Tesi sul tema "Composite propellant"

Much Research on composite solid propellants has been performed over the past few decades and much progress has been made, yet many of the fundamental processes are still unknown, and the development of new propellants remains highly empirical. Ways to enhance the performance of solid propellants for rocket and other applications continue to be explored experimentally, including the effects of various additives and the impact of fuel and oxidizer particle sizes on burning behavior. One established method to measure the burning rate of composite propellant mixtures in a controlled laboratory setting is to use a constant-volume pressure vessel, or strand burner. To provide high-pressure burn rate data at pressures up to 360 atm, the authors have installed, characterized and improved a strand burner facility at the University of Central Florida. Details on the facility and its improvements, the measurement procedures, and the data reduction and interpretation are presented. Two common HTPB/AP propellant mixtures were tested in the original strand burner. The resulting burn rates were compared to data from the literature with good agreement, thus validating the facility and related test techniques, the data acquisition, data reduction and interpretation. After more than 380 successful recordings, an upgraded version of the strand burner, was added to the facility. The details of Strand Burner II, its improvements over Strand Burner I, and its characterization study are presented.
M.S.
Department of Mechanical, Materials and Aerospace Engineering
Engineering and Computer Science
Mechanical Engineering MSME

This project was started in the interest of supplementing existing data on additives to composite solid propellants. The study on the addition of iron and aluminum nanoparticles to composite AP/HTPB propellants was conducted at the Combustion and Energy Systems Laboratory at RPI in the new strand-burner experiment setup. For this study, a large literature review was conducted on history of solid propellant combustion modeling and the empirical results of tests on binders, plasticizers, AP particle size, and additives.

The study focused on the addition of nano-scale aluminum and iron in small concentrations to AP/HTPB solid propellants with an average AP particle size of 200 microns. Replacing 1% of the propellant's AP with 40-60 nm aluminum particles produced no change in combustive behavior. The addition of 1% 60-80 nm iron particles produced a significant increase in burn rate, although the increase was lesser at higher pressures. These results are summarized in Table 2. The increase in the burn rate at all pressures due to the addition of iron nanoparticles warranted further study on the effect of concentration of iron. Tests conducted at 10 atm showed that the mean regression rate varied with iron concentration, peaking at 1% and 3%. Regardless of the iron concentration, the regression rate was higher than the baseline AP/HTPB propellants. These results are summarized in Table 3.

Solid rocket motors consist of a thin metallic or composite shell filled with a soft rubbery propellant. Such motors are vulnerable and prone to buckling due to sudden external pressures produced by nearby detonation. The stability conditions of rocket motors subjected toaxisymmetric, external pressure loading are examined. The outer cases of motors are considered as isotropic (metallic) or anisotropic (composite), thin and high-strength shells, which are the main structures of interest in the stability analyses. The inner, low-strength elastic cores are modeled as linear and nonlinear elastic foundations. A general, refined, Sanders' nonlinear shell theory, which accounts for geometric nonlinearity in the form of von Karman type of nonlinear strain-displacement relations, is used to model thin-walled, laminated,composite cylindrical shells. The first order shear deformable concept is adopted in the analyses to include the transverse shear flexibility of composites. A winkler-type of linear and nonlinear elastic foundation is applied to model the internal foundations. Pasternak-foundation constants are also chosen tomodify the proposed elastic foundation model for the purpose of shear interactions. A set of displacement-based finite element codes have been formulated to determine critical buckling loads and mode shapes. The effect of initial imperfections on the structural responses are also incorporated in the formulations. A variety of numerical examples are investigated to demonstrate the validity and efficiency of the purposed theory under various boundary condiitions and loading cases. First, linear eigenvalue analysis is used to examine approximate buckling loads and buckling modes as well as symmetric conditions. An iterative solution procedure, either Newton-Raphson or Riks-Wempner method is employed to trace the nonlinear equilibrium paths for the cases of stress, buckling and post-buckling analyses. Both ring and shell-type models are applied for the structural analyses with different internal elastic foundations and initial imperfections.
Ph. D.

The purpose of this study is to examine the burning behaviour of composite solid propellants (CSP) in the presence of nanoscale, heterogenous catalysts. The study targets the decomposition of am- monium perchlorate (AP) as a key component in the burning profile of these propellants, and seeks to identify parameters of AP decomposition reaction that can be affected by catalytic additives. The decomposition behavior of AP was studied in the presence of titanium dioxide nanoparticles in varying configurations, surface conditions, dopants, morphology, and synthesis parameters with the AP crystals. The catalytic nanoparticles were found to enhance the decomposition rate of the ammonium perchlorate, and promote an accelerated burning rate of CSP propellants containing the additives. Furthermore, different configurations were shown to have varying degrees of effec- tiveness in promoting the decomposition behaviour. To study the effect of the catalyst's configuration in the bulk propellant, controlled dispersion con- ditions of the nanoparticle catalysts were created and studied using differential scanning calorime- try, as well as model propellant strand burning. The catalysts were shown to promote the greatest enthalpy of reaction, as well as the highest burn rate, when the AP crystals were recrystalized around the nanoparticle additives. This is in contrast to the lowest enthalpy condition, which cor- responded to catalysts being dispersed upon the AP crystal surface using bio-molecule templates. Additionally, a method of facile, visible light nanoparticle tracking was developed to study the effect of mixing and settling parameters on the nano-catalysts. To accomplish this, the titania nanoparticles were doped with fluorescent europium molecules to track the dispersion of the cat- alysts in the propellant binder. This method was shown to succesfully allow for dispersion and agglomeration monitoring without affecting the catalytic effect of the TiO2 nanoparticles.
M.S.M.S.E.
Masters
Materials Science Engineering
Engineering and Computer Science
Materials Science and Engineering

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.

Aeronautical structures, such as aircraft or missiles, are usually highly sophisticated systems often subjected to random vibration environment. Thus, in various design, development, and production stages, laboratory random vibration testing of sampled solid rocket motors on electromagnetic or hydraulic shakers are routinely performed as an important experiment-oriented quality control strategy. Nevertheless, it is crucial to understand the dynamic structural behavior of these layered viscoelastic cylinders such as solid rocket motors under random vibration tests analytically. In this study, a methodology has been developed to deal with the random vibration of a general class of composite structures with frequency-dependent viscoelastic material properties as represented by the example of solid rocket motors. The method combines the finite element method, structural dynamics, strain energy approach, and random vibration analysis concepts. The method is a more powerful technique capable of treating sophisticated random vibration problems with complicated geometry, nonhomogeneous materials, and frequency-dependent stiffness and damping properties. Before the random vibration analysis could proceed, a microcomputer-based dynamic mechanical analyzer system was used together with time-temperature superposition principle to obtain the frequency-dependent dynamic viscoelastic properties of the solid propellant. The strain energy approach has been used to calculate the frequency-dependent equivalent viscoelastic damping which is in turn judiciously represented by a combination of viscous damping and structural damping to accommodate this frequency dependent material property. Modal analysis data together with half power band width calculated at each natural frequency are highly useful guides in the harmonic analysis to achieve computational efficiency. On one hand, the technique used in this study has a hybrid taste in the sense that it makes use of best features and capabilities of both modal analysis and harmonic analysis to achieve the goal of random vibration analysis in addition to the power of finite element technique. The displacement, acceleration and stress power spectra have been obtained for significant points on the rocket model together with their root mean square values. These data can be used for various analyses, testing, design, and other purposes as discussed in later sections of this study.
Ph. D.

Ces travaux de thèse portent sur le développement d’une loi de comportement viscoélastique non-linéaire pour les propergols solides composites. Une base expérimentale mettant en évidence le comportement à modéliser est construite à l’aide du propergol d’étude. Puis, les origines microscopiques de ce comportement macroscopique sont investiguées, au moyen d’éprouvettes spécialement conçues à cet effet. Les résultats de l’étude montrent que le frottement et la cavitation sont deux mécanismes prépondérants. Les relations mathématiques entre ces micromecanismes et les propriétés mécaniques du matériau sont déterminées par homogénéisation, puis introduites dans un cadre viscoélastique isotrope tridimensionnel. Les paramètres du modèle ainsi obtenu sont identifiés sur la base expérimentale, suite à quoi la loi est capable de restituer la majeure partie des non-linéarités du comportement exprimées sous sollicitations cycliques. Après intégration dans un code de calcul par éléments finis, la loi est finalement validée sur des cas d’application réels. Les résultats montrent qu’une meilleure restitution du comportement du propergol au cours de son cycle de vie permet d’améliorer le dimensionnement des chargements de manière significative
This work describes the development of a viscoelastic nonlinear constitutive law for solid composite propellants. An experimental basis showing the nonlinear behavior expressed by solid propellants is constructed. Then, microscopic sources of this macroscopic behavior are investigated using new samples specifically designed. Results show that friction and cavitation are responsible for the major parts of the nonlinearities. Homogenization is used to determine mathematical relations between these two mechanisms and the mechanical properties of the material. The relations are then integrated in a viscoelastic, isotropic, tridimensional model. Parameters are identified using the experimental basis. The model shows a good ability to reproduce and predict the propellant behavior nonlinearities expressed under cyclic loads. After completion of the development, the model is used into a design method and finite element calculation are performed on real objects. Results validate the new method and show that improving the behavior prediction also improves the design method and generates profits

Les explosifs sont des matériaux qui, bien que potentiellement sensibles, sont conçus pour être stables en conditions normales, ainsi que lors de sollicitations mécaniques, chimiques ou thermiques " faibles ". Pourtant, sous sollicitations mécaniques de faible intensité, comme les impacts basse vitesse, ils peuvent réagir de manière intempestive. Les propergols, et plus particulièrement la butalite, objet de notre étude, présentent ce caractère : on observe des " réactions " pour des vitesses d'impacts inférieures à 100 m.s-1, dont l'origine est probablement liée à l'endommagement microstructural du matériau. Dans ce contexte, le but ultime du CEA Gramat est d'obtenir un outil de prédiction de la vulnérabilité des matériaux énergétiques pour les impacts à basse vitesse de type " tour de chute ". Pour ce faire, il est essentiel de disposer de données sur la morphologie et le comportement (thermo)mécanique macroscopique du matériau considéré, de ses phases constitutives à l'échelle mésoscopique et de ses interfaces. Ainsi l'objectif de la thèse est de déterminer le type et le niveau de(s) endommagement(s) apparaissant(s) dans une " butalite inerte " suite à un impact mécanique dit " à basse vitesse " (i.e., inférieure à 100 m.s-1) réalisé à l'aide d'un dispositif de type tour de chute modifié, associant un suivi par vidéo numérique rapide et une analyse microtomographique ante- et post-essai, en étudiant le ou les phénomènes physiques à l'origine des réactions sous " faibles " sollicitations, leur évolution et leur(s) origine(s) physique(s). Les grains sont modélisés par une loi de comportement purement élastique et la matrice en PBHT est décrite par une loi visco-hyper-élastique (couplage d'une série de Prony et du modèle de Mooney-Rivlin).

Solid composite rocket propellants usually contain ammoniumperchlorate embedded in an elastic polymer binder. The bindercan be based on a liquid prepolymer such as hydroxyl-terminatedpolybutadiene, HTPB, or poly(3-nitratomethyl-3-methyl oxetane,PolyNIMMO. HTPB is today widely used for this purpose whereasPolyNIMMO has not yet found its way to an application. Bothprepolymers can be cured with diisocyanates to formpolyurethane rubber, yielding solid and elastic rocketpropellants. It is essential that the solid propellant has goodmechanical properties to ensure that the rocket will perform asintended. The propellant must also retain its elasticproperties down to the minimum service temperature and thus alow glass transition temperature is important. In fact, themajor cause of failure of solid rocket motors is linked to themechanical properties of the propellants. HTPB has a very lowglass transition temperature but in some applications itstensile strength is insufficient. PolyNIMMO, on the other hand,has too high a glass transition temperature and a suitableplasticizer is needed. The purpose of this work is to increasethe knowledge of the mechanical properties of polymers bystudying how to increase the tensile strength of HTPB and howto decrease the glass transition temperature of PolyNIMMO.

The tensile strength of HTPB was studied by increasing thehard segment content, 1,4-butanediol and 1,4-cyclohexanedimethanol being used as chain extenders. The materials werecrosslinked with either isophorone diisocyanate,1,6-hexamethylene diisocyanate or dicyclohexylmethane4,4'-diisocyanate. The results show that the tensile strengthincrease strongly with the addition of up to two moles of diolper mole HTPB. The highest tensile strength was obtained byusing dicyclohexylmethane 4,4'-diisocyanate and1,4-butanediol.

The depression of the glass transition temperature ofPolyNIMMO was studied by using a new energetic plasticizer,2,2-dinitro-1,3-bis-nitrooxy-propane. Two commercial energeticplasticizers, namely bis(2,2-dinitropropyl) acetal/formal andN-N-butyl-N-(2-nitroxy-etyl)nitramine were used for comparison.2,2-Dinitro-1,3-bis-nitrooxy-propane andN-N-butyl-N-(2-nitroxy-etyl)nitramine were found to interactstrongly with PolyNIMMOand they were thus very effective inlowering the glass transition temperature.Bis(2,2-dinitropropyl) acetal/formal on the other hand was noteffective, and the depression of the glass transitiontemperature in this case was due only to dilution of thesample.

Propellants based on cross-linked Hydroxy Terminated PolyEther (HTPE) binders are being used as alternatives to Hydroxy Terminated PolyButadiene (HTPB) compositions. HTPE propellants have similar mechanical properties to HTPB propellants but they give a less severe response in ‘slow cook-off’ tests for IM compliance. A literature review is presented on the development and properties of HTPE propellants in an attempt to place them in relation to recent trends in Insensitive Munitions. To gain a better understanding of the behaviour of HTPE propellants an HTPE pre-polymer and a range of binder network samples with different NCO/OH equivalence ratios, with and without plasticizer, have been synthesised and characterised by a range of techniques. The thermal decomposition of the HTPE binder network and propellant samples were also studied. Desmodur N-3200 was used as a curing agent and n-BuNENA as an energetic plasticizer. Similar analyses were performed on analogous HTPB pre-polymer and binder network samples and the results were compared with those obtained for the corresponding HTPE samples. Two kinds of HTPE propellant were manufactured containing HTPE pre-polymer, n-BuNENA, 2NDPA and either AP or AP+PSAN as oxidiser. Also HTPB propellant was prepared. Small cook-off test vehicles (SCTV) were filled with HTPE and HTPB propellants and slow cook-off tests were performed. In contrast to HTPB binders, which become harder during slow heating, it was found that the HTPE binders soften under the same conditions. This behaviour is possibly due to chain scission of the soft and hard segments of the HTPE polymer matrix. Thermooxidative processes and reactions of the energetic plasticizer decomposition products are believed to be the responsible for the scission of the polymeric matrix. From the binder characterisation and slow cook-off results it is concluded that there is a relation between the degree of polymeric matrix scission during slow heating and the violence of the response at the point of self ignition. This underlies the main difference between HTPB and HTPE propellants in slow cook-off. While HTPB compositions become harder and more brittle, HTPE propellants become softer and have a lower surface area at the self ignition point.

Propellants based on cross-linked Hydroxy Terminated PolyEther (HTPE) binders are being used as alternatives to Hydroxy Terminated PolyButadiene (HTPB) compositions. HTPE propellants have similar mechanical properties to HTPB propellants but they give a less severe response in ‘slow cook-off’ tests for IM compliance. A literature review is presented on the development and properties of HTPE propellants in an attempt to place them in relation to recent trends in Insensitive Munitions. To gain a better understanding of the behaviour of HTPE propellants an HTPE pre-polymer and a range of binder network samples with different NCO/OH equivalence ratios, with and without plasticizer, have been synthesised and characterised by a range of techniques. The thermal decomposition of the HTPE binder network and propellant samples were also studied. Desmodur N-3200 was used as a curing agent and n-BuNENA as an energetic plasticizer. Similar analyses were performed on analogous HTPB pre-polymer and binder network samples and the results were compared with those obtained for the corresponding HTPE samples. Two kinds of HTPE propellant were manufactured containing HTPE pre-polymer, n-BuNENA, 2NDPA and either AP or AP+PSAN as oxidiser. Also HTPB propellant was prepared. Small cook-off test vehicles (SCTV) were filled with HTPE and HTPB propellants and slow cook-off tests were performed. In contrast to HTPB binders, which become harder during slow heating, it was found that the HTPE binders soften under the same conditions. This behaviour is possibly due to chain scission of the soft and hard segments of the HTPE polymer matrix. Thermooxidative processes and reactions of the energetic plasticizer decomposition products are believed to be the responsible for the scission of the polymeric matrix. From the binder characterisation and slow cook-off results it is concluded that there is a relation between the degree of polymeric matrix scission during slow heating and the violence of the response at the point of self ignition. This underlies the main difference between HTPB and HTPE propellants in slow cook-off. While HTPB compositions become harder and more brittle, HTPE propellants become softer and have a lower surface area at the self ignition point.

Composite propellants are mainly composed of: crystalline oxidizer, metallic fuel, and polymeric binder. Additives, such as plasticizers, catalysts, bonding agents and curing agents may also be incorporated to propellant compositions in small amounts. These ingredients should be mixed rigorously in order to obtain a uniform microstructure throughout the cast propellant profile. The quality of the propellant mixture has to be determined quantitatively to improve the product quality and to reduce costs. In this study, it was aimed to develop an easy, cost effective and rapid test method for determining the optimum mixing conditions for the manufacturing process of solid rocket propellants. An analytical method used in the literature for assessing mixing quality in highly filled polymeric systems is wide-angle x-ray diffractometry (WA-XRD). After finding out the concentration distribution of the components indirectly by WA-XRD, degree of mixing was identified using statistical methods. To accomplish this, series of samples were taken from various locations of the mixing chamber and analyzed by WA-XRD. Degree of mixing calculations based on ratio of intensity arising from aluminum phase over total crystal intensity, and the ratio of intensity arising from ammonium perchlorate phase over total crystal intensity gave satisfactory results. Radial mixing efficiency of planetary mixer was determined, and it was found that mixing at the center was more effective than mixing at the outer regions. Also, by scanning electron microscopy technique (SEM), interactions between binder and solid loading during mixing process were observed. It was seen that polymeric matrix gradually encloses solid particles during mixing.

Orientadores : Sergio Persio Ravagnani, Choyu Otani
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica
Made available in DSpace on 2018-08-14T23:33:08Z (GMT). No. of bitstreams: 1 Libardi_Juliano_D.pdf: 1948644 bytes, checksum: 8e209152ac6e1264f50427fa51a998f2 (MD5) Previous issue date: 2009
Resumo: Os propelentes compósitos à base de polibutadieno líquido hidroxilado (PBLH) utilizados na produção dos motores foguete a propelente sólido (MFPS), desenvolvidos no Instituto de Aeronáutica e Espaço (IAE), podem sofrer alterações em suas propriedades físicas devido ao processo de difusão de plastificantes entre as interfaces das camadas de propelente e de proteção térmica, que reveste a parede interna deste motor. A ocorrência deste fenômeno afeta diretamente a integridade estrutural dos motores e conseqüentemente seu desempenho. O objetivo deste trabalho foi desenvolver um programa computacional, em linguagem FORTRAN, para calcular os coeficientes de difusão a partir das concentrações dos plastificantes dioctilazelato (DOZ), dibutilftalato (DBF) e dioctilftalato (DOP) presentes nas camadas do propelente sólido, liner e borracha isolante, respectivamente. Para a realização dos cálculos computacionais foi adotado o modelo matemático proposto pela segunda Lei de difusão de Fick. O coeficiente de difusão foi obtido por meio da solução da equação não linear deste modelo com auxílio de métodos numéricos iterativos. Os dados de concentração utilizados no software foram obtidos em amostras contendo as interfaces de propelente/liner/borracha envelhecidas a 50°C e a 80°C. Na primeira condição, foi adotado o período de envelhecimento entre 30 a 125 dias após a cura do propelente. As amostras utilizadas nesta etapa foram preparadas com o liner LHNA que é produzido à base do polímero polibutadieno líquido hidroxilado e curado com o tolueno diisocianato. Foi verificado, por meio dos resultados obtidos, que houve pouca variação nos valores das concentrações dos plastificantes ao longo do envelhecimento, indicando que neste período a difusão entre as interfaces estudadas apresentou um estado próximo ao equilíbrio. Neste caso, os coeficientes não foram calculados devido ao modelo adotado executar os cálculos com base nas diferenças de concentração do plastificante na região estudada ao longo do tempo. Na segunda condição pesquisada as amostras foram envelhecidas a 80°C por um período entre 0 e 31 dias após o término da cura do propelente. Neste caso, os corpos de prova foram preparados com dois tipos diferentes de liner: LHNA e LHNT, este último também é produzido à base do polímero PBLH, no entanto, o LHNT é curado com o isoforona diisocianato que promove maior do reticulação do liner. O programa realizou os cálculos com sucesso e os coeficientes obtidos revelaram que a aplicação de um "liner" com maior densidade de ligações cruzadas reduz, como esperado, o processo de difusão dos plastificantes. Os dados experimentais e os simulados pelo programa exibiram bom ajuste entre si, revelando que o modelo aplicado é válido. Para verificar o efeito da difusão dos plastificantes sobre a dureza do propelente foram realizados testes de dureza Shore A em diferentes regiões dos corpos de prova. Alterações nesta propriedade, ao longo do envelhecimento, podem comprometer a integridade estrutural do motor foguete. Os testes foram executados em amostras de propelente envelhecidas a 80°C e a temperatura ambiente por um período máximo de 54 dias após a cura. Para as amostras mantidas à temperatura ambiente foi verificado o aumento dos valores de dureza ao longo de tempo de envelhecimento e para as amostras armazenadas a 80°C os valores diminuíram no mesmo período de análise.
Abstract: The hydroxyl-terminated (HTPB) based solid composite propellant used in the production of solid rocket motors, developed in the Institute of Aeronautics and Space (IAE), can suffer changes of physical properties due to the diffusion process of plasticizers between the interfaces layers of propellant and thermal insulation. The occurrence of this phenomenon affects directly the structural integrity of the rocket motor and consequently its performance. The aim of this work was to develop a computational program, in FORTRAN language, to calculate the diffusion coefficient, from the concentration data, of plasticizers dioctyl azelate (DOZ), dibutyl phthalate (DBF) and dioctyl phthalate (DOP) contained into layers of propellant, liner and insulation rubber, respectively. The mathematical model proposed by Fick's second law of diffusion was used in computational calculus. The diffusion coefficient was obtained by solution of non liner equation of this model which is solved with assistance of iterative numeric methods. The concentration data used by the software were obtained from samples containing the interfaces of propellant/liner/rubber aged at 50°C and 80°C. In the first condition, the aging was executed between 30 and 125 days after the end of cure. From these results was verified that diffusion process practically reached the equilibrium state. In this case, the diffusion coefficients were not calculated once the mathematical model is based on concentration differences of plasticizers over aging. In the second condition, the samples were aged at 80°C between 0 and 31 days after the end of cure. In this case, the samples were prepared with two different types of liners: LHNA and LHNT, which has higher crosslinking density and is also hydroxyl-terminated polybutadiene based, however, the LHNT is cured with isophorone diisocyanate which is responsible for higher crosslinking. The program executed the calculus with success and the results obtained revealed that the diffusion process is reduced by the application of the liner with higher crosslinking density. It was observed good agreement between the experimental and simulated results showing that the model applied is valid. The Shore A tests was achieved to verify the effects of diffusion on hardness of propellant in different regions of the sample. Changes in propellant hardness over the aging may compromise the structural integrity of the rocket motor. In this study, the analyses were executed in samples aged up to 54 days after the end of cure and submitted to 80°C and room temperature conditions. To samples stored at room temperature the hardness values increased with time while it decreased for samples at 80°C at the same period.
Doutorado
Ciencia e Tecnologia de Materiais
Doutor em Engenharia Química

Thesis (M.S.)--University of Missouri-Columbia, 2006.
The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on May 7, 2009) Includes bibliographical references.

Thèse (M.Eng.) -- Université du Québec à Chicoutimi, programme extensionné à l'Université du Québec à Rimouski, 2003.
Bibliogr.: f. 107-112. Document électronique également accessible en format PDF. CaQCU

Structural energetic materials (SEM) are a class of multicomponent materials which may react under various conditions to release energy. Fragmentation and impact induced reaction are not well characterized phenomena in SEMs. The structural energetic systems under consideration here combine aluminum with one or more of the following: nickel, tantalum, tungsten, and/or zirconium. These metal+Al systems were formulated with powders and consolidated using explosive compaction or the gas dynamic cold spray process. Fragment size distributions of the indicated metal+Al systems were explored; mean fragment sizes were found to be smaller than those from homogeneous ductile metals at comparable strain rates, posing a reduced risk to innocent bystanders if used in munitions. Extensive interface failure was observed which suggested that the interface density of these systems was an important parameter in their fragmentation. Existing fragmentation models for ductile materials did not adequately capture the fragmentation behavior of the structural energetic materials in question. A correction was suggested to modify an existing fragmentation model to expand its applicability to structural energetic materials. Fragment data demonstrated that the structural energetic materials in question provided a significant mass of combustible fragments. The potential combustion enthalpy of these fragments was shown to be significant. Impact experiments were utilized to study impact induced reaction in the indicated metal+Al SEM systems. Mesoscale parametric simulations of these experiments indicated that the topology of the microstructure constituents, particularly the stronger phase(s), played a significant role in regulating impact induced reactions. Materials in which the hard phase was topologically connected were more likely to react at a lower impact velocity due to plastic deformation induced temperature increases. When a compliant matrix surrounded stronger, simply connected particles, the compliant matrix accommodated nearly all of the deformation, which limited plastic deformation induced temperature increases in the stronger particles and reduced reactivity. Decreased difference between the strength of the constituents in the material also increased reactivity. The results presented here demonstrate that the fragmentation and reaction of metal+Al structural energetic materials are influenced by composition, microstructure topology, interface density, and constituent mechanical properties.

Ce travail de thèse vise à identifier les mécanismes par lesquels la fraction volumique de charges, la distribution de tailles des charges, le comportement mécanique du liant et les propriétés d’adhésion liant/charge des propergols composites influent sur le comportement mécanique jusqu’à rupture de ces matériaux. Des calculs de microstructures 2D par éléments finis sont mis en œuvre pour caractériser qualitativement l’évolution de la microstructure du composite au cours d’une sollicitation de traction uniaxiale à faible vitesse de déformation. Ils prennent notamment en compte un modèle de zone cohésive pour représenter la décohésion à l’interface liant/charge et un critère original de ruine de la microstructure. Les résultats numériques sont favorablement comparés aux tendances obtenues expérimentalement sur propergols composites industriels et modèles. Par ailleurs, une validation de l’approche qualitative précédente est conduite en effectuant une confrontation quantitative du comportement mécanique et de la variation volumique d’un composite modèle, obtenus par simulation de microstructures 3D et par caractérisations expérimentales. Enfin, la tenue du propergol dans un assemblage propergol/lieur soumis à un test de pelage est étudiée expérimentalement
This work aims at understanding the relationship between solid propellants particles volume fraction, particles size distribution, binder mechanical properties and binder/particles bonding with the mechanical behavior up to failure of these materials. Finite elements analyses on 2D microstructures are performed in order to qualitatively characterize the microstructure evolution throughout uniaxial tensile loading at small strain rate. These simulations account for the binder/particles debonding with a cohesive zone model and implement an original failure criterion. Simulation and experimental results are consistent. Besides, a quantitative comparison between simulations on 3D microstructures and experimental data is drawn in order to validate the above qualitative results. It is performed on a model composite and compares both the mechanical behavior and the volume variations. At last, the propellant failure during a peeling test of the liner/propellant structure is studied experimentally

This thesis examines the effects of nanoparticle, metal-oxide additives on the burning rate of composite solid propellants. Recent advancements in chemical synthesis techniques have allowed for the production of improved solid rocket propellant nano-scale additives. These additives show larger burning rate increases in composite propellants compared to previous additive generations. In addition to improving additive effectiveness, novel synthesis methods can improve manufacturability, reduce safety risks, and maximize energy efficiency of nano-scale burning rate enhancers. Several different nano-sized additives, each titania-based, were tested and compared for the same baseline AP/HTPB formulas and AP size distributions. The various methods demonstrate the evolution in our methods from spray-dried powders to pre-mixing the additive in the HTPB binder, and finally to a method of producing the additive directly in the binder as a nano-assembly. Burning rate increases as high as 80% at additive mass loadings of less than 0.5% were seen in non-aluminized, ammonium perchlorate-based propellants over the pressure spectrum of 500 psi (3.5 MPa) to 2250 psi (15.5 MPa). Increases in burning rate up to 73% were seen in similarly formulated aluminized propellants. During the past several years, the research team has refined laboratory-scale techniques for quickly and reliably assessing the mixing and performance of composite propellants with catalytic nanoparticle additives. This thesis also documents some of the details related to repeatability, accuracy, and realism of the methods used in the team’s recent nano-additive research; it also introduces the latest techniques for producing propellants with nano-sized additives and provides new burning rate results for the entire scope of additives and mixing methods. Details on the propellant characterization methods with regard to physical and combustion properties are provided. Snapshots from atmospheric propellant combustion videos taken with a Photron FASTCAM SA3 high-speed camera are included along with existing pressure and light-emission responses.

Presented in this thesis is a study of the effects of nano-sized particles used as a catalytic additive in composite solid propellant. This study was done with titanium oxide (titania)-based particles, but much of the findings and theory are applicable to any metal oxide produced by a similar method. The process required for efficiently producing larger batches of nanoparticle additives was seen to have a significant impact on the effectiveness of the additive to modify the burning rate of composite propellant consisting of ammonium perchlorate (AP) and hydroxyl terminated polybutadiene (HTPB). Specifically, titania was seen to be both an effective and ineffective burning rate modifier depending on how the nanoparticle additive was dried and subsequently heat treated. Nanoadditives were produced by various synthesis methods and tested in composite propellant consisting of 80 percent AP. Processability and scale-up effects are examined in selecting ideal synthesis methods of nanoscale titanium oxide for use as a burning rate modifier in composite propellant. Sintering of spray-dried additive agglomerates during the heat-treating process was shown to make the agglomerates difficult to break up during mixing and hinder the dispersion of the additive in the propellant. A link between additive processing, agglomerate dispersion mechanics and ultimately catalytic effect on the burning rate of AP/HTPB propellants has been developed by the theories presented in this thesis. This thesis studies the interaction between additive dispersion and the dispersion of reactions created by using fine AP in multimodal propellants. A limit in dispersion with powder additives was seen to cause the titania catalyst to be less effective in propellants containing fine AP. A new method for incorporating metal oxide nanoadditives into composite propellant with very high dispersion by suspending the additive material in the propellant binder is introduced. This new method has produced increases in burning rate of 50 to 60 percent over baseline propellants. This thesis reviews these studies with a particular focus on the application and scale-up of these nanoparticle additives to implement these additives in actual motor propellants and assesses many of the current problems and difficulties that hinder the nanoadditives’ true potential in composite propellant.

Composite propellants are composed of a solid oxidizer that is mixed into a hydrocarbon binder that when polymerized results in a solid mass capable of self-sustained combustion after ignition. Plateau propellants exhibit burning rate curves that do not follow the typical linear relationship between burning rate and pressure when plotted on a log-log scale, and because of this deviation their burning behavior is classified as anomalous burning. It is not unusual for solid-particle additives to be added to propellants in order to enhance burning rate or other properties. However, the effect of nano-size solid additives in these propellants is not fully understood or agreed upon within the research community. The current project set out to explore what possible variables were creating this result and to explore new additives. This thesis contains a literature review chronicling the last half-century of research to better understand the mechanisms that govern anomalous burning and to shed light on current research into plateau and related propellants. In addition to the review, a series of experiments investigating the use of nanoscale TiO2-based additives in AP-HTPB composite propellants was performed. The baseline propellant consisted of either 70% or 80% monomodal AP (223 μm) and 30% or 20% binder composed of IPDI-cured HTPB with Tepanol. Propellants’ burning rates were tested using a strand bomb between 500 and 2500 psi (34.0-170.1 atm). Analysis of the burning rate data shows that the crystal phase and synthesis method of the TiO2 additive are influential to plateau tailoring and to the apparent effectiveness of the additive in altering the burning rate of the composite propellant. Some of the discrepancy in the literature regarding the effectiveness of TiO2 as a tailoring additive may be due to differences in how the additive was produced. Doping the TiO2 with small amounts of metallic elements (Al, Fe, or Gd) showed additional effects on the burning rate that depend on the doping material and the amount of the dopant.

碩士
國立成功大學
航空太空工程學系碩博士班
101
With improved miniaturization and MEMS (microelectromechanical) technology, new satellites become smaller and versatile. The large and high Isp attitude control system is no longer the dominant design consideration for new satellites. Instead, “green” and nontoxic propellants are becoming an attractive design issue. Green propellant such as high concentration hydrogen peroxide will play the key role in the new era. It is non-toxic, cost-effective and has a minor impact to the environment. In particular, it has special impact on Taiwan’s space technology development in view of the restriction of the export license. Although the HTP (High Test Peroxide) mono-propellant propulsion system for satellite attitude control has attracted intensive research attention, it has not been commercialized on the market and realized on the space mission. The critical technique of the HTP mono-propellant thruster is the catalyst and the design of catalyst bed. The concept and feasibility of composite catalyst bed previously proposed by our team has been validated in the high altitude tests on board of the Sounding rocket VIII program, which has been successfully launched in June 2013. This study tries to expand the idea of composite catalyst bed and proposed a novel design concept of segmentation of the composite catalyst bed. The design focus on improve life span and stability of the catalyst bed of the HTP thruster. A special design of a transparent catalyst bed reaction chamber is constructed to study the reaction mechanism of hydrogen peroxide decomposition in the composite catalyst bed and the effects of catalyst bed segmentation. This is very different from the past research that treated the reaction chamber as a black box. Base on the catalyst reaction between liquid hydrogen peroxide and composite catalyst bad to infer the cause of hydrogen peroxide incomplete decomposition on catalyst bed. Then experiment results are applied as design guidelines for the segmentation of the composite catalyst bed. The concept is further validated on a 1 lbf-level HTP monopropellant thruster. Results from segmented and unsegmented composite catalyst beds are compared. The results show that the reaction chamber pressure oscillation drops from 23% to 7%, Isp is 120s, decomposing efficiency (ηC*) reaches 88%. The comparison shows that the design of segmentation composite catalyst bed can effectively improve the stability in reaction chamber of the HTP thruster.

碩士
元智大學
機械工程學系
95
Recently, the military faced to a thorny problem that deals with masses of waste ammunitions or over storage life of missiles. Because of environmental pollution and explosives harm factor, It is necessary to develop some technologies that separate, recovery and purify the explosives to reduce the problems from the disposal of waste ammunitions. The present paper takes ammonium perchlorate of the oxidant of the guided missile solid composite propellant as the object of study. In this study, we select methanol, acetone and ethyl ether as extract solvent to extract ammonium perchlorate from solid composite propellant by Soxhlet extraction method. The results show that the extraction results can be affected by the Dielectric constant of solvent. And the methanol will extract 90% of ammonium perchlorate from solid composite propellant in 12 hours and approximate 100% of ammonium perchlorate will be extracted from solid composite propellant in 24 hours. The purity of extracted ammonium perchlorate is over 96%, but it is not meet the requirement of military. Must purify more can conform to the specification. The ammonium perchlorate of the oxidant of solid composite propellant collected from Soxhlet extraction method, by using single solvent through continuous extraction and recovery. That can build a simple model for separation and recovering procedure and provide a noteworthy suggestion for conducting the waste ammunition problem in the future. ii i The recovery process of ammonium perchlorate of the oxidant of the guided missile solid composite propellant will develop by the plant scale in the future, other parameters still need to set up. Therefore, we should still estimate about over storage life of missiles, recycling demand, standard of safety, equipment investment, the contamination control and processes, effect of the other extract method (supercritical fluid extraction method, microwave extraction method, acceleration solvent extraction method), and purifies process, etc, it is consult to providing reference for follow-up research and recycle of high energy explosives.

This work presents the development and/or application of several laser diagnostics for studying the flame structure of composite propellant flames. These studies include examining the flame structure of novel energetic materials with potential as propellant ingredients, the near-surface flame structure of basic composite propellants, and the global flame structure of propellants containing metal additives.

First, the characterization of the deflagration of various novel energetic cocrystals is presented. The synthesis and development of novel energetic materials is a costly and challenging process. Rather than synthesizing new materials, cocrystallization provides the potential opportunity to achieve improved properties of existing energetic materials. This work presents the characterization of the effect of cocrystallization on the deflagration of a 2:1 molar cocrystal of CL-20 and HMX as well as a 1:1 molar cocrystal of CL-20 and TNT. A hydrogen peroxide (HP) solvate of CL-20 as well as a polycrystalline composite of HMX and ammonium perchlorate (AP) were also studied. A physical mixture of each material was also tested for comparison. The burning rate of each material was measured as a function of pressure. Flame structure during self-deflagration was examined using planar laser-induced fluorescence (PLIF) of CN and OH. The burning rate of the HMX/CL-20 cocrystal and the CL-20/HP solvate closely matched that of CL-20, but the burning rate of the TNT/CL-20 cocrystal was between the burning rate of its coformers. All HMX/AP materials had a higher burning rate than either HMX or AP individually and the burning rate of a physical mixture was found to be a function of particle size. The differences in the burning rate of the physical mixtures and composite crystal of HMX/AP can be explained by changes in the flame structure observed using PLIF. Burning rates and flame structure of the cocrystals were found to closely match those of their respective physical mixtures when smaller particle sizes were used (approx. less than 100 um). The results obtained demonstrate that the deflagration behavior of the coformers is not indicative of the deflagration behavior of the resulting physical mixture or cocrystal. However, changes in the resulting flame structure greatly affect the burning rate.

Next, PLIF of nitric oxide (NO) was utilized to characterize the near surface flame structure of composite propellants of AP and hydroxyl-terminated polybutadiene (HTPB) containing varying particle sizes of AP burning at 1 atm in air. In all propellants, the NO PLIF signal was strongest close to the burning propellant surface and fell to a non-zero constant value within ~1 mm of the surface where it remained throughout the remainder of the flame. Distinct diffusion-flame-like structure was observed above large individual burning AP particles in the propellant containing a bimodal distribution of 400 and 40 um AP. In contrast, the flame of a propellant containing only fine AP (40 um) behaved like a homogeneous, premixed flame. The flame of the propellant containing a bimodal distribution of 200 and 40 um AP also showed similar behavior to a premixed flame with some heterogeneous structure indicating that, at this pressure, the propellant is approaching a limit where the particle sizing is small enough that the flame behaves like a homogeneous, premixed flame. Additionally, propellants containing aluminum were tested. No significant differences were observed in the NO PLIF behavior between the propellants with and without aluminum suggesting that, at these conditions, the aluminum does not have a significant effect on the AP/HTPB flame structure near the burning surface.

The effect of aluminum particle size on the temperature of aluminized-composite-propellant flames burning at 1 atm is also presented. In this work, measurements of 1) the temperature of CO (within the flame bath gas) and 2) the temperature of AlO (located primarily within regions surrounding the burning aluminum particles) within aluminized, AP-HTPB-propellant flames were performed as a function of height above the burning propellant surface. Three aluminized propellants with varying aluminum particle size (nominally 31 um, 4.5 um, or 80 nm) and one non-aluminized AP-HTPB propellant were studied while burning in air at 1 atm. A wavelength-modulation-spectroscopy (WMS) diagnostic was utilized to measure temperature and mole fraction of CO via mid-infrared wavelengths and a conventional AlO emission-spectroscopy technique was utilized to measure the temperature of AlO. The bath-gas temperature varied significantly between propellants, particularly within 2 cm of the burning surface. The propellant with the smallest particles (nano-scale aluminum) had the highest average temperatures and far less variation with measurement location. At all measurement locations, the average bath-gas temperature increased as the initial particle size of aluminum in the propellant decreased, likely due to increased aluminum combustion. The results support arguments that larger aluminum particles can act as a heat sink near the propellant surface and require more time and space to ignite and burn completely. On a time-averaged basis, the temperatures measured from AlO and CO agreed within uncertainty at near 2650 K in the nano-aluminum propellant flame, however, AlO temperatures often exceeded CO temperatures by ~250 to 800 K in the micron-aluminum propellant flames. This result suggests that in the flames studied here, and on a time-averaged basis, the micron-aluminum particles burn in the diffusion-controlled combustion regime, whereas the nano-aluminum particles burn within or very close to the kinetically controlled combustion regime.

The study of the effect of aluminum particle size on the temperature of aluminized, composite-propellant flames was then extended to characterize the same propellants burning at elevated pressures ranging from 1 to 10 atm. A novel mid-infrared scanned-wavelength direct absorption technique was developed to acquire measurements of temperature and CO in particle-laden propellant flames burning at up to 10 atm. The results from the application of this diagnostic are among the very first measurements of gas properties in aluminized composite propellant flames burning at pressures above atmospheric pressure. In all propellants, the flame temperature and combustion efficiency of the propellant flames increased with an increase in pressure. In addition, the propellants with smaller aluminum particle sizes achieved higher flame temperatures as the particles were able to ignite and react faster. However, the propellants containing nano-scale and the smallest micron-scale aluminum powders had similar global flame temperatures suggesting that at some point a decrease in particle size results in minimal gains in the overall flame temperature. The results demonstrate how well measurements of gas properties can be used to understand the behavior of the aluminum particle combustion in the flame.

Last, the design, development, and application of a laser-absorption-spectroscopy diagnostic capable of providing quantitative, time-resolved measurements of gas temperature and HCl concentration in flames of aluminized, composite propellant flames is presented. This diagnostic utilizes a quantum-well distributed-feedback tunable diode laser emitting near 3.27 um to measure the absorbance spectra of one or two adjacent HCl lines using a scanned-WMS technique which is insensitive to non-absorbing transmission losses caused by metal particulates in the flame. This diagnostic was applied to characterize the spatial and temporal evolution of temperature and/or HCl mole fraction in small-scale flames of AP-HTPB composite propellants containing either an aluminum-lithium alloy or micron-scale aluminum. Experiments were conducted at 1 and 10 atm. At both pressures, the flame temperature of the aluminum-lithium propellant, on a time-averaged basis, was 80 to 200 K higher than that of the aluminum-propellant (depending on location in the flame) indicating more complete combustion. In addition, the mole fraction of HCl in the aluminum-lithium propellant flame reached values 65-70% lower than the conventional aluminum-propellant flame at the highest measurement location in the flame. The measurements at both pressures showed similar trends in the reduction of HCl in the aluminum-lithium propellant flame but at 10 atm this occurred on a length scale an order of magnitude smaller than the flame at atmospheric pressure. The results presented further support that the use of an aluminum-lithium alloy is effective at reducing HCl produced by the propellant flame without compromising performance, thereby making it an attractive additive for solid rocket propellants.

Composite propellants are composed of a solid oxidizer that is mixed into a hydrocarbon binder that when polymerized results in a solid mass capable of selfsustained combustion after ignition. Plateau propellants exhibit burning rate curves that do not follow the typical linear relationship between burning rate and pressure when plotted on a log-log scale, and because of this deviation their burning behavior is classified as anomalous burning. It is not unusual for solid-particle additives to be added to propellants in order to enhance burning rate or other properties. However, the effect of nano-size solid additives in these propellants is not fully understood or agreed upon within the research community. The current project set out to explore what possible variables were creating this result and to explore new additives. This thesis contains a literature review chronicling the last half-century of research to better understand the mechanisms that govern anomalous burning and to shed light on current research into plateau and related propellants. In addition to the review, a series of experiments investigating the use of nanoscale TiO2-based additives in AP-HTPB composite propellants was performed. The baseline propellant consisted of either 70% or 80% monomodal AP (223 μm) and 30% or 20% binder composed of IPDI-cured HTPB with Tepanol. Propellants’ burning rates were tested using a strand bomb between 500 and 2500 psi (34.0-170.1 atm). Analysis of the burning rate data shows that the crystal phase and synthesis method of the TiO2 additive are influential to plateau tailoring and to the apparent effectiveness of the additive in altering the burning rate of the composite propellant. Some of the discrepancy in the literature regarding the effectiveness of TiO2 as a tailoring additive may be due to differences in how the additive was produced. Doping the TiO2 with small amounts of metallic elements (Al, Fe, or Gd) showed additional effects on the burning rate that depend on the doping material and the amount of the dopant.

碩士
國防大學理工學院
化學工程碩士班
101
The major components of the double-based propellants generally include nitrocellulose and nitroglycerine, which have been studied for years. In order to enhance the performance, the existing studies show that adding metal and solid fuels can enhance the combustion energy and affect the performance of the double-based propellants. The purpose of this research is to enhance the performance of the double-based propellants by adding micro and nano-sized metal aluminum powders and ammonium perchlorate. Firstly, the suitable propellant formulations were songht with NASA Code, and differential scanning calorimetry (DSC) and thermogravimetry wed used to meaeured the characteristics of double-based propellants,which contained micro and nano sized aluminum powders and ammonium perchlorate.Then small-sized double-based propellants were prepared,and dispersed offset inside the double-based propellants were obtaineal by using scanning electro microscope(SEM). Finally,burning rate meter was operated to explore combustion characteristics of the modified double-based propellants.Furthermore, the pull-testing machine was conducted to evaluate the mechanical properties. The results showed that the modified double-based propellants,which prepareal by solvent method ,had better dispersion and experiments showed that had better propellant ballistic performance, mechanical properties, density and stability than double-based propellants excellent.

碩士
國防大學理工學院
化學工程碩士班
101
In this study, the optimum formulations were simulated from NASA Code; andthen the composite modified double base propellants where prepared by solvent method which which have been developed for many years and have matured for production skikks. In order to promote the performance of the double base propellants, the domestic and international studies show that adding metal and solid fuel can enhance the combustion energy and affect the performance of the double base propellants. The purpose of this research is to enhance the performance of the double base propellant by adding micro and nano-sized aluminum and RDX. Firstly, the reaction characteristics of the double base propellants containing the micro and nano-sized aluminum powders and solid fuel (RDX) will be measured using differential scanning calorimetry (DSC) and thermogravimetry (TGA), and the difference between their properties will be analyzed; and then the proper dispersed technique will be evaluated by using scanning electron microscope (SEM) to observe the dispersed effect of micro and nano-sized aluminum, RDX powders in the double base propellants. The above-mentioned research will contribute to the development of advanced double base propellants for military.

The following dissertation describes an investigation of the structural response behaviour of a composite solid rocket motor nozzle subjected to thermal and pressure loading during the motor ignition period, derived on the basis of a multidisciplinary numerical simulation approach. To provide quantitative and qualitative context to the results obtained, comparisons were made to the predicted aerothermostructural response of the nozzle over the entire motor burn period. The study considered two nozzle designs – an exploratory nozzle design used to establish the basic simulation methodology, and a prototype nozzle design that was employed as the primary subject for numerical experimentation work. Both designs were developed according to fundamental solid rocket motor nozzle design principles as non-vectoring nozzles for deployment in medium sized solid rocket booster motors. The designs feature extensive use of spatially reinforced carbon-carbon composites for thermostructural components, complemented by carbon-phenolic composites for thermal insulation and steel for the motor attachment substructures. All numerical simulations were conducted using the ADINA multiphysics finite element analysis code with respect to axisymmetric computational domains. Thermal and structural models were developed to simulate the structural response of the exploratory nozzle design in reference to the instantaneous application of pressure and thermal loading conditions derived from literature. Ignition and burn period response results were obtained for both quasi-static and dynamic analysis regimes. For the case of the prototype nozzle design, a flow model was specifically developed to simulate the flow of the exhaust gas stream within the nozzle, for the provision of transient and steady loading data to the associated thermal and structural models. This arrangement allowed for a more realistic representation of the interaction between the fluid, thermal and structural fields concerned. Results were once again obtained for short and long term scenarios with respect to quasi-static and dynamic interpretations. In addition, the aeroelastic interaction occurring between the nozzle and flow field during motor ignition was examined in detail. The results obtained in the present study provided significant indications with respect to a variety of response characteristics associated with the motor ignition period, including the magnitude and distribution of the displacement and stress responses, the importance of inertial effects in response computations, the stress response contributions made by thermal and pressure loading, the effect of loading condition quality, and the bearing of the rate of ignition on the calculated stress response. Through comparisons between the response behaviour predicted during the motor ignition and burn periods, the significance of considering the ignition period as a qualification and optimisation criterion in the design of characteristically similar solid rocket motor nozzles was established.
Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2009.

碩士
國防大學中正理工學院
應用化學碩士班
99
Although the composite propellants with nano-aluminum powder have been studied widely, the nano-aluminum powder with small particle size and large surface area has complicated microstructure, rapid oxidization and easy agglomeration leading to loss it’s activity. Therefore, for improving the properties of solid composite propellant, it is urgent to develop the methods of dispersion and protection of nano powders. The purpose of this research is using the surface modification technology of nano-aluminum powder and the dispersion method to the combustion characteristics of composite propellant with surface modification nano-aluminum powder. The composite propellants containing the macro-sized and nano-sized aluminum powders were prepared by different dispersion techniques. The thermal characteristics of propellants as prepared were measured using differential scanning calorimetry (DSC), then the differences among them were analyzed. The scanning electron microscope (SEM) was used to observe the dispersed effect of nano-sized powders in the composite propellants. Finally, the composite propellants were processed to be small cylindrical pellets, and the burning rate meter, window bomb (WB) and quenched particle collection bomb (QPCB) were used to study the burning properties of composite propellants. The burning phenomenon was also analyzed by mean of the combustion observation technique. Furthermore, the pull-testing machine is conducted to evaluate the mechanical properties. The experimental results show that increasing the dispersion of micro / nano-aluminum powder in the propellant, the coefficient of variation of burning rate is smaller, the combustion is more stable, the mechanical properties is significantly improved.

The performance of solid rocket motors (SRMs) is extremely dependent on propellant formulation, operating pressure, and initial grain geometry. Traditionally, propellant grains are cast into molds, but it is difficult to remove the grains without damage if the geometry is too complex. Cracks or voids in propellant can lead to erratic burning that can break the grain apart and/or potentially overpressurize the motor. Not only is this dangerous, but the payload could be destroyed or lost. Some geometries (i.e. internal voids or intricate structures) cannot be cast and there is no consistent nor economical way to functionally grade grains made of multiple propellant formulations at fines scales (~ mm) without the risk of delamination between layers or the use of adhesives, which significantly lower performance. If one could manufacture grains in such a way, then one would have more control and flexibility over the design and performance of a SRM. However, new manufacturing techniques are required to enable innovation of new propellant grains and new analysis techniques are necessary to understand the driving forces behind the combustion of non-traditionally manufactured propellant.

Additive manufacturing (AM) has been used in many industries to enable rapid prototyping and the construction of complex hierarchal structures. AM of propellant is an emerging research area, but it is still in its infancy since there are some large challenges to overcome. Namely, high performance propellant requires a minimum solids loading in order to combust properly and this translates into mixtures with high viscosities that are difficult to 3D print. In addition, it is important to be able to manufacture realistic propellant formulations into grains that do not deform and can be precisely functionally graded without the presence of defects from the printing process. The research presented in this dissertation identifies the effect of a specific AM process called Vibration Assisted Printing (VAP) on the combustion of propellant, as well as the development of binders that enable UV-curing to improve the final resolution of 3D printed structures. In addition, the combustion dynamics of additively manufactured layered propellant is studied with computational and experimental methods. The work presented in this dissertation lays the foundation for progress in the developing research area of additively manufactured energetic materials.

The appendices of this dissertation presents some additional data that could also be useful for researchers. A more detailed description of the methods necessary to support the VAP process, additional viscosity measurements and micro-CT images of propellant, the combustion of Al/PVDF filament in windowed propellant at pressure, and microexplosions of propellant with an Al/Zr additive are all provided in this section.

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.

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.

碩士
國防大學中正理工學院
應用化學研究所
91
The burning rate pressure exponent (n) is the most important index in composite solid propellants. Various factors which affect this property and a number of different manufacturing processes for controlling the pressure exponent in composite solid propellants of AP/RDX/HTPB/Al system are discussed. They include the effects of (1) different content of HTPB and DOA, (2) the particle size of Al and RDX, (3) the particle size distribution of AP, (4) NQ replacing RDX, and (5) the ballistic modifier additives. The burning rate was measured in a strand burner at 21℃ and 15~105 kg/cm2of nitrogen pressure.From the results of the burning rate analysis, the pressure exponent (n) of propellants：(1) decreased with increasing content of HTPB and DOA, (2) decreased with increasing Al particle size, (3) increased with increasing RDX particle size, (4) increased with decreasing AP particle size, but for the propellants made from the different AP particle sizes, the feeding order and the mixing extent during different manufacturing processes would also affect the burning rate and the pressure exponent, (5) decreased with increasing NQ content which suppressed the burning rate of propellant, and (6) increased with increasing Fe2O3 of ballistic modifier additive, or decreased with increasing C-black, TiO2 and CaCO3 of ballistic modifier additive. The effect of the initial temperature of the 30 mm Al powder propellant on the burning rate also was discussed.

碩士
國防大學中正理工學院
應用化學碩士班
99
The boron powder has high burning heat, so it is a focus for the research of fuel-rich propellants. However, if the boron powder is added to the propellant and mixed together, it will lead to the phenomenon of high viscosity and increase the difficulty of mixed process. Therefore, it is necessary to study the mechanism of viscosity increasing in the mixed process of the boron-based propellants and then to explore the method to reduce their viscosity. This study focuses on the incompatible phenomena between boron powder and binder (Hydroxyl Terminated Polybutadiene, HTPB) in the boron-based fuel-rich propellants. The study is divided into two parts. The first part study the mechanism of viscosity increasing. Firstly, the surface composition of the nano-sized and micro-sized boron is analyzed by X-ray Photoelectron Spectroscope(XPS) and then the pH value of the boron powder is measured by pH meter. Afterward rotation rheometer is used to test the variation of viscosity during mixing of boron and HTPB and determine the reason for increase in viscosity. The second part probe into the improvement of mixing viscosity in boron-based propellants. The first aim at comparing the superiority of the way to improve the rheological properties, then experimental method is used to assess the feasibility of the method that can improve the rheological properties effectively, and the final work is the test of rheological properties. The experimental results show that adding boron powder improved by sodium hydroxide into HTPB can decrease viscosity of the mixed process effectively, and if adding boron powder improved by sodium hydroxide and coated by ammonium perchlorate into HTPB, the effect is more significant.