Introdução: A obesidade e a dislipidemia são grandes contribuintes dos agravos cardiovasculares. O consumo de vegetais, principalmente de suas proteínas, atua de forma protetora na magnitude destes agravos. Há grandes indícios de que a proteína do amaranto possui efeito hipocolesterolemizante pela ação de peptídeos, originários de sua digestão incompleta. Objetivo: Verificar a ação, in vitro, do hidrolisado proteico do amaranto, submetido a diferentes processamentos, na solubilização micelar do colesterol e inibição da atividade enzimática HMGR. Métodos: As farinhas processadas e crua foram analisadas quanto seu teor de aminoácidos. Os isolados proteicos das farinhas do grão de amaranto tostado, extrusado e cru, foram submetidos à hidrólise enzimática e em seguida, foi elaborada uma solução de sais biliares e colesterol para avaliar a capacidade dos hidrolisados proteicos em diminuir a solubilização micelar de colesterol. Utilizaram-se os ultra filtrados (PM menor que 3 kDa) em concentração de 3 mg/mL em equivalentes de albumina, e para os de peso moleculares maiores foram utilizados 10 mg/mL. Com o intuito de verificar o mecanismo de inibição da síntese endógena de colesterol, somente, foram utilizados os hidrolisados ultra filtrados. Nos ensaios de inibição enzimática da HMGR foram utilizadas concentrações de hidrolisados (0,1, 0,5 e 1 mg/mL) para avaliar a inibição e comparar a pravastatina (inibidor conhecido). Resultados: A composição de aminoácidos demonstrou-se adequada, quando comparada a recomendação de aminoácidos essenciais para crianças de 2 a 5 anos. Os aminoácidos hidrofóbicos constituem 30 por cento do total de aminoácidos. Ao avaliar o efeito do hidrolisado na solubilização micelar do colesterol, foi observado que houve diferença (p < 0,004) devido ao processamento. O hidrolisado proteico da farinha crua (IPHc), com peptídeos de peso molecular maior que 3 kDa, reduziu a solubilização micelar do colesterol em 44,09 ± 1,5 por cento , enquanto que os hidrolisados de farinha tostada (IPHt) e extrusada (IPHe) reduziram em 31,24 ± 5,9 por cento e 24,97 ± 4,1 por cento . Já os hidrolisados com peso molecular menor que 3 kDa apresentaram pouca diferença (p < 0,03) em relação ao processamento. A redução da solubilidade micelar observada pelos IPHc e IPHe foi semelhante: 37,21 ± 1,65 por cento e 35,45 ± 0,4 por cento , respectivamente. O IPHt apresentou a menor redução de 22,47 ± 4,6 por cento . Os hidrolisados da farinha de amaranto também foram capazes de inibir a atividade da enzima HMGR em diversas concentrações. O controle da atividade normal da enzima apresentou 0,65 ± 0,05 µmol de NAPH oxidada min/mg equivalente de albumina. O IPHc, em concentrações de 0,1 e 0,5 mg/mL, apresentou efeito similar ao da pravastatina, diferindo do controle (p < 0,05), produzindo: 0,24 ± 0,03 e 0,29 ± 0,13 de µmol de NAPH oxidada min/mg equivalente de albumina. Por outro lado o IPHt apresentou efeito similar ao da pravastatina em concentração superior ao cru; em 1 mg/mL produziu 0,20 ± 0,09 de µmol de NAPH oxidada min/mg equivalente de albumina. O IPHe apresentou efeito inibidor da enzima em concentração de 0,1 mg/mL, porém menor do que o observado para a pravastatina. Conclusões: A proteína do grão de amaranto hidrolisada possui indícios de atividade hipocolesterolêmica. Sendo capaz de atuar tanto na via exógena quanto na via endógena, inibindo a absorção do colesterol e sua síntese de forma indireta. O processamento térmico diminuiu esta capacidade, mas ainda demonstra resultados significativos. Dentre os processamentos, a extrusão mostrou ter diminuído este efeito, embora os seus resultados possam ter sido influenciados pela quantidade de componentes no isolado proteico, como lipídeos e compostos fenólicos. / Introduction: Obesity and dyslipidemia are major contributors of cardiovascular diseases. The consumption of vegetables, especially their protein, acts protectively on the magnitude of these injuries. There is evidence that amaranth protein has a cholesterol-lowering effect by the action of peptides originating from its incomplete digestion. Objective: To assess the effect, in vitro, of the hydrolyzed protein of amaranth, submitted to different processes, on the reduction of the micellar solubilization of cholesterol and on the inhibition of HMGR enzyme activity. Methods: The raw and processed flours were analyzed for their content of amino acids. The isolated protein from amaranth grain flour toasted, extruded and raw, were subjected to enzymatic hydrolysis. Subsequently, it was prepared a solution of bile salts and cholesterol to assess the ability of the hydrolyzed protein to decrease the micellar solubilization of cholesterol. It was used the ultra-filtered peptides (MW up to 3 kDa) at concentration of 3 mg/mL equivalent albumin; and for higher molecular weights, it was used 10 mg/mL. In order to verify the mechanism of inhibition of the cholesterol endogenous synthesis, only it was used the hydrolyzed ultra-filtered peptides with MW < 3 KDa. In the assays of HMGR inhibition, several concentrations of peptides were used (0.1, 0.5 and 1 mg/mL) to compare the inhibition to pravastatin (a known inhibitor). Results: The amino acid composition showed to be adequate when compared to the recommendation of essential amino acids for children 2-5 years. Hydrophobic amino acids compose 30 per cent in total amino acids. When evaluating the effect of the hydrolyzate micellar solubilization of cholesterol has been observed that significant difference (p <0.004) from the processing. The peptides from raw flour hydrolyzed protein (IPHc) with a molecular weight greater than 3 kDa reduced micellar solubilization of cholesterol by 44.09 ± 1.5 per cent , while those from the roasted flour (IPHt) and extruded flour (IPHe) reduced by 31.24 ± 5.9 per cent and 24.97 ± 4.1 per cent . Peptides with a molecular weight up to 3 kDa showed little difference (p < 0.03) due to processing. The reduction of the observed micellar solubility of IPHc and IPHe were similar: 37.21 ± 0.4 per cent and 35.45 ± 1.65 per cent , respectively. The IPHt showed the smallest decrease of 22.47 ± 4.6 per cent . The peptides from amaranth flour were also able to inhibit the activity of the enzyme HMGR in various concentrations. The control of normal enzyme activity showed 0.65 ± 0.05 mol of NAPH oxidized min/mg equivalent of albumin. The IPHc at concentrations of 0.1 and 0.5 mg/mL had an effect similar to that of pravastatin, different from control (p < 0.05), yielding: 0.24 ± 0.03 and 0.29 ± 0.13 mol of the NAPH oxidized min/mg equivalent of albumin. On the other hand, IPHt showed a similar effect to higher concentration of pravastatin in the raw, and in 1 mg/mL produced from 0.20 ± 0.09 mol of oxidized NAPH min/mg equivalent of albumin. The IPHe showed the inhibitory effect on the enzyme concentration as lower as 0.1 mg/mL, but less pronounced than pravastatin. Conclusions: The peptides from hydrolysis of amaranth grain has evidence of hypocholesterolemic activity. They are able to act both in exogenously and endogenous pathways, inhibiting the absorption of cholesterol and its synthesis. The thermal processing reduces this capacity, but still shows significant results. Among the processing, extrusion deserves less attention than other one, although their results may have been influenced by the amount of the isolated protein components, such as lipids and phenolic compounds.

Introdução: A obesidade e a dislipidemia são grandes contribuintes dos agravos cardiovasculares. O consumo de vegetais, principalmente de suas proteínas, atua de forma protetora na magnitude destes agravos. Há grandes indícios de que a proteína do amaranto possui efeito hipocolesterolemizante pela ação de peptídeos, originários de sua digestão incompleta. Objetivo: Verificar a ação, in vitro, do hidrolisado proteico do amaranto, submetido a diferentes processamentos, na solubilização micelar do colesterol e inibição da atividade enzimática HMGR. Métodos: As farinhas processadas e crua foram analisadas quanto seu teor de aminoácidos. Os isolados proteicos das farinhas do grão de amaranto tostado, extrusado e cru, foram submetidos à hidrólise enzimática e em seguida, foi elaborada uma solução de sais biliares e colesterol para avaliar a capacidade dos hidrolisados proteicos em diminuir a solubilização micelar de colesterol. Utilizaram-se os ultra filtrados (PM menor que 3 kDa) em concentração de 3 mg/mL em equivalentes de albumina, e para os de peso moleculares maiores foram utilizados 10 mg/mL. Com o intuito de verificar o mecanismo de inibição da síntese endógena de colesterol, somente, foram utilizados os hidrolisados ultra filtrados. Nos ensaios de inibição enzimática da HMGR foram utilizadas concentrações de hidrolisados (0,1, 0,5 e 1 mg/mL) para avaliar a inibição e comparar a pravastatina (inibidor conhecido). Resultados: A composição de aminoácidos demonstrou-se adequada, quando comparada a recomendação de aminoácidos essenciais para crianças de 2 a 5 anos. Os aminoácidos hidrofóbicos constituem 30 por cento do total de aminoácidos. Ao avaliar o efeito do hidrolisado na solubilização micelar do colesterol, foi observado que houve diferença (p < 0,004) devido ao processamento. O hidrolisado proteico da farinha crua (IPHc), com peptídeos de peso molecular maior que 3 kDa, reduziu a solubilização micelar do colesterol em 44,09 ± 1,5 por cento , enquanto que os hidrolisados de farinha tostada (IPHt) e extrusada (IPHe) reduziram em 31,24 ± 5,9 por cento e 24,97 ± 4,1 por cento . Já os hidrolisados com peso molecular menor que 3 kDa apresentaram pouca diferença (p < 0,03) em relação ao processamento. A redução da solubilidade micelar observada pelos IPHc e IPHe foi semelhante: 37,21 ± 1,65 por cento e 35,45 ± 0,4 por cento , respectivamente. O IPHt apresentou a menor redução de 22,47 ± 4,6 por cento . Os hidrolisados da farinha de amaranto também foram capazes de inibir a atividade da enzima HMGR em diversas concentrações. O controle da atividade normal da enzima apresentou 0,65 ± 0,05 µmol de NAPH oxidada min/mg equivalente de albumina. O IPHc, em concentrações de 0,1 e 0,5 mg/mL, apresentou efeito similar ao da pravastatina, diferindo do controle (p < 0,05), produzindo: 0,24 ± 0,03 e 0,29 ± 0,13 de µmol de NAPH oxidada min/mg equivalente de albumina. Por outro lado o IPHt apresentou efeito similar ao da pravastatina em concentração superior ao cru; em 1 mg/mL produziu 0,20 ± 0,09 de µmol de NAPH oxidada min/mg equivalente de albumina. O IPHe apresentou efeito inibidor da enzima em concentração de 0,1 mg/mL, porém menor do que o observado para a pravastatina. Conclusões: A proteína do grão de amaranto hidrolisada possui indícios de atividade hipocolesterolêmica. Sendo capaz de atuar tanto na via exógena quanto na via endógena, inibindo a absorção do colesterol e sua síntese de forma indireta. O processamento térmico diminuiu esta capacidade, mas ainda demonstra resultados significativos. Dentre os processamentos, a extrusão mostrou ter diminuído este efeito, embora os seus resultados possam ter sido influenciados pela quantidade de componentes no isolado proteico, como lipídeos e compostos fenólicos. / Introduction: Obesity and dyslipidemia are major contributors of cardiovascular diseases. The consumption of vegetables, especially their protein, acts protectively on the magnitude of these injuries. There is evidence that amaranth protein has a cholesterol-lowering effect by the action of peptides originating from its incomplete digestion. Objective: To assess the effect, in vitro, of the hydrolyzed protein of amaranth, submitted to different processes, on the reduction of the micellar solubilization of cholesterol and on the inhibition of HMGR enzyme activity. Methods: The raw and processed flours were analyzed for their content of amino acids. The isolated protein from amaranth grain flour toasted, extruded and raw, were subjected to enzymatic hydrolysis. Subsequently, it was prepared a solution of bile salts and cholesterol to assess the ability of the hydrolyzed protein to decrease the micellar solubilization of cholesterol. It was used the ultra-filtered peptides (MW up to 3 kDa) at concentration of 3 mg/mL equivalent albumin; and for higher molecular weights, it was used 10 mg/mL. In order to verify the mechanism of inhibition of the cholesterol endogenous synthesis, only it was used the hydrolyzed ultra-filtered peptides with MW < 3 KDa. In the assays of HMGR inhibition, several concentrations of peptides were used (0.1, 0.5 and 1 mg/mL) to compare the inhibition to pravastatin (a known inhibitor). Results: The amino acid composition showed to be adequate when compared to the recommendation of essential amino acids for children 2-5 years. Hydrophobic amino acids compose 30 per cent in total amino acids. When evaluating the effect of the hydrolyzate micellar solubilization of cholesterol has been observed that significant difference (p <0.004) from the processing. The peptides from raw flour hydrolyzed protein (IPHc) with a molecular weight greater than 3 kDa reduced micellar solubilization of cholesterol by 44.09 ± 1.5 per cent , while those from the roasted flour (IPHt) and extruded flour (IPHe) reduced by 31.24 ± 5.9 per cent and 24.97 ± 4.1 per cent . Peptides with a molecular weight up to 3 kDa showed little difference (p < 0.03) due to processing. The reduction of the observed micellar solubility of IPHc and IPHe were similar: 37.21 ± 0.4 per cent and 35.45 ± 1.65 per cent , respectively. The IPHt showed the smallest decrease of 22.47 ± 4.6 per cent . The peptides from amaranth flour were also able to inhibit the activity of the enzyme HMGR in various concentrations. The control of normal enzyme activity showed 0.65 ± 0.05 mol of NAPH oxidized min/mg equivalent of albumin. The IPHc at concentrations of 0.1 and 0.5 mg/mL had an effect similar to that of pravastatin, different from control (p < 0.05), yielding: 0.24 ± 0.03 and 0.29 ± 0.13 mol of the NAPH oxidized min/mg equivalent of albumin. On the other hand, IPHt showed a similar effect to higher concentration of pravastatin in the raw, and in 1 mg/mL produced from 0.20 ± 0.09 mol of oxidized NAPH min/mg equivalent of albumin. The IPHe showed the inhibitory effect on the enzyme concentration as lower as 0.1 mg/mL, but less pronounced than pravastatin. Conclusions: The peptides from hydrolysis of amaranth grain has evidence of hypocholesterolemic activity. They are able to act both in exogenously and endogenous pathways, inhibiting the absorption of cholesterol and its synthesis. The thermal processing reduces this capacity, but still shows significant results. Among the processing, extrusion deserves less attention than other one, although their results may have been influenced by the amount of the isolated protein components, such as lipids and phenolic compounds.

<p dir="ltr">Smart energetics are energetic materials (propellants, explosives, and pyrotechnics) with on/off capabilities or in real time modification of combustion behavior. Solid propellants are known for many positive qualities such as their simplicity and low cost but also their glaring lack of active burning rate control. Previous proposed methods of active control of solid propellants include pintle valve actuation and electronically controlled solid propellants, however there is a need for improved methods. Surface area modification is one proposed method and can be employed in real time to affect the burning behavior of solid propellants. To this end, derivations were conducted regarding a slot adjacent to a solid propellant strand and the pressure and slot width threshold conditions that allow for burning to occur inside of the adjacent slot. The derivations considered different modes of combustion (convective and conductive) and combustion threshold conditions. The derivations resulted in five equations that were curve fit to existing literature for validation resulting in high R squared values. A demonstration of the creation of an adjacent slot with a piezoelectric actuator, a mini case study of the adjacent slot proposal, and a discussion of methods to create an adjacent slot as well as the effect of propellant selection on convective burning in slots were all done to follow up on the promising results of the theoretical work. </p><p dir="ltr">Furthermore, flexoelectricity is the coupling between strain gradient and charge generation and has been considered to modify the combustion characteristics of energetic materials. This work measured the flexoelectric properties of polymers and their associated energetic composites including polyvinylidene fluoride (PVDF), micron aluminum (μAl)/PVDF, nano aluminum (nAl)/PVDF, poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)), nAl/P(VDF-TrFE), poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)), μAl/P(VDF-HFP), hydroxylterminated polybutadiene (HTPB), ammonium perchlorate (AP)/HTPB, μAl/AP/HTPB, polytetrafluoroethylene (PTFE), and polydimethylsiloxane (PDMS). The measurements made on PVDF, μAl/PVDF, P(VDF-TrFE), P(VDF-HFP), PTFE, and PDMS were all within or near to the range of measurements from the literature. Novel measurements were made on nAl/PVDF, nAl/P(VDF-TrFE), μAl/P(VDF-HFP), HTPB, AP/HTPB, and μAl/AP/HTPB. Additionally, the effect of porosity, particle additions (μAl, nAl, or AP), and manufacturing method (3D printing, casting, different 3D printers, etc.) on the flexoelectric performance of these samples was investigated. It was found that large pores (millimeter scale) added via the infill pattern of 3D printed PVDF and Al/PVDF samples decreased the effective flexoelectric effect relative to the near full density control samples. This contrasts with previous work showing that adding small (micron scale) pores increases the flexoelectric performance of various polymers and energetic materials. Mixed results were found with respect to the effect of particle additions (μAl, nAl, or AP) on the flexoelectricity of a variety of materials. This may be explained by the competing effect of particle additions adding extra local strain gradients which amplify flexoelectricity but also replace some polymer binder material (PVDF, P(VDF-TrFE), P(VDF-HFP), and HTPB) with the particle additions (μAl, nAl, and AP) which are typically less flexoelectric. Our work demonstrates that manufacturing method does affect the flexoelectric properties of polymers and energetic composites. Lastly, our flexoelectric measurements of P(VDF-HFP) and PTFE may help explain accidents related to Magnesium-Teflon®-Viton® (MTV) flare systems that have, in many cases, been attributed to electrostatic discharge.</p>

<p dir="ltr">Examination of gaseous detonation flow-fields represents a unique experimental challenge. High-speed shock interaction within a reactive mixture manifests combustion modes across a range of spatial-temporal scales. While the kinetics along the leading front are often characterized by adiabatic compression, simultaneously strong shear induces turbulent mixing in downstream portions of the flow. This all occurs within a wave structure typically traveling near 2000 m/s. To advance fundamental understanding, high-resolution diagnostics are required to make quantitative, time-resolved measurements of the unsteady detonation propagation.</p><p dir="ltr">In this work, detonations are experimentally studied in a single-shot, narrow channel using non-intrusive optical diagnostics. The change in wave structure between mixtures fueled by methane and natural gas was characterized using 175 kHz schlieren and CH* chemiluminescence imaging. The effect of the higher order alkanes in natural gas is speed up the reaction kinetics and produce a wave structure with smaller spatial scales and in which reaction occurs closer to the leading shock front.</p><p dir="ltr">A schlieren system operating at a rate of 5 MHz is then implemented to resolve the spatial-temporal oscillation of the leading shock front. These images are used to compute the lead shock normal speed, which enables a statistical analysis of the oscillating shock velocity. The moments of distribution are compared with computed instability levels of sixteen mixtures and a positive correlation is found. Simultaneous chemiluminescence is used to create joint distribution of shock speed and chemical length scale, which are then compared with the quasi-steady reaction zone solution.</p><p dir="ltr">Experiments are performed with highly nitrogen diluted mixtures of methane and oxygen to examine specific flow features. Different regimes of transverse wave reactivity are observed, from nonreactive to detonative. The transverse detonation wave structure is modeled using oblique shock relations and good agreement is found. The chemical length scales within the configuration are compared to the relevant expansion scales to explain the observed near-steady propagation. Distinct reactive processes following transverse wave collision are also captured. In one instance an explosion immediately occurs, while in the other a reactive gas jet grows from the point of collision. An unsteady reaction zone model is applied to understand the reaction mode within the jet.</p><p dir="ltr">Lastly, 300 kHz OH PLIF is performed to study small scale and weak reaction structures within the flow. The evolution of deflagrative burning mechanisms becomes resolvable using this technique, which highlights the benefit of its use.</p>

<p>The ignition of energetic materials, and specifically solid propellants, is a complex process</p> <p>that must be safe, consistent, and precisely controlled. There is a wide range of applications with</p> <p>specific ignition requirements for solid propellants including inflation of airbags, propulsion</p> <p>systems (including rockets), as well as arm and fire devices. Currently, electrical or percussion</p> <p>pyrotechnic igniters are most the commonly used ignition systems. These systems must be</p> <p>carefully designed to deliver the proper amount of energy to a specified surface area of the</p> <p>propellant. A photon light source (i.e. flash or laser-based, ranging from UV to IR wavelengths)</p> <p>can potentially be used to ignite energetic materials with lower input energy and more precise</p> <p>spatial and temporal control, thereby improving safety and reliability by eliminating electrical</p> <p>systems used in pyrotechnic igniters. In addition, they could be potentially safer from stray</p> <p>electrical charges causing unintentional ignition.</p> <p>The purpose of this work is to further explore the potential of optical ignition for energetic</p> <p>systems and identify ideal materials that can be used for optical ignition. In order to identify</p> <p>optically sensitive materials, we will study ignition energies, ignition delays, flame temperatures,</p> <p>and other combustion characteristics for possible energetic materials. This research addresses a</p> <p>gap in understanding of optical ignition for energetic materials, as finding and integrating materials</p> <p>that are optically sensitive while still being practical can be extremely challenging. These</p> <p>challenges include: (1) a lack of absorptivity to optical wavelengths in the UV to low-IR range,</p> <p>and subsequently, a very high sensitivity to input energy at the absorptive wavelengths that makes</p> <p>sustained ignition difficult, (2) a need for full density materials in practical energetic systems,</p> <p>while optically sensitive materials are exceedingly difficult to ignite as packing density increases</p> <p>due to heat transfer, and (3) the lack of research regarding novel fuels/oxidizers for the specific</p> <p>purpose of optical ignition.</p> <p>Metal/fluoropolymer energetic materials have been of interest to the energetic materials</p> <p>community for many years. Due to fluorine’s excellent oxidizing ability, they can be used in</p> <p>composite materials with metal fuels to produce energetic materials for a wide variety of</p> <p>applications. Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polycarbon</p> <p>13</p> <p>monofluoride (PMF), and terpolymers such as tetrafluoroethylene, hexafluoropropylene, and</p> <p>vinylidene fluoride (THV) have already seen extensive use in applications ranging including</p> <p>protective coatings, strain gauges, and electronics. However, when combined with metals such as</p> <p>lithium, magnesium, aluminum, or titanium, they also present an opportunity for a wide variety of</p> <p>energetic materials. For this study, metal/fluoropolymer composites present a novel opportunity</p> <p>for exploring optical ignition of widely absorptive, full-density energetic materials. This work will</p> <p>characterize the combustion and sensitivity of metal/fluoropolymer composites to provide novel</p> <p>materials for optical ignition of energetics.</p> <p>Specifically, this work will begin with finding a suitable energetic composite that is optically</p> <p>sensitive. Once this material has been identified, research will be done to thoroughly characterize</p> <p>the optically sensitive composite by looking at additive manufacturability, flame temperatures, and</p> <p>ignition sensitivities from various methods and formulations. Once the material has been</p> <p>thoroughly characterized, it will be implemented into solid propellants to test the feasibility of the</p> <p>material in practical energetic systems. Finally, the lessons learned from this work will be applied</p> <p>to novel formulations to identify new optically sensitive energetic composites.</p>

<p> Embedding thermally conductive wires in a propellant has been known as an alternative means of increasing the burning rate of the propellant. The wires conduct heat into the propellant, preheating the material surrounding the wire and locally increasing the burning rate around the wire. As the propellant burns, a cone forms around the wire, exposing more burning surface area, which in turn increases the chamber pressure and consequently the bulk burning rate of the propellant. Likewise, embedded reactive wires have been considered in solid propellants for decades. Typically, these wires have been metal-metal reactive materials (intermetalics), but more recently metal-fluoropolymer materials have been considered. These reactive wires are consumable energetic materials that burn faster than the propellant, which allows them to expose more burning surface area by igniting the propellant faster than the burning front can proceed. Some of these reactive wire materials have also been shown to be additively manufacturable, allowing them to be printed in complex geometries, which further increases the tailorability of the burning surface profile. Previous studies on inert wires have largely focused on double base formulations, but few have considered composite propellants. These studies cast the wires against a window in order to visualize the burning that may affect the results. A few studies have also been performed with embedded reactive wires at elevated pressures, again cast against a window, which may have affected the burning dynamics by acting as an additional path for heat loss. This work studied whether the window affected the deflagration dynamics of embedded wire samples by comparing the combustion of windowed samples to full strand samples with propellant surround all sides of the wire and visualized with dynamic X-rays. High purity copper and silver wire were embedded in diameters of 0.405, 0.644, and 0.812 mm (26, 22, and 20 AWG) as inert, thermally conductive wires. A 20 wt. % active nanoscale aluminum and polyvinylidene fluoride reactive wire extruded using a 1.6 mm nozzle was also embedded for comparison to the inert wires. The windowed samples were tested in open air and in a Crawford strand burner at elevated pressures, using a high speed camera to view how the deflagration progressed along the wire against the window. The full strand samples were tested in open air using X-ray radiography to view the cone forming around the embedded wire. A burning rate enhancement was able to be measured from the burning profile around the wire. No statistically significant differences between the average measurements of windowed samples and full strand samples were found except in the case of 20 AWG Ag wire. The burning rate enhancement of the reactive wire was found to increase with increasing pressure, whereas the inert wires showed a decrease in burning rate enhancement. This effect is due to the reaction rate of the reactive wire increasing with pressure, whereas heat conduction along a metal wire is not dependent on pressure. </p>

La réduction des dimensions des dispositifs MOSFET devient de plus en plus complexe a réalisé, et les nouvelles technologies MOSFET se confrontent à de fortes difficultés. Pour surmonter ce problème, une nouvelle technique, appelée intégration 3D VLSI, est étudiée : remplacer la structure plane conventionnelle par un empilement vertical de transistors.En particulier, l’intégration 3D séquentielle ou CoolCube™ au CEA-Leti permet de profiter pleinement de la troisième dimension en fabriquant séquentiellement les transistors. La réalisation d’une telle intégration apporte une nouvelle contrainte, celle de fabriquer le transistor du dessus avec un budget thermique faible (inférieur à 500°C), afin de préserver les performances du transistor d'en dessous. Puisque ce budget thermique est principalement influencé par l'activation des dopants, plusieurs techniques innovatrices sont actuellement investiguées au CEA-LETI, afin de fabriquer le drain et la source. Dans ce manuscrit, nous utiliserons la recristallisation en phase solide comme mécanisme pour activer les dopants (inférieures à 600 °C). L’objectif de cette thèse est donc de fabriquer et de caractériser des transistors dont l’activation des dopants est réalisée grâce à ce mécanisme, afin d’atteindre des performances similaires à des transistors réalisés avec un budget thermique standard. Ce travail est organisé autour de l’activation des dopants, et en trois chapitres, où chaque chapitre est spécifique à une intégration (« Extension Last »/ « Extension First », « Gate Last »/ « Gate First ») et à une architecture (FDSOI, FINFET) considérées. Ces chapitre permettront, grâce aux caractérisations électriques, morphologiques et aux simulations, de développer un procédé de recristallisation stable à 500°C, à la fois pour les nMOS et les pMOS, et de proposer de nouveaux schémas d’intégrations, afin de réaliser des transistors à faible budget thermique et compatibles avec l’intégration 3D Séquentielle. / The down scaling of MOSFET device is becoming harder and the development of future generation of MOSFET technology is facing some strong difficulties. To overcome this issue, the vertical stacking of MOSFET in replacement of the conventional planar structure is currently investigated. This technique, called 3D VLSI integration, attracts a lot of attention, in research and in the industry. Indeed, this sequential stacking of transistor enables to gain in density and performance without reducing transistors dimensions.More specifically, 3D sequential integration or CoolCube™ at CEA-Leti enables to fully benefit of the third dimension by sequentially manufacturing transistors. Implementing such an integration provides the new constraint of manufacturing top transistor with low thermal budget (below 500°C) in order to preserve bottom-transistor performances. As most of the thermal budget is due to the dopant activation, several innovative techniques are currently investigated at CEA-LETI.In this work, solid phase epitaxy regrowth will be used as the mechanism to activate dopants below 600°C. The aim of this thesis is thus to manufacture and to characterize transistors with low-temperature dopant activation, in order to reach the same performance as devices manufactured with standard thermal budget. The work is organized around the dopant activation, and in three chapters, according to each considered integration scheme (Extension Last/ Extension First, Gate Last/ Gate First) and architecture (FDSOI, FINFET). These chapters, assisted by relevant simulations, electrical and morphological characterizations, will enable to develop a new and stable 500°C recrystallization process for both N and P FETs, and to propose new integration schemes in order to manufacture transistors with low thermal budget and compatible with the 3D sequential integration.

Les zones de cisaillement constituent des objets structuraux communs de la lithosphère. À grande échelle, elles sont le siège principal des déplacements entre plaques tectoniques, accommodant de grandes quantités de déformation. La compréhension de leur comportement mécanique dans le temps et l'espace est donc essentielle pour la connaissance générale de la dynamique de la lithosphère. La température joue un rôle majeur sur la loi de comportement rhéologique qui caractérise le domaine ductile (en profondeur), réduisant alors efficacement la résistance mécanique. Chaque roche possède en outre des propriétés mécaniques intrinsèques qui varient en fonction de sa composition minéralogique, de sa texture et de sa structure interne. Or, en l'absence de grandeurs directement mesurables en profondeur, la rhéologie de la lithosphère demeure sujette à diverses interprétations. Le comportement mécanique des zones de cisaillement est d'autant plus méconnu qu'elles sont le siège d'intenses changements de la nature des roches et de perturbations thermiques majeures. En particulier, l'énergie mécanique qui y est convertie en chaleur (shear heating) peut engendrer une étroite interrelation entre thermique et mécanique. Ce travail de thèse vise à contribuer à la connaissance générale de la rhéologie des zones de cisaillement lithosphérique. Une approche originale a été mise en place, se basant sur l'évolution thermique aux abords et au sein des zones de cisaillement. Sur la base de modèles numériques thermo-cinématiques 2-D et de développements analytiques, la variabilité de premier ordre de l'évolution et de la perturbation thermique est analysée et quantifiée au regard de l'influence des trois processus thermiques majeurs que sont la diffusion, l'advection et le shear heating. Les résultats sont confrontés aux signatures thermiques métamorphiques associées aux chevauchements intra-continentaux pour lesquels les influences des processus d'accrétion et d'érosion sont également examinées. Le cas du Main Central Thrust (Himalaya), associé à une inversion thermique métamorphique bien développée, est pris comme exemple de référence. Nos résultats quantitatifs mettent en avant le rôle crucial du shear heating, notamment de la variabilité de la résistance mécanique des zones de cisaillement. L'accent est mis sur l'importance des paramètres de fluage des roches. L'étude de zones de cisaillement centimétriques développées au sein de la granodiorite du Zillertal (fenêtre des Tauern, Alpes) à la faveur de faibles variations de la composition minéralogique révèle l'extrême sensibilité de la rhéologie des roches ignées représentatives de la croûte continentale. Les conséquences de cette variabilité intense à petite échelle sont finalement discutées au regard des rhéologies classiquement considérées dans les modèles qui s'intéressent aux processus qui régissent la dynamique de la lithosphère. / Shear zones are common structural features in the lithosphere and occur at various scales (from microscopic to lithospheric). At the lithospheric scale, they concentrate most of the relative movements between tectonic plates, and therefore, accommodate a high amount of strain. Consequently, the understanding of both their spatial and temporal mechanical behaviour is crucial for the general knowledge of the lithosphe dynamics. Rheology of rocks, which define their mechanical behaviour, is controlled by physical laws that predict how they deform under some stresses. Temperature plays a major role in the creep-dislocation behaviour, which characterizes the ductile domain (in depth), decreasing efficiently the rock strength. Furthermore, each rock has intrinsic mechanical properties, which depend on its mineralogical composition, texture and internal structures. However, due to the lack of data directly measurable deeper than a few kilometres, the lithosphere rheology, and in particular the continental lithosphere remains subject to drastically different interpretations. The mechanical behaviour of major shear zones is not fully understood, as they are the location of intense changes of both the rock internal nature and major thermal perturbations. Especially, the mechanical energy, converted into heat (shear heating) causes a close interaction between thermal ad mechanical evolutions. This thesis aims to better understand the rheological state of lithospheric scale shear zones. For this purpose, we used an original approach, based on the temperature field evolution around and within such shear zones. From 2D numerical thermo-kinematic models and analytical developments, the first order variability of thermal evolution and perturbation is anal- ysed and quantified with respect to the impact of three major thermal processes, defined as diffusion, advection and shear heating. Results are compared to metamorphic thermal signatures associated to intra-continental thrust zones for which the influence of both accretion and erosion was also investigated. The case of the Main Central Thrust (MCT) in the Himalayas, whose the inverse metamorphic thermal zonation has been extensively studied, was chosen as the main natural analogue. Our quantitative results highlight the crucial role of shear heating, and more particularly of mechanical strength variability within shear zones. We thus emphasise on the importance of rock creep parameters. The study of centimetre-scale shear zones, which developed within the granodiorite of the Zillertal nappe (Tauern window, Tyrol, Alps) thanks to little local variations of the mineralogical composition, reveals the extreme sensitivity of igneous rocks rheology, representative of the continental crust. The consequences of such an intense variability, revealed at small scale are finally discussed with regard to rheologies usually considered in models that focus on processes controlling lithosphere dynamics.

<p dir="ltr">Phosphor thermography is an effective technique for making spatially resolved temperature measurements on surfaces, however little consideration has been given to incorporating the phosphors inside crystalline materials to make internal measurements. Doing so would grant optical access to the phosphors through the crystal. In this work, we prepared a thermographic energetic composite via fast crash encapsulation of BaMgAl₁₀O₁₇:Eu (BAM) in ammonium perchlorate (AP) crystals, which enabled the use of phosphor thermography to spatially resolve the temperature of the energetic composite. We demonstrate that the temperature measurements show good agreement with thermocouple measurements. The ability to calibrate the material was also demonstrated and compared to the response in dynamic thermal environments. Usability limits as well as thermal stability issues of the composite were also investigated and discussed. The successful encapsulation of BAM within AP and demonstration of thermographic behavior in the composite, indicate the viability of using encapsulation as a method to produce thermographic energetic composites.</p>

<p dir="ltr">Partial methane oxidation (PMO) to methanol is a desirable route for upgrading natural and shale gas resources to liquid chemical intermediates and has been extensively studied on Cu-zeolites. Prior work has studied the stoichiometric PMO reaction on O₂-activated Cu-zeolites, leading to several proposals for candidate O_x-bridged Cu active site structures. More recent studies have investigated the catalytic PMO reaction and have reported that Cu-chabazite (CHA) zeolites tend to exhibit the highest methane oxidation rate (per Cu) among other Cu-zeolite topologies. Multiple studies have reported that decreasing the Cu site density and increasing the framework Al density increase the selectivity towards methanol, but have proposed different mechanistic explanations. Here, we study the influence of Cu active site distribution, which was altered by varying the extraframework Cu site density and the arrangement of framework Al atoms, on the kinetic parameters governing continuous PMO. The number of redox active Cu species was quantified through linear combination fitting of XANES spectra collected under <i>in situ</i> and transient conditions after reactant (O₂) cut-off, and the Cu speciation was investigated with XAS. Total methane oxidation rates and individual product formation rates (CH₃OH, CO, CO₂), normalized per total Cu, increased with Cu density because this influenced the speciation of Cu formed during the reaction. All Cu-CHA samples showed PMO rates that were nearly first-order in CH₄ pressure, consistent with prior reports that C-H activation in CH₄ is the rate limiting step. Samples with differing framework Al arrangement, but fixed extraframework Cu density, showed formation rates of over-oxidation products (e.g., CO₂) that had different apparent reaction orders in O₂, implying differences in the Cu active sites formed during reaction. Changes to Cu oxidation states were monitored with <i>in situ</i> XAS. Samples were first subjected to an oxidative pretreatment (723 K, 5 kPa O₂) and then to catalytic PMO conditions to reach steady-state. Steady-state XANES spectra collected after O₂ was removed from the reactant stream showed the expected reduction from Cu(II) to Cu(I), and the fraction of CH₄-reducible Cu(II) sites decreased with increasing Cu content; increasing the CH₄ pressure ten-fold increased the number of CH₄-reducible sites by a factor of ~1.5. These spectroscopic and kinetic observations suggest there are a mixture of Cu site types that are present during catalysis, each with different intrinsic reactivity toward CH₄ and selectivity to CH₃OH. To rationalize these observations, a reaction mechanism is proposed for a two-site model and used to derive rate expressions that describe apparent reaction orders for the total CH₄ oxidation rate and product formation rates on Cu-CHA zeolites of varying Cu content.</p><p dir="ltr">Additional routes for CH₄ activation include partial CH₄ oxidation over Fe zeolites that convert CH₄ at ambient temperature following an activation in nitrous oxide (N₂O), or through CH₄ dehydroaromatization (DHA) to benzene over Mo zeolites under non-oxidative conditions. Prior work on PMO over Fe-zeolites has identified candidate active site structures, but the influence of zeolite structural properties on ion-exchanged Fe speciation remains unclear. This work sought to understand the interaction of Fe with the zeolite framework during solvent-assisted deposition procedures and subsequent thermal treatments. In pursuit of this objective, Fe uptake isotherms were measured, and Fe speciation was characterized with UV-Vis spectroscopy and H₂ temperature programmed reduction (H₂ TPR). Increased framework Al site pairing increased the uptake of Fe in CHA zeolites, and high temperature treatments (723 K) resulted in the formation of oligomeric Fe structures as indicated by UV-vis. In CH₄ DHA over Mo-MFI, a principal challenge is the irreversible loss of catalytic reactivity with repeated reaction-regeneration cycles, attributed to dealumination of the zeolite structure during high-temperature oxidative regeneration treatments that produce steam. CHA zeolites are known to be more resistant to dealumination than MFI, but its smaller pore structure prevents diffusion of benzene and other aromatic products leading to rapid coking. This work attempted to address the diffusion limitations for benzene in Mo-CHA by synthesizing crystals with nanoscale dimensions by incorporating a surfactant into the crystallization procedure, generating solids with a flake-like morphology.</p><p dir="ltr">The overarching strategy in this work was to influence the speciation of metal sites and complexes in zeolites by controlling the density and arrangement of anionic Al anchoring sites within the framework and the density of extraframework metal species. In the case of Cu-zeolites, the amount of Cu present on the material influences the structures that form during catalysis that influences both the rate and selectivity of catalytic PMO.</p>