Future work is recommended as investigating either new particle types such as Sulphur hexafluoride in Carbon Nanospheres or mixtures of Carbon Nanospheres and Boron Nitiride.Item The effects of morphological changes and carbon nanospheres on the pseudocapacitive properties of molybdenum disulphide(2016) Khawula, TobileThe use of supercapacitors for energy storage is an attractive approach considering their ability to deliver high levels of electrical power, unlimited charge/discharge cycles, green environmental protection and long operating lifetimes. Despite the satisfactory power density, supercapacitors are yet to match the energy densities of batteries and fuel cells, reducing the competitiveness as a revolutionary energy storage device. Therefore, the biggest challenge for supercapacitors is the trade-off between energy density and power density. This presents an opportunity to enhance the electrochemical capacitance and mechanical stability of an electrode. Previous attempts to get around the problem include developing porous nanostructured electrodes with extremely large effective areas. One of the emerging high-power supercapacitor electrode materials is molybdenum disulfide (MoS2), a member of the transition-metal dichalcogenides (TMDs). Its higher intrinsic fast ionic conductivity and higher theoretical capacity have attracted a lot of attention, particularly in supercapacitors. In addition to double-layer capacitance, diffusion of the ions into the MoS2 at slow scan rates gives rise to Faradaic capacitance. Analogous to Ru in RuO2, the Mo center atom displays a range of oxidation states from +2 to +6. This plays an important role in enhancing charge storage capabilities. However, the electronic conductivity of MoS2 is still lower compared to graphite, and the specific capacitance of MoS2 is still very limited when used alone for energy storage applications. As evident in several literature reports, there is a need to improve the capacitance of MoS2 with conductive materials such as carbon nanotubes (CNT), polyaniline (PANI), polypyrrole (PPy), and reduced graphene (r-GO). Carbon nanospheres (CNS) have, in the past, improved the conductivity of cathode material in Li-ion batteries, owing to their appealing electrical properties, chemical stability and high surface area. The main objective of this dissertation research is to develop nanocomposite materials based on molybdenum sulphide with carbon nanospheres for pseudocapacitors with simultaneously high power density and energy density at low production cost. The research was carried out in two phases, namely, (i) Symmetric pseudocapacitors based on molybdenum disulfide (MoS2)-modified carbon nanospheres: Correlating physico-chemistry and synergistic interaction on energy storage and (ii) The effects of morphology re-arrangements on the pseudocapacitive properties of mesoporous molybdenum disulfide (MoS2) nanoflakes. The physico-chemical properties of the MoS2 layered materials have been interrogated using the surface area analysis (BET), scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray diffraction (XRD), Raman, fourier-transform infrared (FTIR) spectroscopy, and advanced electrochemistry including cyclic voltammetry (CV), galvanostatic cycling with potential limitation (GCPL), repetitive electrochemical cycling tests, and electrochemical impedance spectroscopy (EIS). In the first phase, Molybdenum disulfide-modified carbon nanospheres (MoS2/CNS) with two different morphologies (spherical and flower-like) have been synthesized using hydrothermal techniques and investigated as symmetric pseudocapacitors in aqueous electrolyte. The two different MoS2/CNS layered materials exhibit unique differences in morphology, surface areas, and structural parameters, which have been correlated with their electrochemical capacitive properties. The flower-like morphology (f-MoS2/CNS) shows lattice expansion (XRD), large surface area (BET analysis), and small-sized nanostructures (corroborated by the larger FWHM of the Raman and XRD data). As a contrast to the f-MoS2/CNS, the spherical morphology (s-MoS2/CNS) shows lattice contraction, small surface area with relatively large-sized nanostructures. The presence of CNS on the MoS2 structure leads to slight softening of the characteristic Raman bands (E12g and A1g modes) with larger FWHM. The MoS2 and its CNS-based composites have been tested in symmetric electrochemical capacitors in aqueous 1 M Na2SO4 solution. CNS improves the conductivity of the MoS2 and synergistically enhanced the electrochemical capacitive properties of the materials, especially the f-MoS2/CNS-based symmetric cells (most notably, in terms of capacitance retention). The maximum specific capacitance for f-MoS2/CNS-based pseudocapacitor show a maximum capacitance of 231 F g-1 with high energy density 26 Wh kg-1 and power density 6443 W kg-1. For the s-MoS2/CNS-based pseudocapcitor, the equivalent values are 108 F g-1, 7.4 Wh kg-1 and 3700 W kg-1. The high-performance of the f-MoS2/CNS is consistent with its physico-chemical properties as determined by the spectroscopic and microscopic data. In the second phase, Mesoporous molybdenum disulfide (MoS2) with different morphologies has been prepared via a hydrothermal method using different solvents, water or water/acetone mixtures. The MoS2 obtained with water alone gave graphene-like nanoflakes (g-MoS2) while the other with water/acetone (1:1 ratio) gave a hollow-like morphology (h-MoS2). Both materials are modified with carbon nanospheres as conductive materials and investigated as symmetric pseudocapacitors in aqueous electrolyte (1 M Na2SO4 solution). Interestingly, a simple change of synthesis solvents confers on the MoS2 materials different morphologies, surface areas, and structural parameters, correlated by electrochemical capacitive properties. The g-MoS2 exhibits higher surface area, higher capacitance parameters (specific capacitance of 183 F g-1, maximum energy density of 9.2 Wh kg-1 and power density of 2.9 kW kg-1) but less stable electrochemical cycling compared to the h-MoS2. These findings have opened doors for further exploration of the synergistic effects between MoS2 graphene-like sheets and CNS for energy storage.Item Characterisation of the structural properties of ECNF embedded pan nanomat reinforced glass fiber hybrid composites(2016-10-11) Bradley, PhilipIn this study, hybrid multiscale epoxy composites were developed from woven glass fabrics and PAN nanofibers embedded with short ECNFs (diameters of ~200nm) produced via electrospinning. Unlike VGCNFs or CNTs which are prepared through bottom-up methods, ECNFs were produced through a top-down approach; hence, ECNFs are much more cost-effective than VGCNFs or CNTs. Impact absorption energy, tensile strength, and flexural strength of the hybrid multiscale reinforced GFRP composites were investigated. The control sample was the conventional GFRP composite prepared from the neat epoxy resin. With the increase of ECNFs fiber volume fraction up to 1.0%, the impact absorption energy, tensile strength, and flexural strength increased. The incorporation of ECNFs embedded in the PAN nanofibers resulted in improvements on impact absorption energy, tensile strength, and flexural properties (strength and modulus) of the GFPC. Compared to the PAN reinforced GRPC, the incorporation of 1.0% ECNFs resulted in the improvements of impact absorption energy by roughly 9%, tensile strength by 37% and flexural strength by 29%, respectively. Interfacial debonding of matrix from the fiber was shown to be the dominant mechanism for shear failure of composites without ECNFs. PAN/ECNFs networks acted as microcrack arresters enhancing the composites toughness through the bridging mechanism in matrix rich zones. More energy absorption of the laminate specimens subjected to shear failure was attributed to the fracture and fiber pull out of more ECNFs from the epoxy matrix. This study suggests that, the developed hybrid multiscale ECNF/PAN epoxy composite could replace conventional GRPC as low-cost and high-performance structural composites with improved out of plane as well as in plane mechanical properties. The strengthening/ toughening strategy formulated in this study indicates the feasibility of using the nano-scale reinforcements to further improve the mechanical properties of currently structured high-performance composites in the coming years. In addition, the present study will significantly stimulate the long-term development of high-strength high-toughness bulk structural nanocomposites for broad applications.