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There is a raising need to design a safe and efficient cryogenic fuel tank for the new generation of reusable launch vehicles. The new tank design focuses on composite materials that can achieve the drastic reduction of empty/non-payload and structural weight. In addition to the materials to be compatible with cryogenic temperatures, interior components of the vehicle may be subjected to significantly elevated temperatures due to heat conduction from the vehicle surfaces during and after atmospheric re-entry. Therefore, there is the need to understand the performance of the composites after experiencing extreme thermal environments. Polymer-layered nanocomposites were studied to determine if they can reduce the permeation to the liquid nitrogen used as fuel in the next generation of space vehicles. Due to the non-permeable nature of the silicates and the exfoliated structure they adopt into the polymer matrix the addition of nanoclays into a polymer is expected to reduce the permeation to several gases without sacrificing the mechanical strength of the nanocomposite as well as providing additional improvements such as increase of thermal stability of the nanocomposite. Several types of matrixes modified with different types and content of nanoclays were tested and their permeability coefficient was calculated. The permeability values obtained for the different formulations assisted to understand the transport properties of nanoclay modified composites. In addition to this, thermal characterization was performed with the help of dynamic mechanical analysis, thermogravimetric analyses and differential scanning calorimetry studies. To determine if the nanoclay modified nanocomposites were affected by extreme temperatures the samples were subjected to thermal cycling. Comparison of the transport and thermal properties before and after cycling helped to analyze the effect of the addition of the nanoclays in the nanocomposites. Positron annihilation spectroscopy (PAS) was utilized to comprehend how the distribution of the free volume was affected by the presence of the nanoclays and by the thermal cycling applied. Different permeability models were utilized in an attempt to validate the experimental results of the different nanocomposite structures. This analysis was used to provide additional insight into many aspects of the experimental results obtained in this study.

In the present paper, which was written in collaboration with the Observatory of Paris, thermal models of two CubeSat missions were created. The first goal of this work was to create a nodal simulation of the PicSat satellite to verify the survivability of the system within the extreme space environment. In a second step suitable countermeasures were suggested, if parts of the satellite exceeded a critical temperature limit. Additionally, the impacts of three failure modes were investigated. The second goal was to perform thermal pre-studies of different satellite configurations of the CIRCUS satellite based on the model of PicSat. The simulation conducted in this work showed that PicSat fulfils its thermal requirements, except for three components. Out of the failure modes considered in this study, only an error of the attitude determination and control systems (ADCS) showed a critical impact on the thermal state of PicSat. As the outcome of the pre-studies of CIRCUS, two of the considered configurations were recommended for further analysis. The results of this work will contribute to the future development of the PicSat and CIRCUS missions. / Dans le cadre de ce mémoire, qui a été rédigé en collaboration avec l'Observatoire de Paris, les modèles thermiques de deux missions CubeSat ont été créés. Le premier objectif de ce projet était de d\'velopper une simulation nodale du satellite PicSat afin de vérifier la capacité de survie du système dans les conditions hostiles de l'espace. Dans un second temps, des mesures correctives ont été suggérées si la température de certaines sections du satellite venait à excéder une limite critique. En outre, les impacts de trois défaillances ont été analysés. Le second objectif était de réaliser des pré-études thermiques pour différentes configurations du satellite CIRCUS basées sur le modèle de PicSat. Les simulations réalisées dans le cadre de ce projet ont montré que PicSat remplit ses exigences thermiques, à l'exception de trois composants. Des différentes défaillances étudiées, seule une erreur du système de détermination et de contrôle d'attitude (Attitude Determination and Control System ADCS) a montré un impact critique sur l'état thermique de PicSat. A l'issue des pré-études de CIRCUS, deux des configurations étudiées ont été recommandées pour être l'objet d'une analyse plus avancée. Les résultats de ce projet contribueront au développement à venir des missions des satellites PicSat et CIRCUS.

The objective of this thesis was to evaluate the feasibility of three approaches to thermal imaging that used fiber-optics to decouple the imaging optic from a detector in order to form images without a direct line of sight. All images were formed using 2 m-long fibers, at a working distance of 19 cm, and the ability to detect temperatures between 100 °C to 200 °C. The three approaches were designated active, hybrid, and passive. The active approach involved scanning a single fiber in the image plane to formulate thermal images. Although images had sufficient field of view and spatial resolution, they were not formulated at a frequency of at least 1 Hz using either linear stages or a piezoelectric actuator for scanning. The hybrid approach involved scanning a bundle of fibers in the image plane to formulate a thermal image. Although it was possible to form individual images from fibers within a simple bundle and a seven-fiber bundle with sufficient field of view and spatial resolution, an image formulation frequency of at least 1 Hz was not achieved. While considered feasible, future work is required to identify a suitable motion platform, design a new bundle, and develop a method for stitching images from individual fibers into a single spatially-coherent image in order to achieve an image formulation frequency of at least 1 Hz. Lastly, the passive approach was evaluated in which images were formed using a fixed seven-fiber bundle for direct thermal imaging. The seven-fiber bundle produced images with sufficient field of view and an image formulation frequency on the order of kHz, but without sufficient spatial resolution. Additional work is required to determine the feasibility of designing a passive bundle for a specific spatial resolution, as well as, if overall costs are prohibitive. While no approach satisfied all functional requirements specified herein, evaluation of each approach and a potential solution are provided.

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, in fulfillment of the requirements for the degree of Master of Science. March 28, 2013 / The search for solutions to the important differential equations arising in extended surface heat transfer continues unabated. Extended surfaces, in the form of longitudinal fins are considered. First we consider the steady state problem and then the transient heat transfer models. Here, thermal conductivity and heat transfer coefficient are assumed to be functions of temperature. Thermal conductivity is considered to be given by the power law in one case and by the linear function of temperature in the other; whereas heat transfer coefficient is only given by the power law. Explicit analytical expressions for the temperature profile, fin efficiency and heat flux for steady state problems are derived using the one-dimensional Differential Transform Method (1D DTM). The obtained results from 1D DTM are compared with the exact solutions to verify the accuracy of the proposed method. The results reveal that the 1D DTM can achieve suitable results in predicting the solutions of these problems. The effects of some physical parameters such as the thermo-geometric fin parameter and thermal conductivity gradient, on temperature distribution are illustrated and explained. Also, we apply the two-dimensional Differential Transform Method (2D DTM) to models describing transient heat transfer in longitudinal fins. Furthermore, conservation laws for transient heat conduction equations are derived using the direct method and the multiplier method, and finally we find Lie point symmetries associated with the conserved vectors.

Faculty of Science School of Animal ,Plant and Enviromental Sciences 9707660j McConnachie@ukzn.ac.za / Characteristics comprising an energy budget of Pseudocordylus melanotus melanotus were investigated in terms of limiting factors for the lizard’s distribution, and included measures of thermal biology, metabolism and digestive physiology. Pseudocordylus m. melanotus is rupicolous, is limited to the temperate parts of southern Africa and exhibits adaptations to these environments. The distribution of the lizard was modelled using two different climate envelope modelling techniques, which are discussed in terms of the energy budget and factors limiting the distribution of the lizard. Pseudocordylus m. melanotus exhibits wide thermal tolerances. It can withstand body temperatures (Tb) below freezing, but freezing of body water, which occurs at ca. -5 ºC, is lethal. The lower critical minimum temperature was a surprisingly high measure for an apparently cold-adapted lizard. In the laboratory, the selected body temperature (Tsel) was ca. 30 ºC. In the wild, lizards thermoregulate by shuttling between hot and cold microclimates, modifying body postures and regulating activity times, and select Tbs of ca. 29 ºC in summer and ca. 26 ºC in winter. Energy expenditure was measured over a range of temperatures. MR increases significantly with increasing temperature. Body mass and metabolic rate (MR) were significantly related at 30 ºC only. The lack of significance at other temperatures can be ascribed to the small range of body mass over which measures were made. Energy gain in P. m. melanotus was quantified in terms of prey capture rates and by measuring aspects of digestive physiology. Prey capture attempts were 35 % successful and occurred ca. every 2 h 30 min in the field. Lizards consumed a variety of arthropods, but mainly ate beetles. Digestive rate and appetite increased significantly with increasing temperature. Apparent digestive efficiency (ca. 94 %) and apparent assimilation efficiency (ca. 87.2 %) were not affected by temperature. iii Two energy budgets were calculated; one based mainly on laboratory measures and the other based on the thermal profile of lizard body temperature measured in the field. The laboratory energy budget was approximately half that of the field energy budget. The field energy budget, however, provided a more realistic view of energy expenditure since it covered almost the entire thermal range experienced by lizards. Between 592.53 kJ (field energy budget) and 940.06 kJ (laboratory energy budget) per year is required for a standard 30 g P. m. melanotus to remain in energy balance. This means that lizards need to consume between 73.55 and 116.69 g of mealworms per year, which equates to ca. 740 to 1200 average mealworms. Any energy gained over and above these requirements can be allocated to growth, reproduction and storage. In terms of the lizard’s distribution, it will be excluded from areas where the available thermal environment and prey abundance do not allow the lizard to maintain a positive energy balance. The lizard is apparently at the cold limit of its range, so predicted climate change in southern Africa is unlikely to have a significant effect on the distribution of the lizard. Suitable crevices are essential to the lizard’s survival, particularly during periods of extreme cold when lizards may experience Tbs where they are incapacitated, or effectively ‘comatose’, while in retreats.

South Africa is economically vulnerable to climate change because its economy is powered by electricity generated from coal fired power stations. There is a need to reduce the reliance on fossil fuel energy not only because of greenhouse gas emissions but also energy security. Bamboo is touted as a renewable energy source, however, like other woody biomass material, it has poor physicochemical properties and low energy densities. Therefore, the bamboo samples utilized in this study were subjected to thermal pre-treatment methods to improve on their combustion and physicochemical properties. Bamboo samples of 1, 3 and 4+ years old were subjected to torrefaction at 250°C and 280°C as well as low temperature carbonisation at 350°C and 400°C. A standard HGI method was modified during the course of this research for studying the grindability of the raw and treated bamboo material. The fuel properties and combustibility of these raw and thermally treated bamboo materials were then studied using thermogravimetric analysis. The raw bamboo samples exhibited a CV ranging from 17 MJ/kg to 18 MJ/kg, whereas the torrefied samples and the carbonised samples had a CV ranging from 25 MJ/kg to 28 MJ/kg and 28 MJ/kg to 30 MJ/kg, respectively. The 4 year old bamboo carbonised at 400°C had the highest CV of 30.24 MJ/kg. The CV improvement occurred as a result of molecular modification observed through an increase in fixed carbon content from 16 to 74%. The energy yields ranging from 48 to 74% were achieved for the torrefied samples and 44 to 54% for the low temperature carbonised samples, depending on the age of the bamboo sample. At torrefaction temperatures tested, the 4 year old bamboo had the highest mass and energy yield, whereas at carbonisation temperatures, 3 year old bamboo had the highest. The number of differential thermogravimetric peaks was observed to decrease from 2 to 1 as the thermal treatment temperature increased to a carbonisation range (350-400) °C. This can be attributed to the less VM content in the carbonised samples. The raw bamboo and thermally treated bamboo had higher reactivity, lower ignition and burnout temperatures compared to that for coal. Blending of coal with bamboo (raw and thermally treated) appeared to increase the reactivity and lower the ignition temperature during co-firing. The activation energies of the individual fuels ranged from 56 to 289 kJ/mol, using the Ozawa model. Bamboo samples carbonised at 400°C had the highest activation energy, irrespective of age. The activation energy was also the highest when co-firing a blend with the highest proportion of coal. Based on the co-firing tests undertaken in the TG analyser in which a percentage of coal is blended with various proportions of raw and thermally treated bamboo, the results showed that as the percentage of coal in the blend increases there is less interaction or influence of biomass. The role of biomass is to aid with ignition of devolatilization in the coal at lower temperatures. At the carbonisation stage, biomass behave more like coal in principle. It was confirmed in this study that in terms of combustibility, the torrefied bamboo samples had a greater capacity to provide lower ignition and burnout temperatures over the low carbonised bamboo samples utilized, and this might support its application as a source of fuel in an industrial burning combustor. The carbonised 4 year old bamboo appears to be the preferred alternative source fuel to be fired solely in an existing pulverised boiler in South Africa or co-fired with coal due to the carbonised bamboo samples exhibiting the higher CV and more coal-like combustion profile.

This work is a preliminary attempt to study the effect between thermal shock and abrasive wear in WC-Co alloys. This was done by evaluating the thermal shock resistance of a WC-12wt%Co mining grade as a function of temperature, number of thermal shock cycles and making comparisons between the abrasive wear responses of samples subjected to thermal shock and samples not subjected to thermal shock. A furnace was designed for the thermal shock treatments. Abrasive wear tests were performed on a 2-body sliding wear apparatus using 80-grit SiC abrasive paper as a counter-face. Stereo and electron microscopy as well as microprobe techniques were used to analyse the effects of thermal shock. It is confirmed that thermal shock has a negative effect on the wear rate of WC-12wt%Co. The results showed an initial high mass loss rate during abrasive wear testing, which increased with increasing temperature and a decrease in wear rate with time until the wear rates converged for all samples. The surface analysis after thermal shock indicated voids on and below the surface, stained surfaces, a thin oxide layer and the possibility of WC decarburization which accelerated the wear response.

Orientador: Clóvis Augusto Ribeiro / Banca: Adelino Vieira de Godói Netto / Banca: Mirabel Vieira Cerqueira / Resumo: Aduto (do latin Adductus, "atraidos") é o produto de uma adição direta de duas ou mais moléculas distintas, resultando em um produto de reação simples contendo todos os átomos de todos os componentes, com formação de duas ligações químicas e uma redução na multiplicidade da ligação em pelo menos um dos reagentes. Assim, aduto é uma nova espécie química resultante da união direta de moléculas individuais. A meglumina é um carboidrato que se caracteriza pela sua habilidade em formar adutos altamente solúveis em meio aquoso com ácidos carboxílicos. A indústria farmacêutica foi pioneira em explorar essa propriedade, aplicando-a no aperfeiçoamento de medicamentos já existentes. Diante desse contexto, os ácidos carboxílicos envolvidos na formação de adutos com a meglumina apresentam propriedades farmacológicas, mais especificadamente, pertencem à classe dos anti-inflamatórios não esteroidais (AINEs). Com relação à elucidação estrutural dessas espécies, um único trabalho é descrito na literatura o qual contempla o arranjo cristalino da flunixina-meglumina, primeiro aduto dessa classe a ser comercializado. Neste trabalho a flunixina-meglumina e o diclofenaco-meglumina, este último preparado como proposta do estudo, foram caracterizados a partir das técnicas Espectroscopia de Absorção na Região do Infravermelho (IV) e Ressonância Magnética Nuclear (RMN). O comportamento térmico da flunixina-meglumina e do diclofenaco-meglumina no estado sólido foi avaliado mediante as técnicas termoanalíticas Termogravimetria e Termogravimetria Derivada (TG/DTG); Termogravimetria e Análise Térmica Diferencial Simultânea (TG-DTA) e Calorimetria Exploratória Diferencial (DSC). Foi evidenciado que após a temperatura de fusão das respectivas amostras cristalinas, ocorre a formação de um material com comportamento polimérico sugerindo que os adutos... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: An adduct (from the Latin adductus, "drawn toward") is a product of a direct addition of two or more distinct molecules, resulting in a single reaction product containing all atoms of all components, with formation of two chemical bonds and a net reduction in bond multiplicity in at least one of the reactants.Thus, an adduct is a new chemical specie that results from the direct union of individual molecules. Meglumine is a carbohidrate characterized by its capability to form soluble adducts in aquous solutions with carboxilic acids. Pharmaceuticals industry was the first to explore this property, with application to enhance drugs that already exists. In this context, carboxylic acids related to adducts formation with meglumine present pharmacological properties and are included in the class of nonsteroidal anti-inflamatory drugs (NSAIDs). Actually, it is not well understood the structural and chemical characteristics about adducts formed by association of meglumine and carboxylic acids. Only one work in the literature describes the cristaline sctructure formed by flunixin-meglumine adducts, the first compound in this class to go to market. In this work, two adducts (flunixin-meglumine and diclofenac-meglumine) were characterized by Infrared Absortion Spectroscopy (IR) and Nuclear Magnetic Resonance (NMR). Results sugest that the adduct formation of carboxylic acid-meglumine occurs by deprotonation of carboxylic acid and protonation of meglumine. Both adducts in solid state studied in this work were analyzed by Thermogravimetry - Differential Thermal Analysis (TG-DTA) and Differential Scanning Calorimetry (DSC). The results for DSC curves presented two cristaline forms for both adducts. Besides, it was noted that after the melting temperature of the respectives cristalines compounds, they present an self-assembly process wich leads to supramolecular polymers... (Complete abstract click electronic access below) / Mestre

Thesis submitted in fulfilment of the requirements for the degree Master of Technology: Chemistry in the Faculty of Applied Science at the CAPE PENINSULA UNIVERSITY OF TECHNOLOGY 2014 / Crystal engineering based upon acid: base compounds have been studied in this thesis. Selected phenolic acids such as: vanillic acid (VA), phenylacetic acid (PAA), 4-hydroxyphenylacetic acid (HPAA), 3-chloro-4-hydroxyphenylacetic acid (CHPAA), caffeic acid (CFA), p-coumaric acid (pCA), trans-ferulic acid (tFER), 2-phenylpropionic acid (PPA) and 2-phenylbutyric acid (PBA) were the main compounds investigated. These phenolic acids have formed co-crystals/co-crystal hydrates, salts/salt hydrates and hybrid salt-co-crystals with acridine (ACRI), caffeine (CAF), cinchonidine (CIND), isonicotinamide (INM), isonicotinic acid (INA), nicotinamide (NAM), quinidine (QUID), quinine (QUIN), theobromine (THBR), theophylline (THPH) and urea (U). The two racemic compounds 2-phenylpropionic acid (PPA) and 2-phenylbutyric acid (PBA) were used to study chiral discrimination leading to the understanding of separation enantiomers. Compounds were prepared in different solvents (alcohols, ketone and distilled water) to investigate the relationship between solvents used and the crystalline product obtained. (If there is any effect on the crystalline compound obtained by changing the solvent). The structures were elucidated using single crystal X-ray diffraction. Ground products of obtained compounds were characterized by powder X-ray diffraction (PXRD). Thermal analyses like thermogravimetry (TG), differential scanning calorimetry (DSC) and hot stage microscopy (HSM) were used for the determination of thermal character of the new compounds. IR was also performed to characterize the new compounds. Non-isothermal TG was utilised to obtain kinetic parameters for the water and the methanol release in (pCA−)(QUIN+)•pCA•MeOH•H2O. A selective experiment was done in which quinidine and quinine were used to compete between selected phenolic acids (PAA and HPAA). viii The comparison of the crystal structures determined showed that, changing the phenolic acid while using the same co-crystal former has a significant effect on the type of compounds obtained. The obtained crystal structures were either co-crystal/co-crystal hydrates, salts/salt hydrates or hybrid salt-co-crystals which formed network via means of supramolecular interactions.