Propellants based on hydroxylammonium nitrate (HAN) have shown promise as a hydrazine replacement because of their comparably low toxicity, low vapor pressure, high specific impulse and high density. Herein, the recent history of advanced monopropellant research is explored, and new experimental techniques are presented to investigate the combustion behavior of a potential hydrazine replacement propellant. Nitromethane, a widely available monopropellant with a recent resurgence in research, is utilized in the current study as a proof of concept for the newly designed equipment and as a step towards investigating more-advanced, HAN-based monopropellants. A strand bomb facility capable of supporting testing at up to 340 atm was employed, and experiments were performed between 28 atm and 130 atm. Burning rate data for nitromethane are calculated from experiments and a power correlation is established as r(mm/s) = 0.33[P(MPa)]^1.02. A comparison with available literature reveals this correlation to be very much in agreement to other studies of nitromethane. Other physical characteristics of nitromethane combustion are presented. Updates to the facility and new methods to examine the combustion of liquid propellant are described in detail. Special focus is given to procedures and safety information.

Propelentes sólidos são materiais energéticos que produzem gases em alta pressão por meio de uma reação de combustão. Qualquer propelente sólido inclui dois ou mais dos seguintes componentes: oxidante (nitratos e percloratos); combustível (resinas orgânicas ou polímeros); compostos químicos combinando oxidantes e combustíveis (nitrocelulose ou nitroglicerina); aditivos para facilitar processos de produção ou alterar a taxa de queima e inibidores (fita de etilcelulose), para restringir superfícies de combustão. Pequenas percentagens de aditivos são usadas para modificar diversas propriedades mecânicas, químicas e balísticas dos propelentes sólidos: acelerar ou desacelerar a velocidade de combustão (catalisadores e inibidores de combustão, respectivamente); assegurar a estabilidade química para prevenir a deterioração durante a estocagem; controlar as propriedades de processamento durante a produção de propelente (tempo de cura, fluidez para extrusão ou moldagem, etc.); controlar as propriedades de absorção de radiação no propelente em combustão; aumentar a resistência mecânica e diminuir a deformação elástica; e, finalmente, minimizar a sensibilidade térmica. No caso de propelentes sólidos Base Dupla (mistura de duas bases ativas: a nitrocelulose e a nitroglicerina), é possível alterar sua velocidade de queima principalmente pelo emprego de pequenos teores de modificadores balísticos, em geral sais orgânicos de cobre e chumbo. Neste trabalho, estudou-se a aceleração da velocidade de queima de uma formulação conhecida de propelente Base Dupla - BD, alterando o teor total dos modificadores balísticos cromato de cobre e estearato de chumbo (ou plastabil - nome comercial) na receita original, bem como a proporção entre eles. Estas alterações na formulação original devem, idealmente, preservar os parâmetros de desempenho estabelecidos para as propriedades químicas (estabilidade química) e mecânicas (densidade da massa e ensaios de tração), ao mesmo tempo otimizando o desempenho balístico, pelo aumento da velocidade de queima. Os resultados experimentais mostram que para os parâmetros de qualidade elongação e velocidade de queima a interação entre os fatores, Proporção Sal de Chumbo/Sal de Cobre (Fator A) e Teor de Modificadores Balísticos (Fator B) foram significativos, ou seja, quanto maior os fatores pior o resultado com as propriedades. Com os parâmetros de resistência a tração e densidade da massa, o fator A e B respectivamente influenciam negativamente quando aumentado em sua concentração. Para o parâmetro estabilidade química não houve nenhum sinal de melhora ou influencia dos fatores. No caso da velocidade de queima a interação AB é o que mais influencia. Melhorando significativamente a velocidade de queima. / Solid propellants are energetic materials which produce a considerable amount of high-pressure gases by means of a combustion reaction. Any solid propellant formulation includes at least two of the following items: oxidizer (nitrates and perchlorates); fuel (organic resins or polymers); chemical compounds combining oxidizers and fuels (nitrocellulose or nitroglycerine); additives to easy production operations or to modify the burning rate and inhibitors (tape ethyl-cellulose), to restrict the combustion surfaces. Small amounts of additives are employed to modify the mechanical, chemical and ballistic features of the solid propellants: to accelerate or diminish the burning rate (catalysts and inhibitors of burning, respectively); to assure the chemical stability in order to prevent the deterioration during stocking; to control the processing properties during propellant production (curing time, extrusion or casting rheology); to control the radiation absorption in the burning propellant; to enhance the mechanical resistance and to reduce the strain; and, finally, to get the thermal sensitivity to a minimum level. In the case of Double-Base solid propellants (blend of two energetic bases: nitrocellulose and nitroglycerine), it\'s possible to control its burning rate mainly by the use of small amounts of ballistic modifiers, generally copper and lead organic salts. This work has studied the burning rate acceleration of a known Double-Base propellant formulation, by changing the total amount of the ballistic modifiers copper chromate and lead stearate (commercially known as plastabil) in the original formulation, as well as the proportion between them. These changes at the original recipe should preserve, ideally, the performance levels required for the chemical (chemical stability) and mechanical properties (density and stress-strain evaluation), optimizing, at the same time, the ballistic performance, through the burning rate enhancement. Results show that for the parameters of quality and elongation rate of burning the interaction between factors, Proportion of Lead Salt / Salt Copper (Factor A) and content Ballistic Modifiers (Factor B) were significant, ie, the higher the worst factors result with the properties. With the parameters of tensile strength and mass density, the factor A and B respectively negatively influence increased when its concentration. For the chemical stability parameter there was no sign of improvement or influences of factors. In the case of burning rate AB interaction is what most influences. Significantly improving the speed of burning.

Recently, considerable interest has been devoted to the synthesis of new ferrocene derivatives since properly functionalized ferrocene derivatives could be potential antitumor substances. For this purpose, we have investigated the synthesis of ferrocenyl quinones starting from squaric acid. Thermolysis of ferrocenylsubstituted cyclobutenones, which have been prepared from ferrocenyl cyclobutenediones and alkenyllithiums, affords hydroquinones, which furnish, upon oxidation, ferrocenyl quinones. Ferrocenyl cyclobutenediones have been prepared from known cyclobutenediones by nucleophilic addition of ferrocenyllithiumfollowed by hydrolysis, Pd/Cu-cocatalyzed cross-coupling with (tri-n-butylstannyl)ferrocene or Friedel&amp / #8211 / Crafts alkylation with ferrocene. A mechanism involving electrocyclic ring opening of alkenyl substituted cyclobutenone to dienylketene and consequent electrocyclic ring closure to cyclohexadienone followed by enolization has been proposed to account for the formation of ferocenyl substituted hydroquinones. Rocket design and production is one of the hottest topics in defense industry. On this subject, significant amount of investments have been done and excellent results were obtained. Among the burning rate catalysts for composite rocket propellants, ferrocene derivatives are one of the most famous ones. Although ferrocene derivatives are superior to some other burning rate catalysts, their use has some drawbacks arising from the tendency of migration in the bulk of the material and their sensitivity toward oxidation by air. With the aim of preventing the negative aspects of ferrocene derivatives, we have investigated the synthesis of EDA (ethylenediamine), TEP (tetraethylenepentamine) and DDI (dimeryl-diisocyanate) based ferrocene derivatives.

Propelentes sólidos são materiais energéticos que produzem gases em alta pressão por meio de uma reação de combustão. Qualquer propelente sólido inclui dois ou mais dos seguintes componentes: oxidante (nitratos e percloratos); combustível (resinas orgânicas ou polímeros); compostos químicos combinando oxidantes e combustíveis (nitrocelulose ou nitroglicerina); aditivos para facilitar processos de produção ou alterar a taxa de queima e inibidores (fita de etilcelulose), para restringir superfícies de combustão. Pequenas percentagens de aditivos são usadas para modificar diversas propriedades mecânicas, químicas e balísticas dos propelentes sólidos: acelerar ou desacelerar a velocidade de combustão (catalisadores e inibidores de combustão, respectivamente); assegurar a estabilidade química para prevenir a deterioração durante a estocagem; controlar as propriedades de processamento durante a produção de propelente (tempo de cura, fluidez para extrusão ou moldagem, etc.); controlar as propriedades de absorção de radiação no propelente em combustão; aumentar a resistência mecânica e diminuir a deformação elástica; e, finalmente, minimizar a sensibilidade térmica. No caso de propelentes sólidos Base Dupla (mistura de duas bases ativas: a nitrocelulose e a nitroglicerina), é possível alterar sua velocidade de queima principalmente pelo emprego de pequenos teores de modificadores balísticos, em geral sais orgânicos de cobre e chumbo. Neste trabalho, estudou-se a aceleração da velocidade de queima de uma formulação conhecida de propelente Base Dupla - BD, alterando o teor total dos modificadores balísticos cromato de cobre e estearato de chumbo (ou plastabil - nome comercial) na receita original, bem como a proporção entre eles. Estas alterações na formulação original devem, idealmente, preservar os parâmetros de desempenho estabelecidos para as propriedades químicas (estabilidade química) e mecânicas (densidade da massa e ensaios de tração), ao mesmo tempo otimizando o desempenho balístico, pelo aumento da velocidade de queima. Os resultados experimentais mostram que para os parâmetros de qualidade elongação e velocidade de queima a interação entre os fatores, Proporção Sal de Chumbo/Sal de Cobre (Fator A) e Teor de Modificadores Balísticos (Fator B) foram significativos, ou seja, quanto maior os fatores pior o resultado com as propriedades. Com os parâmetros de resistência a tração e densidade da massa, o fator A e B respectivamente influenciam negativamente quando aumentado em sua concentração. Para o parâmetro estabilidade química não houve nenhum sinal de melhora ou influencia dos fatores. No caso da velocidade de queima a interação AB é o que mais influencia. Melhorando significativamente a velocidade de queima. / Solid propellants are energetic materials which produce a considerable amount of high-pressure gases by means of a combustion reaction. Any solid propellant formulation includes at least two of the following items: oxidizer (nitrates and perchlorates); fuel (organic resins or polymers); chemical compounds combining oxidizers and fuels (nitrocellulose or nitroglycerine); additives to easy production operations or to modify the burning rate and inhibitors (tape ethyl-cellulose), to restrict the combustion surfaces. Small amounts of additives are employed to modify the mechanical, chemical and ballistic features of the solid propellants: to accelerate or diminish the burning rate (catalysts and inhibitors of burning, respectively); to assure the chemical stability in order to prevent the deterioration during stocking; to control the processing properties during propellant production (curing time, extrusion or casting rheology); to control the radiation absorption in the burning propellant; to enhance the mechanical resistance and to reduce the strain; and, finally, to get the thermal sensitivity to a minimum level. In the case of Double-Base solid propellants (blend of two energetic bases: nitrocellulose and nitroglycerine), it\'s possible to control its burning rate mainly by the use of small amounts of ballistic modifiers, generally copper and lead organic salts. This work has studied the burning rate acceleration of a known Double-Base propellant formulation, by changing the total amount of the ballistic modifiers copper chromate and lead stearate (commercially known as plastabil) in the original formulation, as well as the proportion between them. These changes at the original recipe should preserve, ideally, the performance levels required for the chemical (chemical stability) and mechanical properties (density and stress-strain evaluation), optimizing, at the same time, the ballistic performance, through the burning rate enhancement. Results show that for the parameters of quality and elongation rate of burning the interaction between factors, Proportion of Lead Salt / Salt Copper (Factor A) and content Ballistic Modifiers (Factor B) were significant, ie, the higher the worst factors result with the properties. With the parameters of tensile strength and mass density, the factor A and B respectively negatively influence increased when its concentration. For the chemical stability parameter there was no sign of improvement or influences of factors. In the case of burning rate AB interaction is what most influences. Significantly improving the speed of burning.

Orientador: Saulo Philipe Sebastião Guerra / Resumo: Este trabalho teve como objetivo avaliar o comportamento dos briquetes durante a queima, considerando a possibilidade de se aprimorar o índice de combustão de briquetes de biomassa (aqui denominado ICOMa) com o uso de um aplicativo de computador, de forma que esta nova proposta fosse mais sensível às variações dos dados que o ICOM (já existente na literatura), bem como determinar sua taxa de perda de massa em função do tempo de queima. Com esta nova proposta, também era esperado que se percebesse uma correlação entre o ICOMa e o poder calorífico superior da biomassa ensaiada, possibilitando estimar esta grandeza, ainda que de forma aproximada, sem o uso de uma bomba calorimétrica. A fabricação do dispositivo para obtenção do ICOMa foi baseada em trabalhos prévios obtidos na literatura, usando uma balança com porta de comunicação em protocolo RS 232, um termopar tipo K para medição da temperatura e um dispositivo para aquisição automática dos dados, feita por um aplicativo computacional também desenvolvido neste trabalho. Os briquetes usados nos ensaios foram de casca de algodão, toco de eucalipto, bagaço de cana-de-açúcar e madeira de pinus, e foram produzidos especificamente para a determinação do ICOMa. O aplicativo atendeu às necessidades do ensaio para obtenção das variáveis relacionadas aos índices de combustão. O ICOMa foi mais sensível que o ICOM na observação da relação entre consumo de massa e geração de calor, e permitiu observar diferenças estatisticamente signific... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This work aimed to evaluate the behavior of briquettes during burning, considering the possibility of improving the combustion index of biomass briquettes (here called ICOMa) using a software, so that this new proposal to be more sensitive to data variations than ICOM (already existing in the literature), as well as to determine its mass loss rate as a function of burning time. It was also expected with this new proposal, that a correlation between the ICOMa and the higher heating value of the tested biomass could be perceived, making it possible to estimate this magnitude, albeit approximately, without the use of a bomb calorimeter. The manufacture of the device for obtaining the ICOMa was based on previous work obtained in the literature, using a RS 232 communication port scale, a type K thermocouple for temperature measurement, and a device for automatic data acquisition by a computational application, this one developed in this work. The briquettes used in the tests were cotton bark, eucalyptus stump, sugarcane bagasse, and pinewood, and produced specially for the determination of ICOMa. The computational application met the needs of the test to obtain the variables related to the combustion indexes. The ICOMa was more sensitive than the ICOM in observing the relationship between the mass consumption and heat generation, and show a statistical difference between different temperature curves of the materials, unlike the ICOM. The biggest ICOMa found was 0.97 K.h.g-1, and t... (Complete abstract click electronic access below) / Mestre

This document details original numerical studies performed by the author pertaining to solid propellant combustion. Detailed kinetic mechanisms have been utilized to model the combustion of the pseudo-propellants RDX/GAP and AP/HTPB. A particle packing model and a diffusion flame model have been utilized to develop a burning rate and an aluminum agglomeration model. The numerical model for RDX/GAP combustion utilizes a "universal" gas-phase kinetic mechanism previously applied to combustion models of several monopropellants and pseudo-propellants. The kinetic mechanism consists of 83 species and 530 reactions. Numerical results using this mechanism provide excellent agreement with RDX and GAP burning rate data, and agree qualitatively with RDX/GAP pseudo-propellant data. The numerical model for AP/HTPB combustion utilizes the same universal mechanism, with chlorine reactions added for modeling AP combustion. Including chlorine, there are 106 species and 611 reactions. Global condensed-phase reactions have been developed for six AP percentages between 59% and 80% AP. The AP/HTPB model accurately predicts burning rates, as well as temperature and species profiles. The numerical burning rate model utilizes a three-dimensional particle-packing model to generate cylindrical particle packs. Particle-size distributions have been modeled using a three-parameter lognormal distribution function. Pressure-dependent homogenization has been used to capture pressure effects and reduce cpu time. A "characteristic" burning path is found through each particle pack. Numerical results showed that different path-finding approaches work better depending on the propellant formulation and combustion conditions. Proposed future work and modifications to the present model are suggested. The numerical agglomeration model utilizes the same particle packing model and particle-size distribution function as in the burning rate model. Three preliminary models have been developed examining the ideas of pockets, separation distance, and aluminum ignition. Preliminary model results indicate the importance of predicting aluminum particle ignition. In the final model, the surface is regressed numerically through each particle pack. At each surface location, calculations are performed to determine whether aluminum particles combine and/or ignite. Ignition criteria have been developed from the results of the diffusion flame model and an analysis of particle-pack cross-sections. Numerical results show qualitative agreement with each experimentally observed trend. Proposed future work and modifications to the present model are suggested.

The application of emission spectroscopy to monitor combustion products of solid rocket propellant combustion can potentially yield valuable data about reactions occurring within the volatile environment of a strand burner. This information can be applied in the solid rocket propellant industry. The current study details the implementation of a compact spectrometer and fiber optic cable to investigate the visible emission generated from three variations of solid propellants. The grating was blazed for a wavelength range from 200 to 800 nm, and the spectrometer system provides time resolutions on the order of 1 millisecond. One propellant formula contained a fine aluminum powder, acting as a fuel, mixed with ammonium perchlorate (AP), an oxidizer. The powders were held together with Hydroxyl-Terminated-Polybutadiene (HTPB), a hydrocarbon polymer that is solidified using a curative after all components are homogeneously mixed. The other two propellants did not contain aluminum, but rather relied on the HTPB as a fuel source. The propellants without aluminum differed in that one contained a bimodal mix of AP. Utilizing smaller particle sizes within solid propellants yields greater surface area contact between oxidizer and fuel, which ultimately promotes faster burning. Each propellant was combusted in a controlled, non-reactive environment at a range of pressures between 250 and 2000 psi. The data allow for accurate burning rate calculations as well as an opportunity to analyze the combustion region through the emission spectroscopy diagnostic. It is shown that the new diagnostic identifies the differences between the aluminized and non-aluminized propellants through the appearance of aluminum oxide emission bands. Anomalies during a burn are also verified through the optical emission spectral data collected.

Electrolyte and pyrotechnic pellets are two important components of thermal batteries. Both electrolyte and pyrotechnic pellets are produced by cold compaction of constituent powders. These compacts are integrated in the battery as pellets with sufficient green density, green strength, calorific energy and burning rate (for pyrotechnic only) to provide high performance batteries. In this study, effects of physical properties of the used powders such as particle size distribution, average particle size, particle shape and composition of components and applied compression pressure and their interactions on green density and green strength of electrolyte pellets and in addition, calorific energy and burning rate of pyrotechnic pellets were examined. Statistical experimental designs were constructed to investigate the main and interaction effects of studied variables. 24 two factorial statistically designed experiments&rsquo / results for pyrotechnic pellets exhibited that the compression pressure and iron powder morphology were the most significant factors improving green density and break strength of pyrotechnic pellets. It was shown that the compression pressure had a negative effect on burning rate. Both calorific output and burning rate were increased significantly by increasing KClO4 fraction. In addition, decreasing particle size of KClO4 had also a positive effect on burning rate. The maximum calorific output was obtained at maximum KClO4 fraction. 23 two factorial statistically designed green strength and green density experiments&rsquo / results of electrolyte pellets revealed that, compression pressure was again the dominating factor. Moreover, there was a tendency for higher green density with lower MgO fraction and electrolyte powder average particle size. Besides, the positive effect of decreasing average particle size on green strength was investigated distinctly at low green density values. From the thermal battery perspective, main and interaction effects of variables on the characteristics of electrolyte and pyrotechnic pellets were successfully examined.

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<p dir="ltr">Burning rate as a function of pressure is one of the primary evaluation metrics of solid propellants. Most solid propellant burning rate measurements are made at a nearly constant pressure using a variety of measurement approaches. This type of burning rate data is highly discretized and requires many tests to accurately determine the burning rate response to pressure. It would be moreefficient to measure burning rate dynamically as pressures are varied. Techniques used to make transient burning rate measurements are reviewed briefly and initial results using a microwave interferometry (MI) technique are presented. The MI method used in tandem with a closed bomb enables nearly continuous measurement of burning rates for self-pressurizing burns, capturing burning rate data over a wide range of pressures. This approach is especially useful for characterization of propellants with complex burning behaviors (e.g., slope breaks or mesa burning). The burning rates of three research propellants were characterized over a pressure range of 0.101-24.14 MPa (14-3500 psi). One research propellant exhibited a slope break at a pressure of 6.63 MPa (960 psi). Using MI in a closed pressure vessel, 14 propellant strand burns resulted in a nearly continuous burning rate curve over a pressure range of 0.41-24.13MPa (60-3500psi) that reasonably matched conventional burning rate measurements. The development of this technique provides an opportunity to quickly characterize the burning rate curve of solid propellants with greater fidelity and efficiency than traditional quasi-static pressure testing techniques.</p>