A dissertation submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, in fulfilment of the requirements for the degree of Master of Science in Engineering 25 May 2017 / Two 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. / MT 2017

Van der Waals materials and inorganic nanoparticles are two categories of nanomaterials that have been widely investigated in the past two decades. Both of them have been considered to be promising as candidates for the next generation electrical, optical, and mechanical applications. However, both of them have a few limitations that greatly affect the performance of devices, e.g. zero bandgap for graphene; poor contact quality, low mobility and quantum efficiency for MoS2; and poor interparticle conductivity for nanoparticles. This thesis tries to explore a new way of combining these two categories of material into hybrids, so that the intrinsic limitations of materials from each category will be overcome by the other materials that are introduced into the hybrid. This thesis consists of five parts. The first part (Chapter 1) introduces the background and motivation of the thesis. The second part (Chapters 2, 3, 4, and 5) describes the detailed processes and methods, starting from preparing each element to the assembly of these element into a hybrid structure device. This part also includes understanding the mechanisms of 2D and 3D self-assembly of nanoparticles. The third part (Chapter 6 and 7) describes two examples of hybrid structures, including the investigation of electron or molecule transfer inside the hybrid. The fourth part (Chapter 8) introduces other findings and technical innovations, including alternative ways of thin film nanoparticle self-assembly/deposition, and fabrication methods for the band structure analysis of transition metal dichalcogenides by angle resolved photo-electron spectroscopy. The fifth part (Chapter 9) describes several possible future work directions that could be investigated to improve the understanding of the nanoparticle assembly and translating the conceptual device into real applications.

Batteries are complex, multidisciplinary, electrochemical energy storage systems that are crucial for powering our society. During operation, all battery technologies suffer from voltage losses due to energetic penalties associated with the electrochemical processes (i.e., ohmic resistance, kinetic barriers, and mass transport limitations). A majority of the voltage losses can be attributed to processes occurring on/in the battery electrodes, which are responsible for facilitating the electrochemical reactions. A major challenge in the battery field is developing strategies to mitigate these losses. To accomplish this, researchers must i) identify the processes limiting the performance of the electrode, ii) characterize the main, performance-limiting processes to understand the underlying mechanisms responsible for the poor performance, and iii) mitigate the voltage losses by developing strategies which target these underlying mechanisms. In this thesis, three studies are presented which highlight the role of electrochemical engineers in alleviating the performance limiting processes in battery electrodes. Each study is focused on a different step of the research approach (i.e., identification, characterization, and mitigation) and analyzes an electrode from a different battery system. The first part of the thesis is focused on identifying the processes limiting the capacity in nanocomposite lithium-magnetite electrodes. To accomplish this, the mass transport processes and phase changes occurring within magnetite electrodes during discharge and voltage recovery are investigated using a combined experimental and modeling approach. First, voltage recovery data are analyzed through a comparison of the mass transport time-constants associated with different length-scales in the electrode. The long voltage recovery times are hypothesized to result from the relaxation of concentration profiles on the mesoscale, which consists of the agglomerate and crystallite length-scales. The hypothesis was tested through the development of a multi-scale mathematical model. Using the model, experimental discharge and voltage recovery data are compared to three sets of simulations, which incorporate crystal-only, agglomerate-only, or multi-scale transport effects. The results of the study indicate that, depending on the crystal size, the low utilization of the active material (i.e., low capacity) is caused by transport limitations on the agglomerate and/or crystal length-scales. For electrodes composed of small crystals (6 and 8 nm diameters), it is concluded that the transport limitations in the agglomerate are primarily responsible for the long voltage recovery times and low utilization of the active material. In the electrodes composed of large crystals (32 nm diameter), the slow voltage recovery is attributed to transport limitations on both the agglomerate and crystal length-scales. Next, the multi-scale model is further expanded to study the phase changes occurring in magnetite during lithiation and voltage recovery experiments. Phase changes are described using kinetic expressions based on the Avrami theory for nucleation and growth. Simulated results indicate that the slow, linear voltage change observed at long times during the voltage recovery experiments can be attributed to a slow phase change from α¬-LixFe3O4 to β¬-Li4Fe3O4. In addition, simulations for the lithiation of 6 and 32 nm Fe3O4 suggest the rate of conversion from α¬-LixFe3O4 to γ-(4 Li2O + 3 Fe) decreases with decreasing crystal size. The next part of the thesis presents a study aimed at characterizing the formation of PbSO4 films on Pb in H2SO4, which has been previously identified as a performance-limiting process in lead-acid batteries. Transmission X-ray microscopy (TXM) is utilized to monitor, in real time, the initial formation, the resulting passivation, and the subsequent reduction of the PbSO4 film. It is concluded with support from quartz-crystal-microbalance experiments that the initial formation of PbSO4 crystals occurs as a result of acidic corrosion. Additionally, the film is shown to coalesce during the early stages of galvanostatic oxidation and to passivate as a result of morphological changes in the existing film. Finally, it is observed that the passivation process results in the formation of large PbSO4 crystals with low area-to-volume ratios, which are difficult to reduce under both galvanostatic and potentiostatic conditions. In a further extension of this study, TXM and scanning electron microscopy are combined to investigate the effects of sodium lignosulfonate on the PbSO4 formation and the initial growth of PbSO4 crystals. Sodium lignosulfonate is shown to retard, on average, the growth of the PbSO4 crystals, yielding a film with smaller crystals and higher crystal densities. In addition, an analysis of the growth rates of individual, large crystals showed an initial rapid growth which declined as the PbSO4 surface coverage increased. It was concluded that the increase in PbSO4 provides additional sites for precipitation and reduces the precipitation rate on the existing crystals. Finally, the potential-time transient at the beginning of oxidation is suggested to result from the relaxation of a supersaturated solution and the development of a PbSO4 film with increasing resistance. The final part of the thesis presents a study aimed at mitigating the ohmic losses during pulse-power discharge of a battery by the adding a second electrochemically active material to the electrode. Porous electrode theory is used to conduct case studies for when the addition of a second active material can improve the pulse-power performance. Case studies are conducted for the positive electrode of a sodium metal-halide battery and the graphite negative electrode of a lithium-ion battery. The replacement of a fraction of the nickel chloride capacity with iron chloride in a sodium metal-halide electrode and the replacement of a fraction of the graphite capacity with carbon black in a lithium-ion negative electrode were both predicted to increase the maximum pulse power by up to 40%. In general, whether or not a second electrochemically active material increases the pulse power depends on the relative importance of ohmic-to-charge transfer resistances within the porous structure, the capacity fraction of the second electrochemically active material, and the kinetic and thermodynamic parameters of the two active materials.

Zhou, Wenjia = 聚苯乙烯/銀聚合物納米棒陣列的合成、表征與生長的研究 / 周文佳. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references (leaves 69-73). / Text in English; abstracts in English and Chinese. / Zhou, Wenjia = Ju ben yi xi / yin ju he wu na mi bang zhen lie de he cheng, biao zheng yu sheng zhang de yan jiu / Zhou Wenjia. / Chapter I. --- Abstract / Chapter IV. --- Acknowledgement / Chapter V. --- Contents / Chapter 1 --- Introduction / Chapter 1.1 --- Motivations / Chapter 1.2 --- Overview of the thesis / Chapter 2 --- Instruments / Chapter 2.1 --- Introduction to electron microscopes / Chapter 2.2 --- Scanning electron microscope / Chapter 2.2.1 --- Introduction to SEM working principle / Chapter 2.2.2 --- Electron specimen interactions and their applications in SEM / Chapter 2.2.3 --- Specific SEM conditions in the experiments / Chapter 2.3 --- Transmission electron microscope / Chapter 2.3.1 --- Introduction to TEM working principle / Chapter 2.3.2 --- Imaging mode and diffraction mode in TEM / Chapter 2.3.3 --- X-ray microanalysis with TEM / Chapter 2.3.4 --- Specific TEM conditions in the experiments / Chapter 3 --- Anodic aluminum oxide templates with different parameters / Chapter 3.1 --- Introduction to self-ordered anodic aluminum oxide / Chapter 3.1.1 --- Electrochemistry of anodic alumina / Chapter 3.1.2 --- Pore growth mechanism / Chapter 3.1.3 --- Self-ordered alumina by two-step anodization / Chapter 3.1.4 --- Other advanced methods for fabrication of monodomain AAO / Chapter 3.1.5 --- Applications of AAO templates in nanomaterials fabrication / Chapter 3.2 --- Preparation procedures of porous AAO templates we used / Chapter 3.2.1 --- Experimental setup / Chapter 3.2.2 --- General preparation procedures of AAO thin film on Al / Chapter 3.3 --- Experimental data of AAO templates with different parameters / Chapter 3.3.1 --- Different interpore distances / Chapter 3.3.2 --- Different pore depths and pore sizes / Chapter 3.3.3 --- Calibration of AAO templates pore depths and pore sizes at different anodic potentials / Chapter 4 --- Preparation of free standing polystyrene nanorods arrays with different parameters / Chapter 4.1 --- General preparation procedures of free standing polymer nanorods arrays / Chapter 4.2 --- Different rods intervals and diameters / Chapter 4.3 --- Limitations to the rods lengths control / Chapter 4.4 --- Discussion on the polymer properties for the successful preparation of free standing polymer rods arrays / Chapter 5 --- Thermal reduction method to embed Ag nanoparticles inside the polymer rods / Chapter 5.1 --- General preparation procedures of PS/Ag nanorods arrays / Chapter 5.2 --- Analysis method and procedure of Ag nanoparticles inside PS rods / Chapter 5.3 --- Typical TEM images of the three series samples / Chapter 5.4 --- Data analysis of Ag nanoparticles inside PS rods / Chapter 5.5 --- Discussion on Ag particles growth process / Chapter 5.6 --- Conclusion and suggestions for improvement / Chapter 6 --- Conclusion / Reference / Appendix

Polymer materials stand on a very significant position in the materials industry area. The presence of organoclay nanocomposites reinforces polymer materials on many properties like strength, tensile and so on. Most previous studies on the characteristics of organoclays and polymer nanocomposites were based on the experimental approaches such as XRD (X-ray Diffraction) and NMR (Nuclear Magnetic Resonance). These methods have achieved successfully on the basic analysis of chains and layering structures of polymer nanocomposites. However, information on the molecular level cannot be provided by those approaches. MD (Molecular Dynamic) simulation method could be employed to develop further information on the molecular level about organoclays and interlayer structure polymer nanocomposites. In the research of ODTMA-MMT (Octadecyltrimethylammonium-Montmorillonite) organoclay simulation, we find that the strong layering behaviour of interlayer ODTMA molecules is present with the same minimum distance between nitrogen atoms and MMT surface in different T/O (Tetrahedral vs. Octahedral) ratio cases. Nitrogen atoms sit right above the corresponding hexagonal cavities, which is in agreement with the previous research. The interaction energy between surfactants and MMT clay will reach the lowest point when substitution ratio of tetrahedral and octahedral (T/O) is equal to 1:1. Moreover, MSD (Mean Square Displacement) and diffusion coefficient of different models under same CEC (Charge Exchange Capacity) condition are inverse ratio to the T/O proportion. In nylon6 polymer nanocomposites, sodium cations which exist originally in ensemble as charge balancer are absorbed much closer to MMT surface than the organic components in the nylon 6 ODTMA-MMT ensemble. Sodium atoms or nitrogen atoms in surfactants both have higher MSD and coefficients than those atoms in the organic-modified clays. In the exfoliated nylon 6 ODTMA-MMT nanocomposites, pair correlation has been analysed instead of density profile. Layering packing structure is also shown through this analysis, which is also consistent with previous work.

Thesis (Ph. D.)--University of Alabama at Birmingham, 2007. / Title from PDF title page (viewed Jan. 28, 2010). Additional advisors: Derrick R. Dean, Wiliam K. Nonidez, Andrei Stanishevsky, Charles L. Watkins. Includes bibliographical references.

Dissertation (Ph.D.)--Auburn University, 2009. / Abstract. Includes bibliographic references.

D. Tech. Chemical Engineering. / This research aims to improve the current state of wastewater treatment technologies by exploiting the characteristics and capabilities of nanomaterials. Also, it aims at protecting the environment and human health by minimizing exposure of toxic contaminants found in waters sources by treatment with cheaply engineered materials. The nanocomposites that will be employed in this study have shown to be effective for removing a number of heavy metals from aqueous solutions during trial experiment. The study is therefore carried out to reduce the water scarcity in South Africa by minimizing the contamination of remaining water resources. With industrial effluents the main targets, the aim is to design systems that will enable industries to recycle their wastewater instead of discharging into the environment. This study will therefore benefit the communities who solely depend on surface and ground water and again it will safe industrial bodies high costs of treating their wastewater with ineffective conventional methods. The research focuses on the application of polypyrrole-clay nanocomposites for removing heavy metals from wastewater streams. The research conducted hereby highlights the application of polymer based nanocomposites as suitable adsorbents for the remediation of the toxic chromium(VI) [Cr(VI)] from water. The work describes the preparation and characterization of the nanocomposites, their application to wastewater laden with Cr(VI) in both batch and continuous adsorption and finally understanding the adsorbent-adsorbate interactions and sorption mechanisms under various physico-chemical conditions.

M. Tech. Department of Chemical, Metallurgical and Materials Engineering. / Discusses how to synthesize a titanium-manganese oxide composite electrode with improved supercapacitive properties. The research aim was achieved through the following objectives: 1. the mechanisms of the synergistic incorporation of manganese oxide for improving the supercapacitive properties of titanium oxide electrodes. 2. Investigate possible metallurgical interactions and phenomenon during the sintering of the composite. 3. Investigate the electrochemical characteristics of titanium-manganese composite electrodes.

D.Tech. Chemical Engineering / This research emphasizes the potential application of conducting polymer based nanocomposites for the remediation of contaminants from water. This study facilitates the preparation of conducting polymer based nanomaterials for the efficient removal of fluoride and toxic chromium(VI) from water. This work also identifies the importance of understanding the physico-chemical properties of the synthesized nanomaterials which greatly influence the materials performance in removing contaminants from water.