The University of KwaZulu-Natal (UKZN) Phoenix Hybrid Sounding Rocket Programme was established in 2010. The programme’s main objective is to develop a sounding rocket launch capability for the African scientific community, which currently lacks the ability to fly research payloads to the upper atmosphere. In this dissertation, UKZN’s in-house Hybrid Rocket Performance Simulator (HYROPS) software is used to improve the design of the Phoenix-2A vehicle, which is intended to deliver a 5 kg instrumentation payload to an apogee altitude of 100 km. As a benchmarking exercise, HYROPS was first validated by modelling the performance of existing sub-orbital sounding rockets similar in apogee to Phoenix-2A. The software was found to approximate the performance of the published flight data within 10%. A generic methodology was then proposed for applying HYROPS to the design of hybrid propellant sounding rockets. An initial vehicle configuration was developed and formed the base design on which parametric trade studies were conducted. The performance sensitivity for varying propulsion and aerodynamic parameters was investigated. The selection of parameters was based on improving performance, minimising cost, safety and ease of manufacturability. The purpose of these simulations was to form a foundation for the development of the Phoenix-2A vehicle as well as other large-scale hybrid rockets. Design chamber pressure, oxidiser-to-fuel ratio, nozzle design altitude, and fin geometry were some of the parameters investigated. The change in the rocket’s propellant mass fraction was the parameter which was found to have the largest effect on performance. The fin and oxidiser tank geometries were designed to avoid fin flutter and buckling respectively. The oxidiser mass flux was kept below 650 kg/m2s and the pressure drop across the injector relative to the chamber pressure was maintained above 15% to mitigate the presence of combustion instability. The trade studies resulted in an improved design of the Phoenix-2A rocket. The propellant mass of the final vehicle was 30 kg less than the initial conceptual design and the overall mass was reduced by 25 kg. The Phoenix-2A vehicle was 12 m in length with a total mass of 1006 kg. The fuel grain length of Phoenix-2A was 1.27 m which is approximately 3 times that of Phoenix-1A. The benefit of aluminised paraffin wax as a fuel was also investigated. The results indicated that more inert mass can be delivered to the target apogee of 100 km when using a 40% aluminised paraffin wax. / M.Sc.Eng. University of KwaZulu-Natal, Durban 2013.

Nitrocellulose is the main component in many types of ammunition, propellants and explosives. The principles of production for nitrocellulose have not changed much since the 19th century when it started being industrially produced for this purpose. The character of the nitrocellulose has a large effect on the end products abilities. The aim of this study was to develop a method that would be able to characterise and distinguish between nitrocellulose from different manufacturers to be able to relate the character of the nitrocellulose to the properties of ammunition, propellants and explosives. Samples were dissolved in acetone and analysed by GC/MS and data were then analysed by multivariable statistics. FTIR was also used to characterise the nitrocellulose. Results from both methods showed very small differences when chromatograms and spectra were analysed. This study shows that GC/MS and FTIR are not suitable for this type of characterisation. The differences between the data were not sufficient to be able to separate the samples from each other. / Nitrocellulosa är den viktigaste komponenten i många typer av ammunition, drivmedel och sprängämnen. Principerna för produktionen av nitrocellulosa har inte förändrats mycket sedan det börjades produceras industriellt för detta ändamål på 1800 talet. Karaktären av nitrocellulosa har en stor inverkan på slutproduktens egenskaper. Syftet med denna studie var att utveckla en metod som skulle kunna karaktärisera och skilja mellan nitrocellulosa från olika tillverkare för att kunna relatera karaktären av nitrocellulosa till egenskaperna hos ammunition, drivmedel och sprängämnen. Proverna löstes i aceton och analyserades med GC/MS och data analyserades med multivariabel statistik. FTIR användes också för att karakterisera nitrocellulosan. Resultaten för båda proverna visade mycket små skillnader när kromatogram och spektra analyserades. Denna studie visar att GC/MS och FTIR inte är lämpliga för denna typ av karaktärisering. Skillnaderna i data var inte tillräckliga för att kunna skilja proverna från varandra.

Le refroidissement actif par endocarburant permet d’assurer la tenue thermique d’un superstatoréacteur pour le vol hypersonique. Néanmoins, l’utilisation de cette technologie de refroidissement passe par la maitrise du couplage combustion – pyrolyse, qui fait de la définition d’une stratégie de contrôle du moteur un véritable défi. Une étude expérimentale a été réalisée afin d’analyser l’effet du paramètre de commande principal, le débit de combustible, sur des paramètres de sorties pertinents, à l’aide d’un dispositif de test spécifiquement conçu pour appréhender le couplage combustion – pyrolyse. Ceci a permis d’étudier la dynamique d’un circuit régénératif par rapport à ce paramètre de commande. Une étude cinétique paramétrique sur la pyrolyse du carburant a été conduite en parallèle de celle expérimentale afin d’affiner l’analyse et améliorer l’interprétation des expériences. La décomposition du carburant utilisé pour les tests (éthylène) a été prise en compte grâce à un mécanisme cinétique détaillé (153 espèces, 1185 réactions chimiques). / Regenerative cooling is a well-known cooling technique, suitable to ensure scramjets thermal protection. The development of regeneratively cooled engines using an endothermic propellant is a challenging task, especially because of the strong coupling between fuel decomposition and combustion, which makes the definition of an engine regulation strategy very hard. An experimental study, aiming at identifying the effect of fuel mass flow rate variations on a fuel cooled-combustor in terms of system dynamics has been carried out. A remotely controlled fuel-cooled combustor, designed by means of CDF calculations and suitable for the experimental analysis of combustion-pyrolysis coupling, has been used. In order to improve tests results analysis, a parametric study to characterize fuel decomposition has also been realized. The pyrolysis has been modeled by using a detailed kinetic mechanism (153 species, 1185 chemical reactions).

L´objectif du travail présenté dans ce manuscrit consiste à conserver les bonnes propriétés mécaniques du poly(butadiène) dihydroxytéléchélique (PBHT) tout en améliorant sa stabilité. Un des principaux verrous techniques de cette approche réside dans le fait que les doubles liaisons responsables la flexibilité du matériau sont également la cause de son vieillissement par oxydation. Les solutions proposées reposent sur l´utilisation de la métathèse comme outils de synthèse de polymères insaturés. Deux grandes voix de synthèse ont été étudiées : la polymérisation par ouverture de cycle via métathèse (ROMP) ainsi que la dépolymerisation fonctionnalisante (ADMET). Ces deux approches bien que prometteuses n’ont pas permis de sortir de la relation ciseau existante entre flexibilité et stabilité. Finalement, une solution basée sur le mélange entre deux polymères dihydroxytéléchéliques de basse température de transition vitreuse – poly(butadiene) et poly(isobutylene) a permis de répondre dans une certaine mesure aux cahier des charges. En parallèle a ces parties synthèses, une étude physique des relations structure-propriétés visant à améliorer la stabilité des oligomères a été apporté par mesure rhéologique du temps critique de réticulation. / The work reported in the following document is aiming at maintaining the good mechanical properties of diHydroxyTelechelic PolyButadiene HTPB while improving its stability. The major challenge of this approach is that the unsaturations responsible for the outstanding flexibility of the material are also rather sensitive to oxidation. The solutions presented in this study are based on the use of metathesis reactions as a tool for the design of new difunctional unsaturated oligomers. Two functionalization techniques have been investigated, on the one hand, the Ring Opening Methathesis Polymerisation (ROMP) and, on the other hand, the depolymerisation via Acyclic Diene METathesis (ADMET). Although promising, the latters proved to fall into the vicious circle consisting in simultaneously increasing the stability while losing the flexibility. Finally, a blending concept based on the mixture of two dihydroxytelechelic polymers, namely, poly(isobutylene) and poly(butadiene), could enable us to achieve our initial goal. In addition to the chapters focusing on polymer chemistry and synthesis, a physical study of the parameters influencing the aging of unsaturated oligomers have been set-up and the properties relationship using measurements of the critical time.

Physical mechanism for high frequency instability in cryogenic engines at low hydrogen injection temperature has been a subject of debate for long time. Experimental and early developmental studies revealed no instabilities and it was only much later when liquid hydrogen at lower initial temperature (~50 to 100 K) was injected into the combustion chamber that instabilities were detected. From the compilations of the experimental data related to the instability of cryogenic engines by Hulka and Hutt, it was found that the instability was strongly connected to the temperature of hydrogen. Experiments conducted with hydrogen temperature ramping from a higher value to lower values indicated that the temperatures in excess of 90 K favor stability under most practical operating conditions. Even though this has been known for over forty years, there has been no clear and simple explanation for this. Many physical mechanisms have been hypothesized to explain how temperature ramping causes instability, but all appear to have limited range of applicability. Current understanding of cryogenic engine combustion instability has been achieved through a combination of experimental investigation and approximate analytical models as well as CFD tools. Various researchers have tried to link the low hydrogen injection temperature combustion instability phenomena with various potential mechanisms for combustion instability. They involve coupling of combustion acoustics with atomization, vaporization, mixing, chemical kinetics or any combination of these processes. Various studies related to the effect of recess, injector hydrodynamics, acoustic damping of gas liquid scheme injectors and effect of drop size distribution on the stability characteristics of cryogenic engines were compiled in the thesis. Several researchers examined fuel droplet vaporization as the rate controlling mechanism. Recently a new method for the evaluation of stability characteristics of the engine using model chamber were proposed by Russians and this is based on mixing as the rate controlling mechanism. Pros and cons of this method were discussed. Some people examined the combustion instability of rocket engines based on chemistry dynamics. A considerable amount of analytical and numerical studies were carried out by various researchers for finding out the cause of combustion instability. Because of the limitations of their analysis, they could not successfully explain the cause of combustion instability at low hydrogen injection temperature. A compilation of previous numerical studies were carried out. A number of researchers have applied CFD in the study of combustion instabilities in liquid propellant rocket engines. In the present thesis, a theoretical model has been developed based on the vaporization of droplets to predict the stability characteristics of the engine. The proposed concept focuses on three dimensional simulation of combustion instability for giving some meaningful explanations for the experimental work presented in the literature. In the present study the pressure wave corresponding to the transverse modes were superimposed on a three dimensional steady state operating conditions. Steady state parameters were obtained from the three dimensional combustion modeling. The conservation equations for mass, momentum and energy are non dimensionalized for facilitating the order of magnitude analysis. In order to do the stability analysis, variables are represented as the sum of their steady values and deviation from the steady state. A harmonic time dependence is assumed for the perturbations. For the transverse mode of oscillations independent variables of the zeroth order equations are r and θ only and the dependant variables are not functions of the axial distance. The axial dependence comes only through the first order equations. In this analysis, the wave motion in the combustion chamber is assumed to be linear, confining the nonlinearity to the vaporization process only. The reason behind making this assumption is that the vaporization process is the major mechanism driving the instability. Vaporization histories of liquid oxygen drops in a combustor with superimposed transverse oscillations were computed and stability characteristics of the engine were estimated. The stability characteristics of the engine are accessed from the solutions of first order equations. Effects of various parameters like droplet diameter, hydrogen injection temperature and hydrogen injection area on the stability characteristics of cryogenic engines are studied. A comparison of predicted and published experimental results was made which showed general agreement between experiment and computation. The present study and experimental results show clearly that hydrogen injection velocity is the critical parameter for instability rather than hydrogen injection temperature. What has happened in actual experiments when hydrogen injection temperature is varied is an effective alteration of the injection velocity that leads to the situation of instability. For higher relative velocity between hydrogen and liquid oxygen, the response of the vaporization rate in the presence of pressure wave is minimum compared to lower relative velocity. Due to this cryogenic engines will go to unstable mode at lower relative velocity.

<div>Laser-absorption spectroscopy (LAS) is widely used for providing non-intrusive and quantitative measurements of gas properties (such as temperature and absorbing species mole fraction) in combustion environments. However, challenges may arise from the line-of-sight nature of LAS diagnostics, which can limit their spatial resolution. Further, time-resolution of such techniques as scanned direct-absorption or wavelength-modulation spectroscopy is limited by the scanning speed of the laser and the optical bandwidth is often limited by a combination of a laser's intrinsic tunability and its scanning speed. The work presented in this dissertation investigated how recent advancements in mid-IR camera technology and lasers can be leveraged to expand the spatial, temporal, and spectral measurement capabilities of LAS diagnostics. Novel laser-absorption imaging and ultrafast laser-absorption spectroscopy diagnostics are presented in this dissertation. In addition, the high-pressure combustion chamber (HPCC) and high-pressure shock tube (HPST) were designed and built to enable the study of, among others, energetic material combustion, spectroscopy, non-equilibrium and chemistry using optical diagnostics.<br></div><div><br></div>

<div>The new technique of Vibration-Assisted 3D Printing (VAP) offers significant potential for leveraging the geometric flexibility of additive manufacturing (AM) into the realm of solid energetics. The first part of this work compares the print capabilities of a custom-made VAP printer to those of an established commercial direct-write printer using a polymer clay. Characterization tests were conducted and a variety of other shapes were printed comparing the two methods in their turning quality, feature resolution, unsupported overhang angle, negative space feature construction, and less-than-fully-dense self-supported 3D lattices. The porosity and regularity of the printed lattices were characterized using X-ray microtomography (MicroCT) scans. The quality of the shapes was compared using statistical methods and a MATLAB edge-finding code. The results show that the VAP printer can manufacture parts of superior resolution than the commercial printer, due to its ability to extrude highly viscous material through a smaller nozzle diameter. The VAP print speeds were also found to be as high as twenty times higher than those of the direct write printer.</div><div>Following up on this work, a second study explored the possibility of modifying grain geometry through variation of printed infill design using an ammonium perchlorate composite propellant (APCP). In the propellant formulation, a polymer that cures under ultra-violet (UV) light was used instead of the more common hydroxyl-terminated polybutadiene (HTPB). Although this formulation is a less-effective fuel than HTPB, its use enables layer-by-layer curing for improved structural strength during printing. Using VAP, cylindrical propellant charges were prepared using a gyroidal infill design with a range of internal porosities (infill amounts). Some additional propellant grains were prepared with both vertical and concentric layering of different infill amounts. These grains were then burned beginning at atmospheric pressure in a constant-volume Parr cell to measure the resulting pressure output. Analysis of the pressure trace data shows that a less-dense infill increases the maximum pressurization rate, due to the presence of small voids spaced roughly uniformly throughout the grain that increase the burning surface area. We show that additive manufacturing-based propellant grain modification can be used to tailor the pressure-time trace through adjustment of the number and size of small voids. Specifically, this study shows that, using a graded functional geometry, the duration of gas generation can be controlled. This work represents a preliminary effort to explore the possibilities to propellant</div><div>12</div><div>manufacture offered by additive manufacturing and to begin to address the challenges inherent in making it practical.</div>

<div>As small satellites are increasingly used in the space industry, creative solutions for the use of their limited volume will be required. Conformal tanks are one idea to better make use of this volume. These tanks are non-traditionally shaped and non-axisymmetric. Because slosh can have detrimental effects on a spacecraft, it should be understood. However, slosh in these more complicated geometries has not been thoroughly investigated in the past.</div><div><br></div><div>This research looks at slosh within six geometries, five of which are conformal tanks. These geometries are evaluated in both an experiment and using CFD simulations. It was found that the total slosh motion appears to be the sum of slosh behavior along each dimension. Slosh along a line of symmetry will have center of mass movement that stays along that line. Slosh off the line of symmetry will deviate from that line unless slosh frequency is the same in each direction.</div>

The thermal-oxidative degradation of a crosslinked hydroxy-terminated polybutadiene (HTPB)/cycloaliphatic diisocyanate (H12MDI) based polymer, which is commonly used as a polymeric binder in propellants, is investigated at temperatures from 95°C to 125°C with the aim of estimating the lifetime of the material in storage conditions (20°C) using the Arrhenius approach. Furthermore, the effect of antioxidants and to a lesser extent plasticizer on the degradation process was also studied. Diffusion-limited oxidation (DLO) was theoretically modelled and DLO conditions were estimated by gathering oxygen permeability and consumption data from similar studies. It was concluded that DLO-effects might be present at the highest experiment temperature (125°C) depending on the actual properties of the material investigated. The mechanical degradation was monitored by conducting tensile tests in a DMA apparatus and photographs using a microscope was taken to examine potential DLO effects. The degradation process of the stabilized polymer (with antioxidant) did not showcase Arrhenius behaviour, which was confirmed by the failure to construct a satisfactory mastercurve. This was most likely due to loss of antioxidants, resulting in autocatalytic oxidation(acceleration of the oxidation process). However, the induction period of the stabilized polymer showcased Arrhenius behaviour in the temperature region 95-125°C with an ~E_a = 90 kJ/mol. If the activation energy E_a is assumed to remain constant, the lifetime at ambient temperature (20°C) is predicted to be approximately 176 Years for a 2mm thick sample. However, this is probably an overestimation since curvature in the Arrhenius plot has been observed for many rubber materials in the lower temperature region. Assuming the E_a drops from ~90 kJ/mol to~71 kJ/mol, a more conservative lifetime prediction of 58 Years was estimated.

<p>A variety of methods have been developed to enhance solid propellant burning rates, including adjusting oxidizer particle size, modifying metal additives, tailoring the propellant core geometry, and adding catalysts or wires. Fully consumable reactive wires embedded in propellant have been used to increase the burning rate by increasing the surface area; however, the manufacture of propellant grains and the observation of geometric effects with reactive components has been restricted by traditional manufacturing and viewing methods. In this work, a printable reactive filament was developed that is tailorable to a number of use cases spanning reactive fibers to photosensitive igniters. The filament employs aluminum fuel within a printable polyvinylidene fluoride matrix that can be tailored to a desired burning rate through stoichiometry or aluminum fuel configuration such as particle size and modified aluminum composites. The material is printable with fused filament fabrication, enabling access to more complex geometries such as spirals and branches that are inaccessible to traditionally cast reactive materials. However, additively manufacturing the reactive fluoropolymer and propellant together comes attendant with many challenges given the significantly different physical properties, particularly regarding adhesion. To circumvent the challenges posed by multiple printing techniques required for such dissimilar materials, the reactive fluoropolymer was included within a solid propellant carrier matrix as small fibers. The fibers were varied in aspect ratio (AR) and orientation, with aspect ratios greater than one exhibiting a self-alignment behavior in concordance with the prescribed extrusion direction. The effective burning rate of the propellant was improved nearly twofold with 10 wt.% reactive fibers with an AR of 7 and vertical orientation. </p> <p>The reactive wires and fibers in propellant proved difficult to image in realistic sample designs, given that traditional visible imaging techniques restrict the location and dimensions of the reactive wire due to the necessity of an intrusive window next to the wire, a single-view dynamic X-ray imaging technique was employed to analyze the evolution of the internal burning profile of propellant cast with embedded additively manufacture reactive components. To image complex branching geometries and propellant with multiple reactive components stacked within the same line of sight, the dynamic X-ray imaging technique was expanded to two views. Topographic reconstructions of propellants with multiple reactive fibers showed the evolution of the burning surface enhanced by the geometric effects caused by the faster burning fibers. These dual-view reconstructions provide a method for accurate quantitative analysis of volumetric burning rates that can improve the accessibility and viability of novel propellant grain designs.</p>