O objetivo desta pesquisa foi comparar as alterações cefalométricas de pacientes com má oclusão de Classe II divisão 1, tratados com os aparelhos Jasper Jumper e Twin Force Bite Corrector, associados ao aparelho ortodôntico fixo. A amostra foi composta por 120 telerradiografias em norma lateral de 60 pacientes, os quais foram divididos em 3 grupos: Grupo Experimental 1, constituído por 20 pacientes com idade inicial média de 12,39 anos, tratados por meio do aparelho Jasper Jumper associado ao aparelho fixo, por um período médio de 2,42 anos; Grupo Experimental 2, contendo 20 pacientes com idade inicial média de 11,83 anos, tratados com o aparelho Twin Force associado ao aparelho fixo, com tempo médio de tratamento de 2,59 anos; Grupo Controle, composto por 20 jovens, com idade inicial média de 12,13 anos e observados por um período médio de 2,21 anos. As alterações foram comparadas entre os grupos, por meio da Análise de Variância e do teste de Tukey. Observou-se que ambos os tratamentos apresentaram um efeito restritivo na maxila, houve melhora significante da relação maxilomandibular nos dois protocolos de tratamento avaliados e promoveram rotação horária do plano oclusal. O grupo Jasper Jumper, promoveu uma significante limitação do desenvolvimento vertical dos molares superiores em relação aos outros grupos. Os incisivos inferiores exibiram maior protrusão e uma extrusão dos molares inferiores nos grupos 1 e 2. Ambos os aparelhos melhoraram significantemente a relação maxilomandibular, os trespasses horizontal, vertical e a relação molar. Os protocolos de tratamento promoveram retrusão dos lábios superiores. / The aim of this study was to compare the cephalometric changes in patients with Class II Division 1 malocclusion, treated with the Jasper Jumper and Twin Force Bite Corrector, associated with fixed orthodontic appliances. The sample consisted of 120 lateral cephalometric radiographs of 60 patients, divided into 3 groups: Experimental Group 1 comprised 20 patients with initial mean age of 12.39 years, treated with the Jasper Jumper appliance associated with device fixed for an average period of 2.42 years; Experimental group 2 with 20 patients with initial mean age of 11.83 years, treated with Twin Force unit associated with braces, with an average treatment time of 2.59 years; Control Group, composed of 20 individuals, average initial age of 12.13 years and observed for an average period of 2.21 years. The changes were compared between groups by ANOVA followed by Tukey test. It was observed that both treatments presented a restrictive effect on the maxilla; there was significant improvement in the maxillomandibular relationship in the two treatment protocols groups evaluated and clockwise rotation of the occlusal plane. The Jasper Jumper group, provided a significant limitation of the vertical development of the maxillary molars in relation to other groups. The lower incisors showed greater protrusion and extrusion of mandibular molars in groups 1 and 2. Both appliances provided significant improvement of maxillomandibular relationship, overjet, overbite and molar relationship. Groups 1 and 2 presented retrusion of the upper lip.

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.

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.

In this study, shelf life of three different crosslinked double base (XLDB) propellants stabilized with 2-nitrodiphenylamine (2-NDPA) and n-methyl-4-nitroaniline (MNA) were determined by using the stabilizer depletion method. Depletions of the stabilizers were monitored at different aging temperatures using High Performance Liquid Chromatography (HPLC). Kinetic models of pseudo zero, pseudo first, pseudo second and shifting order were used to find the best model equation that fits the experimental data. The rates of depletion of stabilizers were calculated at 45, 55 and 65&deg / C based on the best fit kinetic models. Using the rate constants at different temperatures, rate constants at room temperature were calculated by Arrhenius equation. The activation energies and frequency factors for the depletion of 2-NDPA and MNA were obtained for all XLDB propellants. Moreover, the results were evaluated based on the NATO standard / STANAG 4117 and the propellants were found stable according to the standard. Vacuum thermal stability (VTS) tests were also conducted to evaluate the stability of XLDB propellants. The propellant that includes the stabilizer mixture of MNA and 2-NDPA was found to have less stability than the propellants that include 2-NDPA only. However, there were rejection (puking) and migration of stabilizer derivatives for the aged samples of propellants that were stabilized with only 2-NDPA. Moreover, formation of voids and cracks were observed in block propellant samples due to excess gas generation.

Conventional energetic materials which are based on monomolecular compounds such as trinitrotoluene (TNT) have relatively low volumetric energy density. The energy density can be significantly enhanced by the addition of metal particulates. Among all metals, aluminum is popular because of its high oxidation enthalpy, low cost, and relative safety. Micron-sized aluminum particles, which have relatively high ignition temperatures and burning times, have been most commonly employed. Ignition of micron-sized aluminum particles is typically achieved only upon melting of the oxide shell at 2350 K, thereby resulting in fairly high ignition delay. Novel approaches to reduce the ignition temperatures and burning times and enhance the energy content of the particle are necessary. Recently, there has been an enormous interest in nano-materials due to their unique physicochemical properties such as lower melting and ignition temperatures and shorter burning times. Favorably, tremendous developments in the synthesis technology of nano-materials have also been made in the recent past. Several metal-based energetic materials with nano-sized particles such as nano-thermites, nano-fluids, and metalized solid propellants are being actively studied. The “green” reactive mixture of nano-aluminum particles and water/ice mixture (ALICE) is being explored for various applications such as space and underwater propulsion, hydrogen generation, and fuel-cell technology. Strand burning experiments indicate that the burning rates of nano-aluminum and water mixtures surpass those of common energetic materials such as ammonium dinitramide (ADN), hydrazinium nitroformate (HNF), and cyclotetramethylene tetranitramine (HMX). Sufficient understanding of key physicochemical phenomena is, however, not present. Furthermore, the most critical parameters that dictate the burning rate have not been identified. A multi-zone theoretical framework is established to predict the burning properties and flame structure by solving conservation equations in each zone and enforcing the mass and energy continuities at the interfacial boundaries. An analytical expression for the burning rate is derived and physicochemical parameters that dictate the flame behavior are identified. An attempt is made to elucidate the rate-controlling combustion mechanism. The effect of bi-modal particle size distribution on the burning rate and flame structure are investigated. The results are compared with the experimental data and favorable agreement is achieved. The ignition and combustion characteristics of micron-sized aluminum particles can also be enhanced by replacing the inert alumina layer with favorable metallic coatings such as nickel. Experiments indicate that nickel-coated aluminum particles ignite at temperatures significantly lower than the melting point of the oxide film, 2350 K due to the presence of inter-metallic reactions. Nickel coating is also attractive for nano-sized aluminum particles due to its ability to maximize the active aluminum content. Understanding the thermo-chemical behavior of nickel-aluminum core-shell structured particles is of key importance to both propulsion and material synthesis applications. The current understanding is, however, far from complete. In the present study, molecular dynamics simulations are performed to investigate the melting behavior, diffusion characteristics, and inter-metallic reactions in nickel-coated nano-aluminum particles. Particular emphasis is on the effects of core size and shell thickness on all important phenomena. The properties of nickel-coated aluminum particles and aluminum-coated nickel particles are also compared. Considerable uncertainties pertaining to the ignition characteristics of nano-aluminum particles exist. Aluminum particles can spontaneously burn at room temperature, a phenomenon known as pyrophoricity. This is a major safety issue during particle synthesis, handling, and storage. The critical particle size below which nascent particles are pyrophoric is not well known. Energy balance analysis with accurate evaluation of material properties (including size dependent properties) is performed to estimate the critical particle size for nascent particles. The effect of oxide layer thickness on pyrophoricity of aluminum particles is studied. The ignition delay and ignition temperature of passivated aluminum particles are also calculated. Specific focus is placed on the effect of particle size. An attempt is made to explain the weak dependence of the ignition delay on particle size at nano-scales.

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.

[pt] Analizam-se os principais métodos de Cálculo para determinação dos parâmetros do tiro, segundo modelos que consideram exclusivamente a variação temporal das variáveis envolvidas. Aplicam-se os métodos selecionados a exemplos de tiros reais. Comparam-se resultados teóricos com experimentais. Apontam-se as principais dificuldades relativas a obtenção dos dados relativos às características termodinâmicas e balísticas dos propelentes, determinadas nos testes de bomba manomêtrica. Aplicam-se os conceitos de função de forma geométrica e de vivacidade dinâmica dos propelentes comprovando-se a validade de ambos na previsão dos resultados de tiros. / [en] The principal methods of calculation of the parameters from the shot are analysed, according to models that take into consideration exclusively the time variation of the envolved variables. The selected methods are applied in real shots examples. Experimental and theoretical results are compared. The main difficulties concerning the obtention of data of thermodynamics and ballistics characteristics of the propellants are pointed out through tests developed in manometrics bombs. The concepts of geometric form function and dynamic vivacity of propellants are applied, conforming the validity of both to forecast the effects of the shots.

Les travaux de thèse présentés dans ce manuscrit ont porté sur l’élaboration et la caractérisation de poudres propulsives à sensibilités réduites. Ceci a été effectué par l’utilisation de matériaux énergétiques relativement insensibles ainsi que par l’emploi du procédé de Spray Evaporation Flash (SFE). Ce dernier a permis d’obtenir des poudres nanostructurées de composition ternaire. La caractérisation de ces poudres propulsives par spectroscopie Raman a permis de mettre en évidence le mécanisme de plastification de la nitrocellulose par les plastifiants employés. Des analyses de microscopie électronique à balayage ont été menées pour étudier la granulométrie de ces échantillons. Leur caractérisation par diffraction des rayons X a permis d’étudier leur structure et leur cristallisation. Des mesures de calorimétrie différentielle à balayage, des essais de tirs en tubes et en bombe manométrique, ainsi que des mesures de sensibilités à divers types de sollicitations, ont permis de montrer que les poudres obtenues sont particulièrement insensibles. / The PhD thesis presented in this manuscript focused on the elaboration and characterization of propellants with reduced sensitivities. This was accomplished by the use of relatively insensitive energetic materials, in conjunction with the application of the Spray Flash Evaporation (SFE) process. The latter made it possible to obtain nanostructured propellants of ternary composition.The characterization of these propellants by Raman spectroscopy revealed the mechanisms ruling the plasticization of nitrocellulose by the plasticizers used. Scanning electron microscopy analyzes were conducted to determine the particle size of these samples. Their characterization by X-ray diffraction allowed to study their structure and their crystallization. These propellants were shown to be particularly insensitive through analyses by differential scanning calorimetry,pyrotechnic tests in tubes and manometric vessels as well as sensitivity measurements to various types of solicitations.

Cryogenic propellants are going to be the cornerstone for effective future human space exploration. These propellants need to be stored and maintained at really low temperatures for a long duration. Accurate phase change modeling is necessary for characterizing the thermal state of future cryogenic propellant tanks and for designing systems to alleviate the self pressurization problem. Better understanding about how to properly store and manage cryogenic propellants would help greatly with In-Situ Resource Utilization (ISRU) strategies for future missions to Mars and further. Predicting the fluid flow, heat transfer, and phase change mass transfer in long term cryogenic storage using CFD models is greatly affected by our understanding of the accommodation coefficient. The kinetically limited phase change model governed by the Hertz-Knudsen-Schrage equation is the model of choice for such calculations. The value of the accommodation coefficient required for the model is unknown for cryogenic propellants. Even in the case of water, the value of the accommodation coefficient has been found to vary over three orders of magnitude based on 80 years of measurements. Experiments specifically built to study accommodation coefficient are needed to estimate the value of the accommodation coefficient and understand some of the uncertainties surrounding these models. <div><br></div><div>Two phase change models, viz. the thermally limited and the kinetically limited phase change model are implemented in OpenFOAM. Different approaches to implement the Hertz-Knudsen-Schrage equation in a sharp interface conjugate heat transfer solver are studied. Evaporation and condensation calculations for a liquid hydrogen meniscus inside an aluminum container are compared with experimental measurements. The effect of accommodation coefficient on phase change is then studied with the kinetically limited model by comparing with the thermally limited model and the experimental measurements. The uncertainties associated with the temperature and pressure measurements in the experiment are quantified to show their effect on computational predictions. Since cryogenic propellants are perfectly wetting fluids, modeling the thin-film region close to the contact line leads to a multi-scale computational problem. However, the phase change contribution from the thin-film region is approximated in these computations to show the importance of modeling the contact line region accurately to adequately capture the small local thermodynamics in that region.</div>

<p>  </p> <p>Solid composite propellants are used widely in the aerospace industry due to their desirable mechanical and performance characteristics, including their simplicity, high initial thrust and volume specific impulse. Knowledge of the mechanical properties is needed due to the stresses encountered by a solid rocket motor propellant during thermal cycling while in storage, during rapid ignition transients, and dynamic launch and flight phases. These stresses could damage the propellant grain, leading to an unplanned increase in burning surface area and subsequent catastrophic disassembly. </p> <p>Tensile testing with the conventionally used JANNAF Type C “dogbones” can be material-expensive and time-consuming, particularly if determining the propellant’s response to different strain rates and temperatures. The rapid development of propellants with novel ingredients or formulations is especially hampered by material and time constraints. Using small-scale tests, typically using “micro-dogbone” samples, tensile properties can be characterized with a strong correlation to standard JANNAF Type C samples and only use a fraction of the normally required material. The correlation between the two sample sizes can be demonstrated for a wide range of propellant formulations and environmental conditions, such as extreme temperatures used in test conditions. Propellant characterization can also be relatively slow due to the data analysis time required to ensure that samples did not contain voids or other defects. Using 2-D Digital Image Correlation (DIC) technology, a baseline behavior can be established for propellant samples that contain voids to help screen data faster, leading to a faster characterization time for propellants and reduced cost of the program. Overall, the DIC system is a promising method of non-contact strain measurement that can help characterize and screen solid composite propellants, while micro-dogbones show great promise in being able to reduce the time and cost required for characterizing novel solid propellants. </p>