Kyle Watson - Fast Reaction of Nano-Aluminum: A Study On Fluorination Versus Oxidation

FAST REACTION OF NANO-ALUMINUM: A STUDY ON FLUORINATION VERSUS OXIDATION BY KYLE WATSON, M.S.M.E.
A THESIS IN MECHANICAL ENGINEERING Submitted to the Graduate Faculty of Texas Tech University in Partial Fulfillment of the Requirements for the Degree of MASTER OF SCIENCE IN MECHANICAL ENGINEERING Approved
Michelle Pantoya Chairperson of the Committee Valery Levitas Jordan Berg John Borrelli Dean of the Graduate School
August 2007
Texas Tech University, Kyle Watson, August 2007
Acknowledgments
There are many people who deserve recognition and special thanks for their support and encouragements throughout my academic career. I would like to thank my family and friends for their love and support. To my wife, Heather, thank you for all of your love, selflessness, and support through my struggles, as well as, for all the laughter and joy you bring into my life. I would also like to extend my gratitude to Dr. Michelle Pantoya for her guidance in my research and in my graduate career. She has been an integral part of my intellectual growth as a student researcher and in my preparation for life after academia. I would like to recognize the combustion lab researchers, specifically Charles Crane and Shawn Stacy. Charles, your help with the procurement card and the responsibilities of the lab allowed me to focus more closely on my research. Shawn, your work with the REAL Code (Tim Tec, LLC.) program was an important addition to my research studies. Both are greatly appreciated and helped in the pursuit of my graduate degree. I also extend thanks to Dr. Mark Grimson and the Texas Tech Experimental Sciences staff for their guidance and aide in the taking of the SEM micrographs included in this work. To my Lord and Savior, you are the guiding light and the foundation for all of my accomplishments in life.
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Table of Contents
Acknowledgements............................................................................................................. ii Abstract ................................................................................................................................v List of Tables ..................................................................................................................... vi List of Figures ................................................................................................................... vii Chapter I. Introduction ....................................................................................................................1 1.1 Overview ...................................................................................................................1 1.2 Aluminum as a Fuel ..................................................................................................3 1.3 Teflon vs. Metallic Oxide as an Oxidizer .................................................................8 1.4 Open vs. Confined Burns and the Corresponding Modes of Heat Transfer ...........14 1.5 Objectives................................................................................................................16 II. Experimental...............................................................................................................18 2.1 Sample Preparation .................................................................................................18 2.2 Open Burn Setup .....................................................................................................24 2.3 Confined Burn Setup...............................................................................................25 2.4 Data Acquisition .....................................................................................................26 III. Results and Discussion ..............................................................................................33 3.1 Open Burn Tray Results..........................................................................................33 3.1.1 Results and Initial Observations ........................................................................33 3.1.2 The Effects of Particle Size and the Addition of Teflon ...................................35 3.1.3 Implications .......................................................................................................41 iii
3.2 Confined Burn Tube Results...................................................................................42 3.2.1 Results and Initial Observations (Flame Speed Measurements) .......................42 3.2.2 Results and Initial Observations (Pressure Measurements)...............................44 3.2.3 The Effects of Particle Size and the Addition of Teflon ...................................46 3.2.4 Implications .......................................................................................................54 3.3 The Effects of Confinement ....................................................................................55 IV. Conclusions ...............................................................................................................61 References..........................................................................................................................62 Appendices.........................................................................................................................66
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Abstract
The use of fluorine as an oxidizing agent in thermite reactions yields higher heats of combustion and an increase in gas production. Thus fluorination reactions have the potential to excel in situations that require high pressures, temperatures, and flame speeds. This study compares the propagation behaviors of Al/Teflon, Al/MoO3/Teflon, and Al/ MoO3 in an effort to determine the effects that the replacement of oxygen with fluorine (Teflon is 75% by weight fluorine) has upon the reaction characteristics in both open and confined configurations. Data was collected from pressure sensors and high speed recording of the reactions. The mass percent of Al was varied from 10% 90% for each composite to study the effects of composition. The composites were then further tested at the optimum stoichiometry using either 50 nanometer or 1-3 micrometer Al as the fuel to examine the effect of Al particle size on the reactions. It was found that the addition of Teflon in an open burn configuration hinders the reaction due to a loss of liberated fluorine gas to the surroundings resulting in less energy to propagate the reaction and a higher rate of incomplete combustion. Nanoscale Al produced faster flame speeds as a result of the increased sensitivity and homogeneity associated with the smaller particles. The most significant flame speeds were found in the Al/MoO3 composites in which less energy is lost in the form of escaping gas. Confining the reactions and the intermediate and product gases promotes enhanced convection yielding increased flame speeds. The reactions containing Teflon exhibit much higher pressures which have a dual effect. Initially the increasing pressures result in increasing flame speeds. However, there exists a threshold beyond which an increase in pressure suppresses the reaction and reduces the flame speed. v
List of Tables
1. Material properties of the powders used......................................................................18 2. Al/Teflon composite mass ratios and corresponding equivalence ratios.....................22 3. Al/MoO3/Teflon composite mass ratios and corresponding equivalence ratios..........23 4. Al/MoO3 composite mass ratios and corresponding equivalence ratios......................23 5. Pressure results from the 4th pressure transducer (farthest from ignition) ...................44 6. Properties of the reactions assuming ideal burns with complete combustion .............45 7. Difference between optical and acoustical wave propagation rates ............................53 8. Mach number calculations for the flame speed of the reactions..................................54 9. Approximate maximum diffusive distance for the reactions.......................................57 10. Factor of increase due to confinement of each 50 nm Al composite...........................58
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List of Figures
1. Heat of Combustion for various compositions (Fischer 1998). Al/Teflon reaction heat of combustion calculated using REAL Code (Tim Tec, LLC.), a chemical equilibrium program, under the same thermodynamic conditions assumed to generate the data from Fischer. ....................................................................................................9 2. SEM micrographs of the powders used prior to mixing. (a) 1-3 m Al provided by AAE at 10,000x magnification (b) 50 nm Al provided by Nanotechnologies at 50,000x magnification (c) 44 nm MoO3 provided by Nanotechnologies at 50,000x magnification (d) 200nm Zonyl MP-1150 (Teflon) provided by Dupont ..........................................19 3. SEM micrographs of the post-mixed composites. (a) 50 nm Al/Teflon composite (b) 50 nm Al/MoO3 composite (c) 50 nm Al/MoO3/Teflon composite All images taken at 75,000x magnification .................................................................21 4. Photograph of the open burn apparatus. Each interval corresponds to 1 cm increments used for defining a length scale for flame speed calculations. ....................................24 5. Picture of a prepared burn tube....................................................................................26 6. Picture of the instrumented confined burn apparatus. .................................................26 7. Schematic illustrating the test setup.............................................................................27 8. Consecutive still images displaying a typical confined burn. Each image corresponds to one frame at a sample rate of 40,000 fps. The front edge of luminous activity is used to calculate flame speed.......................................................................................28 9. Typical pressure trace for a 50nm Al/Teflon confined burn........................................29 10. Al/Teflon open tray burn results. .................................................................................33 11. Al/MoO3/Teflon open tray burn results. ......................................................................34 12. Al/MoO3 open tray burn results...................................................................................34 13. Gas generation in the Al/Teflon, Al/MoO3/Teflon, and Al/MoO3 reactions. Values determined using the REAL Code (Tim Tec, LLC.) chemical equilibrium program..36 vii
14. Adiabatic flame temperature in the Al/Teflon, Al/MoO3/Teflon, and Al/MoO3 reactions. Values determined using the REAL Code (Tim Tec, LLC.) chemical equilibrium program. ...................................................................................................37 15. Al/Teflon confined apparatus burn results...................................................................42 16. Al/MoO3/Teflon confined apparatus burn results........................................................43 17. Al/MoO3 confined apparatus burn results....................................................................43 18. Burning velocities of propane/air mixtures. Figures against curves show percentage C3H8. (Egerton & Levevbre, 1954)..............................................................................49 19. Effect of pressure on the combustion rate of thermite mixtures: 1) BaO2/Zr 2) MoO3/Mg 3) PbO2/Zn (Ivanov et al., 1979) .....................................................................................................50 20. 50 nm Al open and confined burn results for all composites. .....................................56
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Chapter I Introduction
1.1 Overview
The introduction of nanoscale particles into energetic materials, specifically thermite composites, has provided the means to greatly alter the combustion characteristics such as sensitivity, stability, and energy release (Aumann, Skofronick, & Martin, 1995; Miziolek, 2002). The traditional thermite reaction is defined as an exothermic reaction which involves a metal reacting with a metallic or a non-metallic oxide to form a more stable oxide and the corresponding metal or non-metal of the reactant oxide (Wang, Munir, & Maximov, 1993). A new class of thermites referred to as metastable intermolecular composites (MIC) has been defined as mixtures of nanoscale powders of reactants that exhibit thermite (high exothermicity) behavior (Miziolek, 2002). This new class of composites utilizes nanoscale powders that result in much higher propagation rates and ignition sensitivity. For example, aluminum (Al) and molybdenum tri-oxide (MoO3) composites, when using average particle sizes between 20 and 50 nanometers, have been shown to react more than 1000 times faster than traditional thermites (Aumann et al., 1995). These nanoscale composites are also capable of energy output 2 times that of high explosives (Miziolek, 2002) and producing temperatures above 3000 K (Valliappan, Swaiakiewicz, & Puszynski, 2005). The enhancement of the combustion characteristics is often credited to the decrease in diffusive distance, increased surface area, and increased homogeneity of the composite when using 1
nanoscale reactants that have smaller nominal sizes and larger surface area to volume ratios (Kubota & Serizawa, 1987). Before the introduction of MIC, classical thermites were limited in their applications due to their relatively slow energy release rate, incomplete combustion, and inability to support rapid detonation (Yang, Wang, Sun, & Dlott, 2004b). Wang et al. (1993) reported on the useful applications of thermite compositions with emphasis on synthesis and processing of materials. With the increased performance and sensitivity of MIC, the applications have become much broader. This is also attributed to the fact that MIC is semi tunable in that the reactive power, reaction propagation rate, and reactive zone temperature can be partially controlled by altering parameters such as the particle size, oxide layer thickness, density, and equivalence ratio (Miziolek, 2002; Aumann et al., 1995; Valliappan et al., 2005). The increased versatility of MICs translates into more diverse applications particularly of interest to the Department of Defense. One particularly interesting MIC is the Aluminum (Al) and Teflon composite. For the Al/Teflon reaction the fluorine from Teflon replaces oxygen from the metal oxide as the oxidizer. The reaction of Al with Teflon generates 21 GJ/m3, and the best molecular explosive generates less than 12 GJ/m3 (Yang, Wang, Sun, & Dlott, 2004a). Many thermite reactions occur in the gasless regime because their reactants and products are of condensed form (Wang, Munir, & Maximov, 1993). The Al/Teflon reaction differs as it produces a significant amount of gas. This may have substantial effects on combustion and propagation characteristics when the reaction is confined. This study compares the reaction of Al/Teflon composites, ternary composites of Al/Teflon/MoO3, and Al/MoO3 composites in both open and confined configurations while varying Al 2
particles sizes and mass percent of Al in the composition. The objective is to compare the effects of using fluorine in place of oxygen by examining flame speeds and pressure histories. Tests were conducted using nano-sized Teflon particles and/or nano sized MoO3 particles combined with nano or micron sized Al particles to compare the effects of fuel particle size in fluorination versus oxidation reactions. The composites were ignited and flame propagation behaviors were examined in both open and confined configurations.
1.2 Aluminum as a Fuel

Aluminum particles have been used extensively in energetic materials because Al is readily available and has desirable properties as a fuel in reductionoxidation reactions such as high heats of combustion and high flame temperatures (Fischer & Grubelich, 1998). One example is the addition of nano Al particles to solidrocket propellants which has improved density and specific impulse, making it a major component in many formulations (Dokhan, Price, Seitzman, & Sigman, 2002). Traditionally the Al particles used have been on the micron scale (10-6 m). Technology in materials processing has provided the means to produce nanoscale (10-9 m) aluminum powders in bulk. Particles are typically considered nano-particles at or below 100 nm diameter or at or below 100 nm in at least one dimension. The reduction of particle size from the micron to nanoscale has significant effects on the physical and material properties of Al. As particle size decreases it has been shown that there is a decrease in melting enthalpy and melting temperature, therefore a nanoscale particle will exhibit a lower 3
melting temperature than its micrometer counterpart (Eckert, Holzer, Ahn, Fu, & Johnson, 1993; Revesz, 2005; Zhang, Lu, & Jiang, 1999). This is thought to be an effect of the increase in fraction of surface atoms with the decrease in particle size (Eckert et al., 1993; Revesz, 2005; Zhang et al., 1999). The changes in thermal properties in Al are thought to have some impact upon reactions that utilize nanoscale Al particles when compared to reactions that utilize micron scale Al particles, but these effects are largely unexplored. The physical changes that occur when Al particles are reduced in size from the micron to the nanoscale play a significant role in the increased reactivity and performance of the powder mixture. As the particle size decreases the surface to volume ratio increases dramatically (i.e., on the order of 1/radius). When mixed as a composite this increase allows for an increase in the number of contact points with the oxidizer and improved mixture homogeneity (Valliappan, Swaiakiewicz, & Puszynski, 2005). The smaller size of nano particles also allows for better distribution throughout the reactant matrix leading to a more homogeneous mixture. Inherent with Al particles is an aluminum oxide (Al2O3) coating, typically a few nanometers in thickness, which acts as a passivation layer for the pure Al core (Pesiri, Aumann, Bigler, Booth, Carpenter, Dye et al., 2004). Aluminum is pyrophoric, therefore having no Al2O3 shell would result in the pure metallic particles spontaneously reacting with oxygen in the ambient air. Lips (1977) conducted experiments firing hybridpropellant rocket motors using highly aluminized fuels. High-speed photography and chemical analysis revealed that many of the Al particles only partially combusted. They believed this was largely due to the oxide layer inhibiting the reaction (Lips, 1977). One 4
side effect of using nanoscale Al particles as fuel is the increased percentage of Al2O3 which decreases the overall purity of the Al powder. Aumann, Skofronick, and Martin (1995) studied the effects of oxide layer and the use of ultra-fine grain Al on ignition sensitivities in an effort to decrease reaction sensitivity to electrical spark and friction making the composites more stable and safer to handle in bulk. They found that ignition threshold energies did not significantly decrease with increases in oxide layer thickness of up to two times. However they did note significant decreases in ignition threshold energies for ultra-fine grain Al when compared to bulk flat Al. Typically, oxidizers must diffuse through the Al2O3 shell before interaction with the pure Al core. Sometimes the oxide shell will reach its melting point (~ 2050C), which is higher than that of the pure Al core (~ 660C), allowing the already molten Al to escape and the oxidizer to react directly with the Al bypassing the diffusion stage (Friedman & Macek, 1962; Revesz, 2005). It has been shown in recent studies by Levitas, Asay, Son, and Pantoya (2005) that direct contact with the pure Al can occur under rapid heating conditions through an alternate mechanism, referred to as a dispersion mechanism, which promotes enhanced burn rates. Levitas et al. (2005) concluded that the different thermal expansion rates of Al and Al2O3 and the volumetric strain from the melting of Al lead to a tremendous build up of pressure on the interior Al core. This pressure increase causes a large mechanical stress on the oxide shell eventually leading to its failure and potential spallation. In micron scale particles, pressure within the particle does not have the opportunity to build up because the shell is weaker. In these larger particles failure most often appears as a crack occurring at a material defect in the Al2O3 shell that allows the pure molten Al to escape and interact 5
with the surrounding oxidizer. Rai, Lee, Park, and Zachariah (2004) showed the cracking of an oxide shell and subsequent outflow of molten Al with a hot-stage TEM. Levitas et al. (2005) also states that in nanoscale particles the oxide shell is virtually free of defects and its strength approaches the theoretical strength. This allows the stress to build to a point of ultimate failure, resulting in the rupturing of the Al2O3 shell. The rupture and subsequent release of pressure disperses molten pure Al on the atomic scale throughout the surrounding oxidizer. These dispersed Al clusters lack and oxide shell and are not dependent on diffusion. The dispersion mechanism is valid only when the Al particles are subjected to rapid heating. The expansion of the pure Al core during melting causes the core to be under compression while the oxide shell is under tension (Rai et al., 2004). This leads to the oxide shell being dynamically unstable. Rai et al. (2004) show through molecular dynamics that there is a higher pressure rise in small particles and that the increased curvature of oxide shell in small particles leads to higher tension. The higher pressure and increase tension on the oxide shell lead to an increased likelihood for smaller particles to spallate, consistent with the theory by Levitas et al. (2005). Several studies have shown the effects of using nano particle Al in thermite reactions. Moore, Pantoya, and Son (2007) conducted ignition and flame speed experiments on Al/MoO3 composites for bimodal nano and micron Al particle size distributions. Their results showed that ignition delay was reduced by up to 2 times when using 80% nano particle and 20% micro particle Al when compared to tests using 100% micro particle Al. They also reported significant increases in combustion flame speed as the percent of nano particle Al was increased. Mench, Yeh, and Kuo (1998) studied the effect of particle size in aluminized propellants by replacing 30 micrometer conventional 6
Al particles with 180 nanometer Alex ( Alex is a trade name for nanometer scale Al particle manufactured by Argonide, Inc. using the exploding wire technique) particles and igniting in an optical strand burner. The addition of the Alex particles substantially enhanced the propagation rates and increased the temperature sensitivity of the solid propellants. They also found that the ignition delay time is several orders of magnitude shorter for propellants using Alex particles. Valliappan, Swaiakiewicz, and Puszynski (2005) studied the effect of nanoscale Al particles with various metallic oxides including tungsten tri-oxide (WO3), molybdenum tri-oxide (MoO3), copper oxide (CuO), and Iron Oxide (Fe2O3). Their results show flame speeds on the order of several hundreds metersper-second (up to 412 m/s) in unconfined burning configurations compared to flame speeds in the range of centimeters-per-second for micron-scale thermites in an unconfined burning configuration. Pantoya and Granier (2005) examined Al/MoO3 composites in the form of pellets as functions of Al particle size, equivalence ratio, and density. They ignited the samples with a CO2 laser and recorded ignition and flame propagation characteristics. They also conducted DSC tests to study reaction kinematics. Their results showed that the composites using nano particle Al had reduced ignition delay times of up to two orders of magnitude and that the combustion propagation rate decreased as density increased. Bockman, Pantoya, Son, Asay, and Mang (2005) studied the effects of varying the Al particle size in Al/MoO3 composite reactions. Their experiments were conducted under a confined state using an instrumented burn tube apparatus. They found that as the Al particle size was decreased the flame speed increased. They reported increases from 750 m/s to 950 m/s when decreasing the Al particle size from 121 nanometers to 80 nanometers. Further reduction of Al particle size 7
did not yield any more significant increases in flame speed suggesting the possibility of a critical diameter at which flame speed may no longer increase (Bockman et al., 2005). Malchi, Foley, Son, and Yetter (in press 2007) examined the effects of increasing the Al2O3 content in nano aluminum and copper oxide composites. The increase of Al2O3 effectively decreases the reaction flame temperature and reaction pressures due to the less efficient and complete combustion associated with adding a diluting agent into the composition. They conducted experiments in a constant volume pressure cell, open burn tray, and instrumented burn tubes. They noted substantial drops in peak pressure and pressurization rate with the increase in Al2O3. Their experiments also show a drop in flame speed with the increase of Al2O3. Malchi et al. (in press 2007) conclude that the gaseous products are of great importance to the propagation in Al/CuO composites and that adding Al2O3 effectively reduces the gas in the system inhibiting the role of convection. The decreased convective heat transfer results in slower propagation rates and combustion instabilities (Malchi et al., in press 2007)).
1.3 Teflon vs. Metallic Oxide as an Oxidizer

Teflon, C2F4, as an oxidizer is atypical because it utilizes fluorine as the oxidizing agent rather than oxygen. Fluorine is the most electronegative element making it an excellent candidate as an oxidizer in a reduction-oxidation reaction. It has the potential to exceed oxygens reactive power as illustrated in Figure 1.
C4 H8 N8 O8 (HMX) C3 H6 N6 O6 (RDX)
KJ/m^3 KJ/kg
C7 H5 N3 O6 (TNT)
Al+MoO3
4Al+3C2F4
6Al+MoO3+3C2F4 0 5000 10000 15000 20000 25000 30000 35000 40000 Heat of Combustion
Figure 1: Heat of Combustion for various compositions (Fischer 1998). Al/Teflon reaction heat of combustion calculated using REAL Code (Tim Tec, LLC.), a chemical equilibrium program, under the same thermodynamic conditions assumed to generate the data from Fischer.
Similarly, Kubota and Serizawa (1987) found magnesium (Mg) with fluorine produces a heat of combustion of 16.8 MJ/kg of Mg which is higher than the heat of combustion produced by magnesium with oxygen. Lips (1977) showed that using highly fluorinated oxidizers, in the form of liquid fluorine-oxygen mixtures, in combination with highly aluminized rocket fuels resulted in more efficient combustion of aluminum particles than reactions that contained no fluorine. The highly fluorinated reactions also exhibited an increase in regression rate and maintained the performance of nonfluorinated reactions (Lips,1977). Reactions containing fluorine may have many
favorable characteristics for specific applications, such as higher gas production, that are not attainable with the traditional reactions containing oxygen. Teflon, or polytetrafluoroethylene, is a prime candidate as a fluorine source for use in fast fluorination reactions. Manufactured by Dupont under the name Teflon, polytetrafluoroethylene is composed of a C2F4 molecular structure and has a 75% weight percent of fluorine (Kubota & Serizawa, 1987). When added to metal/metal reactions, Teflon results in a fluorine gas that improves reactivity and energy release (Parker, Ladouceur, & Russell, 2000). Mass production of polytetrafluoroethlyene began in 1946 (Koch, 2002a). Most likely Teflon was discovered to be a viable oxidizer shortly after it became commercially available (Koch, 2002a). One of the first extensively researched fluorocarbon based pyrolant was a composite of magnesium, Teflon, and the binder Viton (hexafluoropropene-vinylidenfluoride-copolymer), also known as MTV. MTV is assumed to have first been developed in the mid 1950s and was held in governmental secrecy for around 10 years due to its potential use as an infrared decoy material (Koch, 2002a). Since being released to the public, MTV has been subjected too much research and has been found to be useful in many military applications such as flares, tracers, and countermeasures as well as other applications including incendiaries, propellants, and more (Koch, 2002a). The discovery that decreasing the reactants particle sizes leads to enhanced combustion behavior has led to the desire to decrease the size of the Mg particles in MTV to achieve even better performance. Kubota and Serizawa (1987) determined that burning rate in MTV does increase as Mg particle size is decreased. The limitation of MTV is the physical particle size of Mg, which is not yet available commercially on the nanoscale. With research confirming the benefits to using nano 10
particles in energetic materials, a substitute nanoscale material with properties similar to Mg is desired. Aluminum has been studied as a viable substitute for Mg, as it can exhibit similar combustible behavior and is readily available in the nanoscale market. The Al/Teflon composite was found to have a similar stoichiometric composition when compared to Mg/Teflon composites, with Al/Teflon being 26.5% Al and Mg/Teflon being 32.7% Mg (Cudzillo & Trzcinski, 2002). Poehlein, Shortridge, and Wilharm (2001) conducted a study of the effect of adding nanoscale Al particles in the form of Alex to MTV composites. They found that mixtures containing Alex exhibited increased burn rates and similar sensitivities when compared to control MTV composites. Mg/Teflon has advantages over Al/Teflon such as a higher heat of combustion (Cudzillo & Trzcinski, 2002), but the ability to use Al particles on the nanoscale and the benefits associated with using the nanoscale particles has led to an increased interest in the Al/Teflon composite. Several studies have been conducted in an attempt to further understand the Al/Teflon reaction under various conditions. Cudzillo and Trzcinski (2002) performed calorimetric studies and differential thermal analysis (DTA) to determine heat of reaction and explore the decomposition characteristics of Al/Teflon. Their studies were conducted using 50 micrometer Al and heating the composite at 10 Kelvin per minute in nitrogen for the DTA. They found the heat of combustion to be around 7800 kJ/kg. Their DTA studies revealed 2 endothermic peaks, one occurring between 600 and 650 K and the other around 933K, and 2 exothermic peaks, both between 800 and 900 K. The endothermic peaks correspond to the melting points of both Teflon and then Al. The exothermic peaks represent the Al/C2F4 Reaction. A third endothermic reaction, proposed 11
to be corresponding to the degrading of Teflon causes the dip between the two exothermic peaks. Dolgoborodov, Makhov, Kolbanev, Streletskii, and Fortnov (2005) studied detonation in Al/Teflon mixtures. The experiments utilized the action of a shock wave on the samples to initiate the steady detonation regime. Flame speeds varied between 700 and 1300 m/s dependent upon percentage composition and density. They found that porosity had a large effect upon detonation and that burn rates would increase as stoichiometric conditions were approached. McGregor and Sutherland (2003) conducted plate impact experiments on highly porous Al/Teflon mixtures at 40% theoretical mass density (TMD) to determine conditions required for the onset of the reaction. They found that the onset of the reaction did not occur at the shock front. It occurred after the passage of the initial shock wave, possibly after the material was shocked to a higher pressure by a second larger shock wave. Parker, Ladouceur, and Russell (2000) studied Al/Teflon mixtures to examine its combustion behavior under extreme conditions. They used spectroscopy to investigate reaction mechanisms and rates. They conducted their experiments under high pressures initiating the reaction with a laser pulse. Their results showed a two stage combustion reaction. First the initial Al combustion occurred followed by the resulting carbon condensing to form graphite. Tachibana and Kimura (1988) examined the ignition and combustion control of solid propellants including Al/Teflon and HTPB-AP-Al, a conventional solid propellant, by using arc discharge. Tachibana and Kimura calculated that certain compositions of Al/Teflon composites will have a higher heat of combustion than HTPB/AP/Al. They showed that dc arc discharge coupled with a high-frequency-discharge arc initiator is
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efficient in igniting and extinguishing reactions in Al/Teflon mixtures in certain fueloxidizer ratio ranges. Burn rates could also be varied by altering the arc intensity. For the fluorine in Teflon to be available for interaction, the Teflon must first be degraded. The thermal decomposition of Teflon is the reverse reaction of its polymerization. It requires an energy input equal to the heat released during its formation, which is approximately 172 kJ/kg (Koch, 2002b). Teflon decomposes starting around 803 K and completing around 893 K (Kubota & Serizawa 1987). During this decomposition an exothermic gasification reaction occurs (Koch, 2002a) and fluorine is abundantly produced (Tachibana & Kimura, 1988). Once degraded, fluorine ions are available for interaction with the surrounding fuel. Osborne and Pantoya (in press 2007) showed via differential scanning calorimetry (DSC) and thermo-gravimetric analysis (TGA) that much of fluorine in Al/Teflon composites utilizing micron scale Al particles escaped the reaction zone before interaction with Al when subjected to slow heating conditions. This is evident by the Teflon decomposition not overlapping with the phase change in Al2O3. This means that the fluorine is available before there is a pathway for contact with the Al enabling fluorine to leave the reaction zone before interacting with the fuel. They found that the mixture lost ~25% of its mass before the reaction with Al occurred meaning that only ~17% of the Teflon reacted with the Al. Osborne and Pantoya (in press 2007) found that this did not occur when the same experiments were conducted using nanoscale Al in the Al/Teflon composites. The decomposition of Teflon and oxide layer phase change corresponds for the composites using nanoscale Al. This mixture only lost ~6% of its mass before the reaction with Al implying that 75% of the Teflon reacted with the Al. It 13
is believed that this is because of the increased sensitivity of the nano Al particles which are able to react with the fluorine oxidizer before it escapes the reaction zone. Based upon the Osborne and Pantoya (in press 2007) results the Al/Teflon composites utilizing micrometer Al particles may lose much of its fluorine oxidizer to the atmosphere before it can react with the Al fuel.
1.4 Open vs. Confined Burns and the Corresponding Modes of Heat Transfer
Conduction, convection, radiation, and acoustic/compaction are four possible modes of heat transfer in a thermite reaction. The primary mode responsible for the heat transfer will have a large effect on the combustion characteristics of any reaction. Conduction and convection are the predominant modes in most energetic materials with radiation and acoustic/compaction becoming more important upon detonation (Asay, Son, & Busse, 2004). Classical thermites are typically considered to be conduction controlled due to the slow reaction rates and the lack of gas to promote convective burning. These conduction controlled reactions typically propagate at low speeds on scales of mm/s to cm/s (Brown, Taylor, & Tribelhorn, 1998). Brown et al. (1998) found a qualitative connection between the propagation rate and the number of contact points of the fuel and oxidizer. Due to the different thermal and chemical properties of different systems, there is no direct correlation between propagation rate and the number of contact points over the different systems. However, altering the number of contact points within a single system revealed that an increase in contact points yielded an increase in flame speeds (Brown et al., 1998). Therefore, particle size will play an important role in the combustion 14
characteristics of conduction controlled reactions due to the increased in number of contact points improving the thermal transport properties of the mixture. Density effects can also inhibit the role of convective burning and promote conduction dominant reactions. When thermite powders are pressed into high density pellets, the interstitial voids are decreased. The decrease in voids inhibits gaseous fluid movement resulting in a shift towards a conductive dominant heat transfer mechanism (Prentice, Pantoya, & Gash, 2006). Convective dominant burning has been described as the deep penetration of hot product gases preheating the unreacted composites (Asay, Son, & Bdzil, 1996). The transition from conduction to convective dominant reactions leads to a substantial increase in flame speeds and energy release rates. Asay, Son, and Busse (2004) have shown flame speeds on the order of m/s to km/s for convective controlled reactions compared to the conduction controlled reactions reported by Brown, Taylor, and Tribelhorn (1998) that proceed on the order of mm/s to cm/s. Highly porous materials are more prone to convective burning due to increased gas penetration. Loose powders tend to have increased convective heat transfer because of increased bulk fluid movement (Prentice, Pantoya, & Gash, 2006). Asay et al. (2004) studied the heat transfer mechanism in MIC. They conducted confined burns in barrier, pressure, and vacuum experiments. Their experiments led to the conclusion that convection is the primary mode of heat transfer in MIC materials. Radiation and acoustic/compaction heat transfer are often not considered to be significant in classical thermite reactions. In MIC, radiation has been shown to have a negligible impact on the overall energy transfer (Begley and Brewster, in press 2007) but 15
acoustic/compaction heat transfer may play a more important role as the speeds of over Mach 1 may result in acoustical shockwaves. Further study is needed to determine the extent of acoustical/compaction roles in heat transfer through MIC. Confining reactions may change the dominant mode of energy transfer. When the reaction is confined the product gases are not able to escape the reaction zone and are propelled forward through the composite, possibly causing enhancement of the convective heat transfer (Malchi, Foley, Son, and Yetter, in press 2007). The inability for the gases to escape will also greatly increase the pressure within the tube conceivably increasing the heat transfer from acoustical/compaction. Therefore under confinement both classical thermites and MIC combustion behaviors will be greatly affected by the change in mode of heat transfer and often will exhibit much higher flame speeds.
1.5 Objectives
The Al/Teflon reactions have the potential to show increased flame speeds based on the increased amount of product gases produced from the reaction when compared to oxidation reactions as well as the higher heat of reaction as seen in Figure 1. Also by confining micron Al/Teflon reactions the fluorine is no longer able to escape the reaction zone, as seen in the experiments by Osborne and Pantoya (2007), and may exhibit a more complete and faster reaction. The objective of this study is to examine the influence of Teflon in the Al/Teflon and Al/MoO3/Teflon reactions for loose powder mixtures burning in a confined apparatus compared to burning in an open state. These reactions were also compared to the Al/ MoO3 reactions in order to better resolve the role of Teflon as an oxidizer in the reaction. This study will also examine the role of fuel particle size on the 16
reaction behaviors by examining both nano and micron scale Al fuel particles while the Teflon and MoO3 particles are constant nanoscale particles. Experiments were performed using photographic data to resolve flame speeds and piezoelectric pressure transducers to measure transient pressure behaviors. These results will impact the safe handling and usage of thermites containing Teflon as a reactant.
17
Chapter II Experimental
2.1 Sample Preparation
Sample powders of Teflon (Dupont Zonyl MP1150) and/or MoO3 were combined with either 50 nanometer or 1 -3 micrometer Al powder. The material properties and manufactures are provided in Table 1.
Table 1: Material properties of the powders used.
Particle Material Manufacturer Size Atlantic Aluminum Equipment Engineers (AEE) Aluminum Zonyl Dupont MP1150 MoO3 Nanotechnologies 44 nm 200 nm Nanotechnologies 50 nm 1 -3 m
Surface Morphology Area
Purity (%)
<1 m2/g *
Spherical
99
39.8 m2/g 510 m2/g >50 m2/g

*
Spherical Spherical Rectangular
75 99 100 99
* Estimated values
Nanotechnologies uses x-ray diffraction, TEM imaging, and BET surface area analysis to verify particle size ranges and purities. Dupont and AEE use laser microtrac systems to determine particle size ranges. Scanning electron microscopy (SEM) images 18
of the materials are provided, in Figure 2, to illustrate the extent in particle size range and amount of agglomeration in the pre-mixed state.
Figure 2: SEM micrographs of the powders used prior to mixing. (a) 1-3 m Al provided by AAE at 10,000x magnification (b) 50 nm Al provided by Nanotechnologies at 50,000x magnification (c) 44 nm MoO3 provided by Nanotechnologies at 50,000x magnification (d) 200nm Zonyl MP-1150 (Teflon) provided by Dupont
19
The powders were mixed by mass percent of pure Al ranging from 10% - 90%. The oxidizer consisted of 100% Teflon, 100% MoO3, or a mass ratio of 60% MoO3 and 40% Teflon. The Equations 2.1 - 2.3 represent the stoichiometric reactions for these mixtures.
4 Al + 3(C 2 F4 ) 4 AlF3 + 6C
(2.1)
6 Al + 3(C 2 F4 ) + MoO3 4( AlF3 ) + ( Al 2 O3 ) + 6C + Mo
(2.2)
2 Al + MoO3 ( Al 2 O3 ) + Mo
(2.3)
The mixtures are prepared by measuring the appropriate amount of powder for the desired composition and suspending the mixture in hexanes. The solution was subjected to ultrasonic waves using a Misonix Sonicator 3000 which promoted improved mixture homogeneity and breaks up agglomerates. This process consisted of applying ultrasonic waves in ten second intervals for a total of seventy seconds via a probe vibrating at ultrasonic speeds. There was a ten second span between each interval to prevent temperature buildup and possible thermal damage to the sample. The solution was transferred to a glass pan and placed on a hotplate at 90C for 10 minutes. This evaporated the hexanes leaving only the powder mixture. The powder mixture was reclaimed using a brush to collect the powder. Figure 3 displays the SEM images of the mixed powders that help visualize the homogeneity obtained in this mixing procedure. 20
Figure 3: SEM micrographs of the post-mixed composites. (a) 50 nm Al/Teflon composite (b) 50 nm Al/MoO3 composite (c) 50 nm Al/MoO3/Teflon composite All images taken at 75,000x magnification
The equivalence ratio of the powder mixtures is determined by Equation 2.4. Only pure Al, excluding the oxide layer, was considered when calculating equivalence 21
ratio. The mixing ratios and corresponding equivalence ratios are shown in Tables 2 through 4.
F A ACT = F A STO
(2.4)
Where: F= Mass of the fuel A = Mass of the oxidizer
Table 2: Al/Teflon composite mass ratios and corresponding equivalence ratios. Al size Mass % Pure Al 10 20 30 40 50 60 70 80 90 10 20 30 40 50 60 70 80 90 Mass Al Powder 10 20 30 40 50 60 70 80 90 13.33 26.67 40 53.33 66.67 80 93.33 106.67 120 Mass C2F4 Powder 90 80 70 60 50 40 30 20 10 90 80 70 60 50 40 30 20 10 Equiv. Ratio 0.231676 0.521271 0.893607 1.390056 2.085084 3.127626 4.865196 8.340337 18.76576 0.231676 0.521271 0.893607 1.390056 2.085084 3.127626 4.865196 8.340337 18.76576
50 nm Al
1 - 3 m Al
22

Table 3: Al/MoO3/Teflon composite mass ratios and corresponding equivalence ratios. Al size Mass % Pure Al 10 20 30 40 50 60 70 80 90 10 20 30 40 50 60 70 80 90 Mass Al Powder 10 20 30 40 50 60 70 80 90 13.33 26.67 40 53.33 66.67 80 93.33 106.67 120 Mass MoO3 54 48 42 36 30 24 18 12 6 54 48 42 36 30 24 18 12 6 Mass C2F4 Powder 36 32 28 24 20 16 12 8 4 36 32 28 24 20 16 12 8 4 Equiv. Ratio 0.22854362 0.514223146 0.881525393 1.371261722 2.056892583 3.085338874 4.799416027 8.227570331 18.51203325 0.22854362 0.514223146 0.881525393 1.371261722 2.056892583 3.085338874 4.799416027 8.227570331 18.51203325
50 nm Al Al size
1 - 3 m Al
Table 4: Al/MoO3 composite mass ratios and corresponding equivalence ratios. Mass % Pure Al 10 20 30 40 50 60 70 80 90 10 20 30 40 50 60 70 80 90 Mass Al Powder 10 20 30 40 50 60 70 80 90 13.33 26.67 40 53.33 66.67 80 93.33 106.67 120 Mass MoO3 90 80 70 60 50 40 30 20 10 90 80 70 60 50 40 30 20 10 Equiv. Ratio 0.296372 0.666836 1.143148 1.778231 2.667346 4.001019 6.223807 10.66938 24.00611 0.296372 0.666836 1.143148 1.778231 2.667346 4.001019 6.223807 10.66938 24.00611
50 nm Al
1 - 3 m Al
23
2.2 Open Burn Setup

The open burn experiments consisted of the combustion of evenly distributed lines of loose powder composites. The loose powder was loaded evenly into a channel milled into an acrylic block. The block is of dimensions 152 x 30 x 12 mm, and the channel is of dimensions 107.95 x 3.175 x 2.54 mm. A small piece of nicrome wire was secured at one end of the channel to provide an ignition source. An illustration of the open burn block is shown in Figure 4.
Figure 4: Photograph of open burn apparatus. Each interval corresponds to 1 cm increments used for defining a length scale for flame speed calculations.
24
The testing was conducted in an inert argon chamber to eliminate any interaction of Al with ambient air. The argon chamber is fitted with acrylic viewing windows to allow the reaction to be recorded with a high-speed camera. The reaction was initiated by applying a voltage to the nicrome wire. Propagation data was recorded via the highspeed camera.
2.3 Confined Burn Setup

The confined burn experiments consisted of the burning of the loose powder composites in an instrumented tube similar to that originally designed by Bockman et al. (2005). Polycarbonate tubes of 3.175 mm inner diameter, 25.4 mm outer diameter, and 107.95 mm length were used. The polycarbonate was chosen due to its high strength and optical clarity for viewing of the reaction. A nicrome wire was secured into one end of the tube for use as an ignition source. The powder was loaded into the tube maintaining constant mass at each composition. The sample mass varied with changes in composition due to the change in density associated with different compositions. The tubes were lightly tapped to eliminate any large voids without mechanically packing the powder. A prepared tube is shown in Figure 5. The tube was inserted into a 25.4 mm diameter opening bored through the center of a 50.8 mm square by 107.95 mm long steel testing block instrumented with 4 PCB model # 113A22 pressure transducers at 25.4 mm increments. The testing block also had an 82.55 x 25.4 mm viewing window to allow the reaction to be captured by high-speed camera. The polycarbonate tube has small (<1mm) holes that align with the pressure sensors. These 25
holes provide ports for the pressure to escape and contact the pressure sensors. The instrumented testing block is shown in Figure 6.
Figure 5: Picture of prepared burn tube.
Figure 6: Picture of instrumented confined burn apparatus.
The experiments were also conducted in the argon chamber described in section 2.2 to eliminate any possible reaction with the ambient air. The reaction was initiated by a voltage applied to the nicrome wire. Data collection was triggered manually and there was no synchronization to the application of voltage to the nicrome. Thus ignition sensitivity data was not collected and alterations in ignition sensitivity were not observed. Data was recorded in the form of flame propagation rate information from the high-speed camera and pressure histories from the pressure sensors.
2.4 Data Acquisition

A schematic illustrating the test setup is displayed in Figure 7. Data was collected in the form of high-speed video and voltage signals from pressure transducers. 26
Figure 7: Schematic illustrating the test setup.
Data is captured from a high-speed video camera and pressure transducers illustrated in Figure 9. Images from the high-speed camera are used to determine flame speed. This was accomplished by tracking the flame front, considered here as the front edge of luminous activity. A series of consecutive frames shows the progression of the flame front in the confined state in Figure 8.
27
Figure 8: Consecutive still images displaying a typical confined burn. Each image corresponds to one frame at a sample rate of 40,000 fps. The front edge of luminous activity is used to calculate flame speed.
The high-speed camera used was a Vision Research Phantom vs. 7.1. The open burn experiments were recorded at 20000 frames-per-second (fps). Confined burn experiments were recorded at 40,000 fps. The Phantom software was used to determine reaction flame speeds. The software will deduct the flame speed given a user defined length scale and a time scale dependent upon the sample rate of the recording. The scale was defined for each test using the marked 1 cm increments seen in Figures 4 and 6. The pressure transducers were used to measure pressures generated in the confined burns. The pressure transducers were not used in the open burn set-up. The 28
PCB model # 113A22 transducers are routed to a PCB model # 482A22 signal conditioner and subsequently to a National Instruments BNC-2110 data acquisition board, as shown in Figure 7. The National Instruments board was controlled using Labview version 8.0. Sample rates for tests with micron scaled Al were 50,000 pointsper-second (pps), and sample rates for tests with nanoscale Al were 100,000 pps. A typical pressure trace is displayed in Figure 9.
12 10
Pressurization Rate (dp/dt)
Peak Pressure
Pressure (MPa)
8 6 4 2
Initial Pressure Rise (used to

determine propagation rates)
Sensor 1 Sensor 2 Sensor 3 Sensor 4
Rise Time
(time from initial rise to peak )
0 0.3091 -2
0.3093
0.3095
0.3097
Time (sec)
Figure 9: Typical pressure trace for a 50nm Al/Teflon confined burn.
Peak pressure, pressure rise time, pressurization rate, and pressure wave propagation rate were determined from the pressure history data for the fourth sensor. This sensor location was chosen for detailed analysis because at this location the reaction achieved steady-state and yielded the most consistent data. Figure 9 shows that peak pressure was found as the maximum pressure recorded. This value is directly related to the amount of gas produced during reaction which has a significant impact upon the 29
reaction. The rise time is the time difference between the maximum pressure and the initial rise in pressure. The rise time is a good indication of the order of magnitude for the reaction time and is sometimes referred to as the characteristic reaction time. Diffusive distances, the distance that oxidizing gases will diffuse into the fuel oxide shell, can be approximated as a function of rise time using Equation 2.5. If the estimated diffusive distance is less than the thickness of the oxide shell, then diffusion can be eliminated as a dominant reaction mechanism.
l d = 2 D
Where: d = Diffusive Distance
(2.5)
D = Diffusivity for oxygen and aluminum in alpha-alumina at 800C (D 10-19 cm2/s according to Bergsmark, Simensen, and Kofstad (1989)) = Order of magnitude of the reaction time ( the pressure rise time) The reactive power of a reaction can be estimated using the pressure rise time as well. The reactive power will approximate how much energy can potentially be extracted in an ideal combustion reaction. It can be calculated using Equation 2.6.
RP =
H Rx M
(2.6)
Where: HRx/ = Heat of reaction (based on mass) M = Mass of reactants = Order of magnitude of the reaction time ( the pressure rise time)
30
The pressurization rate is the slope of the increasing pressure versus time curve and is taken over the most constantly increasing segment of that curve (i.e., from 5 to 95 % peak pressure) as seen in Figure 9. The pressurization rate can give insight to the amount of gas released over a specific time. A slower pressurization rate can mean a slower release of gases in the reaction. This coupled with the pressure rise time can give a good indication of the amount of gas released and the time scale of gas being released for a reaction. The pressure wave propagation rate is found using the known distance between the pressure sensors and the difference between arrival times (point of first rise for each sensor as depicted in Figure 9) of a sensor and its preceding sensor. The pressure wave propagation will tell how fast the pressure is moving through the confined space. This can be used to determine if the reaction reaches the point of detonation or if it is a deflagration. If the pressure wave proceeds equal or faster than that of the optical propagation wave the reaction can be considered to have reached detonation. If the pressure wave propagates slower than the optical wave the reaction will be a deflagration. The optical propagation rate, or flame speed, is deduced from the high-speed camera data. It is primarily used as quantification for the speed of the reaction, but can also give indication of detonation when compared to the pressure wave propagation rate as described above. Another interesting characteristics derived from the optical propagation rate is the Mach number achieved by the reaction. In many MIC reactions, flame speeds can approach and exceed 1000 m/s, which would be in excess of Ma 3 if the surroundings where considered to be air at room temperature. The achieving of such Mach numbers could mean that there are significant acoustic effects in the reaction. However, the reaction proceeds within the flame zone assumed to be at the adiabatic 31
flame temperature for the reaction. This extreme temperature environment reduces the Ma number calculation significantly. The Mach number can be estimated by the use of Equations 2.7 and 2.8.
Ma =
V C
(2.7)
Where: V = Optical propagation rate C = Speed of sound in surrounding media (Calculated by Equation 2.8)
And
C = RT
(2.8)
Where: = Cp/Cv (Constant pressure specific heat/Constant volume specific heat) R = Gas constant of surrounding media T = Temperature of surrounding media
32
Chapter III Results and Discussion

3.1 Open Burn Tray Results
3.1.1 Results and Initial Observations
The open burn tray flame speeds collected via high-speed camera are displayed in Figures 10 through 12 (Error bars are provided but may be smaller than the point marker. For error values see detailed Tables in Appendices). A detailed account is provided in Tables 11 and 12 located in Appendix A. Peak flame speeds of 4.249 m/s, 410.636 m/s, and 456.559 m/s were obtained for the nano Al samples of Al/Teflon, Al/ MoO3/Teflon, and Al/ MoO3 composites, respectively. Peak flame speeds of 1.382 m/s, 0.334 m/s, and 4.116 m/s were found for the micron Al samples of Al/Teflon, Al/ MoO3/Teflon, and Al/ MoO3 composites, respectively.
5.0 4.5 Flame Propagation (m/s) 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0% 20% 40% 60% 80% 100% Mass Percent Aluminum
Figure 10: Al/Teflon open tray burn results
50 nm Al 1-3 m Al
33
450 Flame Propagation Rate (m/s) 400 350 300 250 200 150 100 50 0 0% 20% 40% 60% 80% 100% Mass Percent Aluminum
Figure 11: Al/MoO3/Teflon open tray burn results
50 nm Al 1-3 um Al
600 Flame Propagation Rate (m/s) 50 nm Al 500 400 300 200 100 0 0% 20% 40% 60% 80% 100% Mass Percent Aluminum
Figure 12: Al/MoO3 open tray burn results.
1-3 um Al
34
It is immediately noticeable that reducing the Al particle size has immense impact upon flame speed independent of composition. In each case the flame speed increases significantly with the decrease in particle size. The most significant impacts on flame speed when decreasing particle sizes were seen in the composites that contained MoO3 which increased by factors of over 100 at the optimal ratio compared to a factor of only 3 for the Al/Teflon reaction at its optimal ratio. In the micron Al experiments, the Al/Teflon composite reached a flame speed faster than that of Al/MoO3/Teflon composite but slower that the Al/MoO3 composite. In the nano Al experiments the Al/Teflon composite was outperformed by both the Al/MoO3/Teflon and Al/MoO3 composites. For the nano-mixtures there is a similarity in the flame speed trends for mixtures containing MoO3 but not for the Al/Teflon composite. The Al/Teflon composite exhibits a peak flame speed 100x slower than the reactions containing MoO3, and the Al/Teflon composite differs in its optimal composition, from 40% for the composites containing MoO3 to 50% for the Al/Teflon composite.
3.1.2 The Effects of Particle Size and the Addition of Teflon

The reduced flame speed associated with the Al/Teflon reaction may be attributed to fluorine gas escaping the reaction zone as seen in experiments by Osborne and Pantoya (in press 2007). These open tray experiments do not trap gaseous intermediates or products, thus gas escaping the flame zone would not participate in propelling the flame front forward. A large portion of energy in the reaction escapes with the liberated fluorine gases instead of contributing to accelerating the flame front. Thermodynamic 35
equilibrium calculations using REAL Code (Tim Tec, LLC.) assuming thermal equilibrium exists during reaction indicate the quantity of gas production as a function of aluminum content for the binary and ternary mixtures (Figure 13). Figure 14 shows the adiabatic flame temperatures associated with the studied reactions also determined from thermal equilibrium calculations using REAL Code (Tim Tec, LLC.).
1 Gas Production (kg/kgreactant) 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0% 20% 40% 60%
Al/C2F4 Al/MoO3 Al/MoO3/C2F4
80%
100%
Mass Percent Aluminum

Figure 13: Gas generation in the Al/Teflon, Al/MoO3/Teflon, and Al/MoO3 reactions. Values determined using the REAL Code (Tim Tec, LLC.) chemical equilibrium program.
36
4000.00 Adiabatic Flame Temperature (K) 3500.00 3000.00 2500.00 2000.00 1500.00 1000.00 500.00 0.00 0% 20%
Al/C2F4 Al/MoO3/C2F4 Al/MoO3
40% 60% 80% Mass Percent Aluminum
100%
Figure 14: Adiabatic flame temperature in the Al/Teflon, Al/MoO3/Teflon, and Al/MoO3 reactions. Values determined using the REAL code chemical equilibrium program.
The micron Al reactions containing Teflon exhibited flame speeds two orders of magnitude lower than the Al/MoO3 reaction. It was also observed that the micron Al/Teflon reaction proceeded at higher flame speed than that of the micron Al/MoO3/Teflon reaction. The higher flame speed in the micron Al/Teflon composite when compared to the Al/MoO3/Teflon composite is interesting. The Al/MoO3/Teflon reaction may be expected to exhibit a higher flame speed because the mixtures containing MoO3 have lower gas production and a similar flame temperature as seen in Figures 13 and 14. However, this is not the case. It is possible that the reaction in the Al/MoO3/Teflon proceeds with Al reacting primarily with MoO3 because Teflon, which has decomposed at 322C (Osborne & Pantoya, in press 2007), is not available at the 37
Al/MoO3 reaction ignition temperature of ~960C (Pantoya & Granier, 2005). This would lead to incomplete combustion and lower heats of combustion because of the relatively low content of MoO3 and the limited contribution from Teflon particles. In the micron Al/Teflon reaction there is an abundance of fluorine gas produced as the oxidizer is entirely Teflon. Much of the liberated fluorine gas will escape the reaction zone but due to the high quantity produced some of the fluorine gas will remain long enough to react with the Al. Even though only a portion of the available fluorine may be reacting, the fluorine that does react contains more energy than the oxygen reacting in the micron Al/MoO3/Teflon reaction. Therefore, it may be that in both the micron Al/Teflon and micron Al/MoO3/Teflon only a portion of the supplied oxidizer reacts (the fluorine unable to escape in the Al/Teflon reaction and the supplied MoO3 in the Al/MoO3/Teflon reaction) and the Al/Teflon proceeds at a higher flame speed due to the higher energy content of fluorine compared to oxygen (i.e. the heat of reaction in the Al/Teflon reaction is greater than that of the Al/MoO3 reaction as seen in Figure 1). As stated above, only reacting with a portion of the oxidizer would lead to incomplete combustion in these reactions. It is noted that these experiments were performed in an inert argon environment such that oxygen from the ambient air does not contribute to the reaction. The incomplete combustion would lead to slower heating rates with lower combustion temperatures. The Al/MoO3 reaction having little gas production will not lose as much energy to the surroundings and will experience a more complete combustion. The slower propagation rates, in comparison to the Al/MoO3 reaction, seen in the composites containing Teflon may be a result of the incomplete and inefficient combustion in these composites. 38
For nanometer Al reactions, the peak flame speed of the Al/Teflon reaction is two orders of magnitude less than for both of the reactions containing MoO3. As in the micron Al reactions the gaseous intermediates and products are not contained and energy is allowed to escape. Therefore the reactions containing Teflon are prone to lose more energy to the surrounding because much of the energy is in the form of liberated fluorine gas that can escape the reaction zone. The increased sensitivity of nanoscale Al allows the Al to react with more of the fluorine before it escapes than in the reactions containing micron Al. The increased amount of fluorine reacting before it is able to leave the reaction zone due to the increased sensitivity of the nanometer Al as well as the increased homogeneity associated with using nanoscale particles explains the increase in the flame speed of the nano Al/Teflon composite in comparison to its micron counterpart. However this increase is small in comparison to that seen in the reactions containing MoO3. Much of the liberated fluorine gas may still escape the reaction zone explaining some of this difference in the amount of increase in flame speed. The Al/MoO3/Teflon reaction, which proceeded at a slower rate than the Al/Teflon reaction when using micron Al, proceeds at a much higher flame speed than the Al/Teflon reaction when using the nanoscale Al. On the micron scale it was surmised that the Al/MoO3/Teflon reaction proceeds slowly as a result of the Teflon not reacting in the Al/MoO3/Teflon reaction. With the increased sensitivity of Al some of the Teflon may now be reacting before it leaves the reaction zone. This would account for some increase in flame speed as less energy is lost and more energy is applied towards the acceleration of the reaction. However, much of the fluorine would still escape and only a slight increase between the micron and nano Al reaction, such as what was seen in the Al/Teflon reaction, would be 39
expected. Therefore another mechanism must be responsible for the large increases of flame speed in the reactions containing MoO3. The large increases in flame speed seen when comparing the micron and nano Al reactions containing MoO3 in an unconfined configuration may be a result of a change in the reaction mechanism. The micron Al reactions propagate at rates slow enough to suggest that the reaction mechanism is predominantly diffusion. The nanoscale Al reactions containing MoO3 propagate quickly enough and create heating rates fast enough to promote the melt dispersion mechanism, causing the Al particles to spallate. The melt dispersion mechanism in the nano Al composites containing MoO3 would explain the two orders of magnitude increase in flame speeds. In the Al/Teflon reaction, the flame speeds were not fast enough to suggest melt dispersion may be occurring. Therefore, there is most likely no change in the dominant combustion mechanism and the reaction will remain predominantly diffusion controlled. Thus the reaction would remain diffusion controlled for the nano Al/Teflon reaction when going from the micron to nano Al particles; whereas, the nano Al/MoO3/Teflon and nano Al/MoO3 would experience a change to the melt dispersion mechanism with the decrease in particle size. The lack of a change in reaction mechanism between the micron and nano Al/Teflon reactions would explain only having a slight increase in flame speed as the only contributing factor would be the increased amount of fluorine reacting due to the higher sensitivity of nanoscale Al particles and the increased homogeneity of the composite. The shift to melt dispersion in the reactions containing MoO3 would explain the similarity of the flame speed curves and the large increase in flame speeds seen when comparing these reactions to the micron reactions containing MoO3. 40
3.1.3 Implications
For unconfined burning environments, adding Teflon to the mixture produces fluorine gas that escapes from the flame zone allowing the loss of energy to the surroundings. This energy is no longer contributes to the enhancement of the flame propagation. With gaseous intermediates escaping, it is likely that incomplete combustion occurs as only a portion of the oxidizing agent is reacting. Therefore, the addition of Teflon to unconfined reactions allows energy to escape the reaction zone and results in incomplete combustion and overall hinders the transfer of energy to the accelerating flame front resulting in slower flame speeds. Composites that produce little gas contain more energy within the reactants themselves. In the unconfined state this energy still attributes to accelerating the flame front as it is not in gaseous form where it can readily escape the reaction zone. This allows for faster heating rates and higher flame speeds. When using nanoscale Al as the fuel, heating rates can be attained that promote the melt dispersion mechanism resulting in substantial increases in flame speed. In high gas reactions this was not achievable as there was not enough energy retained within the reaction zone to create heating rates fast enough for the melt dispersion mechanism to occur. These results imply that achieving high flame speeds in an open environment can be accomplished using nano aluminum particles combined with a metallic oxide that does not produce a significant amount of gas.
41
3.2 Confined Burn Tube Results

3.2.1 Results and Initial Observations (Flame Speed Measurements)
The Figures 15 through 17 show the confined burn results which are listed in detail in Tables 13 and 14 found in Appendix A (Error bars are provided but may be smaller than the point marker. For error values see detailed Tables in Appendices). Composites with the 50nm Al particles exhibited peak flame speeds of 837.498 m/s, 957.216 m/s, and 960.234 m/s for the Al/Teflon, Al/MoO3/Teflon, and Al/MoO3 composites, respectively. The 1-3 micron Al experiments yielded peak flame speed of 348.279 m/s, 163.902 m/s, and 244.019 m/s for the respective composites of Al/Teflon, Al/MoO3/Teflon, and Al/MoO3.
900 800 Flame Propagation (m/s) 700 600 500 400 300 200 100 0 0% 20% 40% 60% 80% 100% Mass Percent Aluminum
Figure 15: Al/Teflon confined apparatus burn results.
50 nm Al 1-3 m Al
42
1200 50 nm Al Flame Propagation (m/s) 1000 800 600 400 200 0 0% 20% 40% 60% 80% 100% Mass Percent of Aluminum
Figure 16: Al/MoO3/Teflon confined apparatus burn results.
1-3 m Al
1200 Flame Propagation Rate (m/s) 50 nm Al 1000 800 600 400 200 0 0% 20% 40% 60% 80% 100% Mass Percent Aluminum
Figure 17: Al/MoO3 confined apparatus burn results.
1-3 um Al
43
As in the open burn configurations, it is evident that particle size plays a major role in the flame speeds. Each composite exhibits a significant increase in flame speed with the decrease in particle size. In the confined state the increase in flame speed due to the change in particle size was more consistent than in the open burn configuration. Each composition increased by a factor less than 10 at its optimal composition. The Al/Teflon reaction exhibited the fastest flame speed in the micron Al reactions. However the Al/Teflon reaction had the slowest flame speed in the nano Al reactions. The nanoscale Al experiments all yielded curves with similar peak flame speeds at an optimal ratio of 40% mass Al. Also noted is the shift in optimal composition when decreasing particle size in both experiments containing Teflon in the composition.
3.2.2 Results and Initial Observations (Pressure Measurements)

Pressure data was obtained at the optimal ratio for each composite and the final sensor data (the farthest sensor from the point of initiation) is displayed in Table 5. A more detailed account is provided in Tables 15 and 16 of Appendix B.
Table 5: Pressure results from the 4th pressure transducer (farthest from ignition). Optical Mass Pressure Peak Rise PressurizPropag% Compo- Mass PropagaPressure Time ation Rate ation Pure sition (mg) tion Rate (MPa) ( sec) (MPa/sec) Rate Al (m/s) (m/s) Al/Teflon 201.2 10.75 84.0 181746.25 762.00 837.50 40 Al/MoO3/ 211.8 5.45 78.0 95877.06 846.67 957.22 40 Teflon 1.46 63.3 44922.16 823.15 960.23 Al/MoO3 196.6 40 50 60 40 Al/Teflon Al/MoO3/ Teflon Al/MoO3 400.6 384.2 362.7 4.18 0.38 0.82 784.0 2105.0 245.0 29968.49 241.75 3336.10 186.27 58.56 240.10 348.28 163.90 244.02
Al Size
50 nm Al 1-3 m Al
44
An increase in peak pressure is consistent with the increase in flame speed when the Al particle size is decreased. Also noted are the faster rise times, pressurization rates and wave speeds associated with the composites containing 50 nm Al particles. One observation is the slower optical and pressure propagation rates in the nanoscale Al/Teflon reaction despite yielding the highest pressure and fastest pressurization rate. The reactive power was calculated for each reaction using Equations 2.6. This value along with the adiabatic flame temperatures and estimated gas production found using the Real Code (Tim Tec, LLC.) chemical equilibrium program are displayed in Table 6.
Table 6: Properties of the reactions assuming ideal burns with complete combustion. Al Size 50 nm Al 1-3 m Al Mass % Pure Al 40 40 40 50 60 40 Composition Adiabatic Flame Temp (K) 2769 2738 2956 2769 2738 2956 Heat of Reaction (kJ/kg) 14309 10277 4979 14309 10277 4979 Gas Generation (kg/kgreactant) 0.81 0.39 0.03 0.81 0.39 0.03 Reactive Power (KW) 3.43E+04 2.79E+04 1.55E+04 7.31E+03 1.88E+03 7.37E+03
Al/Teflon Al/MoO3/Teflon Al/MoO3 Al/Teflon Al/MoO3/Teflon Al/MoO3
The reactive power (mass based) and gas generation are the largest for the Al/Teflon reaction. This implies that the Al/Teflon will have the highest amount of convective heat transfer due to the large amounts of gas produced as well as having the highest energy content of the composites tested.
45
3.2.3 The Effects of Particle Size and the Addition of Teflon

In confined configurations, the intermediate gases cannot escape and instead enhance the convective mode of energy propagation. Under confinement the composites containing Teflon produced higher peak pressures as expected with the increased gas generation (see Figure 13). In the micron Al reactions, the Al/Teflon composite exhibited the highest flame speed corresponding with the highest peak pressure. This may be a result of the increased convective heat transfer associated with the higher gas production. The gases are forced through the composite instead of escaping to the atmosphere. This results in preheating the reactants and leads to faster flame speeds. Also, unlike in the open burn configurations, a large portion of the fluorine is most likely reacting as it is unable to escape the reaction zone. The reaction with gaseous fluorine results in more complete combustion enhancing the flame speed. The preheating of the composite due to convective heat transfer as well as the more complete combustion associated with the confinement of the gaseous oxidizer results in the higher flame speeds in comparison to the open configuration reactions. The micron Al/MoO3 reaction exhibited a higher flame speed than that of the micron Al/MoO3/Teflon reaction. This was unexpected because the Al/MoO3/Teflon reaction would be expected to have more gaseous byproducts and should experience a larger increase in convective heat transfer when confined. However, according to the peak pressures displayed in Table 5, the 1-3 m Al/MoO3 reaction produced a larger amount of gas than the1-3 m Al/MoO3/Teflon reaction. This would lead to higher levels of convective heat transfer in the micron Al/MoO3 reaction than in the micron Al/MoO3/Teflon reaction. The lower than expected gas production and the slower flame 46
speed in the Al/MoO3/Teflon may still be attributed to escaping fluorine gas as seen in the open configuration burns. As discussed in the open burns, fluorine is available before the reaction of Al/MoO3, since Teflon degrades at ~322C (Osborne & Pantoya, in press 2007) and the ignition temperature of micron Al with MoO3 is not until ~960C (Pantoya & Granier, 2005). The liberation of the fluorine prior to the ignition of the Al and MoO3 is evident by the much slower pressurization rate and much longer rise time associated with the Al/MoO3/Teflon reaction. Given the time between its liberation and the reaction initiation the fluorine may still escape the reaction zone despite being confined. As in the open burn configuration, the loss of some fluorine gas would again result in incomplete combustion and lower flame speeds than what would be achievable if no fluorine was able to escape. This incomplete combustion would also explain the low gas production in the micron Al/MoO3/Teflon reaction as the main contributing oxidizer is the MoO3 which does not result in high amounts of gas. The micron Al/MoO3 reaction exhibits a higher gas production because it experiences a more complete combustion and contains almost 2x as much MoO3. The 1-3 m Al/Teflon reaction may also experience the same phenomenon of escaping fluorine gas. However, the abundance of fluorine produced when using 100% Teflon as the oxidizer would result in the higher pressurization rate and rise time leading to the increased flame speed and the higher pressure. Nanometer scale aluminum is more sensitive to ignition. The composites containing nm Al and Teflon produced twice the peak pressure than mixtures with micron Al and Teflon. These results suggest that the main influence of particle size is in the reactivity of the mixture. The nm Al particles are easier to initiate and more completely react with the fluorine gas from the decomposed Teflon. That energy assists 47
in the flame propagation. In the nano particle Al confined tests the flame speeds are similar for all composites. Each reaction resulted in significant increases, on the order of 2 to 6 times, when reducing the particle size from the micron to nanoscale. The nm Al particles exhibit rise times on the order of 80 microseconds, which can be considered the characteristic time for a reaction to occur. These time scales are too fast for a diffusive mechanism. According to Equation 2.5, 80 microsecond rise times will yield diffusive distances on the order of 5 x 10-5 nanometers which is smaller than the oxide shell thickness of the Al particles. Therefore these time scales are more consistent with the melt dispersion theory. Achieving heating rates fast enough to promote the melt dispersion mechanism as well as the increased homogeneity and sensitivity associated with using nano particles explains the increases in flame speed when compared to the reactions using micron Al. The increased pressure associated with the more complete combustion leads to enhanced convective heat transfer promoting the increases in flame speed. The high levels of gas produced in the Al/Teflon would lead to higher levels of convective heat transfer than seen in the Al/MoO3/Teflon and Al/MoO3 reactions. However, the nano Al/Teflon reaction exhibited the slowest flame rate as well as the highest peak pressure when confined. In this case, pressure may play a dual role, promoting convection and enhancing flame speeds until a limiting pressure threshold is achieved at which point the pressure than acts to suppress the reaction and flame propagation. Kuo (2005) shows that in gaseous systems flame speeds are reduced as pressure increases according to:
S L p 1 / 2 where SL, is flame speed and P is pressure.

48
This effect was shown in experiments by Egerton and Levevbre (1954) in which they determined burning velocities of methane, propane, ethylene, and propylene while varying pressure from to 9 atm. Their results for the burning of the propane/air mixtures are displayed in Figure 18.
Figure 18: Burning velocities of propane/air mixtures. Figures against curves show percentage C3H8. (Egerton & Levevbre, 1954).
These results show in gaseous mixtures the increase of pressure does retard the flame speed of the reaction. This same principle can be applied to thermites as shown by Ivanov, Surkov, and Viktoranko (1979). Ivanov et al. (1979) studied the effects of pressure on various thermite composites including BaO2/Zr, MoO3/Mg, and PbO2/Zn. The studies were conducted in a constant-pressure bomb with pressures varying from 1 to 80 atm. Figure 19 shows their results for the above-mentioned thermites.
49
Figure 19: Effect of pressure on the combustion rate of thermite mixtures: 1) BaO2/Zr 2) MoO3/Mg 3) PbO2/Zn (Ivanov et al., 1979)
As seen in Figure 19, increasing pressure initially causes an increase in flame speed in the thermite composites. However, there exists some point at which the increase of pressure will begin to reduce the flame speed of the reaction. If this point, or threshold pressure, is exceeded then the effect of the increasing pressure will be to retard instead of enhance the reaction propagation rate. In the confining of these reactions there is a substantial increase of pressure that should retard the flame rates. However the confining of these gases also leads to the higher levels of convective heat transfer and a shift in reaction mechanism that enhances the flame rate. Thus by confining the reaction the flame speed experiences both the 50
retarding effects of the increasing pressure and the enhancing effects of the increased convection and the shift in combustion mechanism. The large increases in flame speed when compared to the open configuration burns suggest that the influence of the increased convective heat transfer and change in combustion mechanism have a larger impact on the reaction than the retarding effects of the pressure. However, the retarding effect of the pressure would explain the lower flame speed in the nanoscale Al/Teflon confined reaction. The amounts of gas produced by the Al/Teflon reaction leads to a pressure double that of the other reactions. Therefore the retarding effects of the pressure will be significantly larger, ~2x. There may be a threshold pressure that if exceeded the effects of the pressure begin to overcome the increases in flame speed from the convection and combustion mechanism. This would lead to the flame speed increasing with the increase of pressure until this threshold pressure is achieved. After the threshold pressure is exceeded the flame speed would begin diminishing as the pressure is further increased. The Al/Teflon reaction, having double the pressure of the other reactions, may have exceeded this threshold pressure causing its flame speed to begin diminishing. This would explain the slower flame speed in the Al/Teflon reaction despite it exhibiting the highest pressure and potential reactive power. The reactions do not seem to achieve a detonation as evident by comparing the optical and pressure propagation waves. If detonation was achieved the pressure propagation rate would be equal to or exceed that of the optical wave. In all cases the pressure propagation was slightly slower than the optical wave as shown in Table 7. This suggests that detonation is not achieved. However in the nanoscale Al reactions, the addition of Teflon, resulting in additional gas and higher pressures, seems to narrow the 51
gap between the optical and pressure propagation rates. This infers that adding oxidizers that result in high gas generation to nanoscale thermites may draw the reaction closer to a detonation. However, as discussed above, too much gas and resulting pressure may actually begin to hinder the reaction and could possibly prevent the detonation from occurring. The opposite effect was seen in the micron scaled Al reactions. The addition of Teflon and resulting higher gas content broadened the gap between the optical and pressure propagation rates. The lower homogeneity associated with the using the micron particles results in a less complete combustion and subsequent lower gas production. The gas produced does effectively increase convective heat transfer which subsequently increases the flame speed. Due to the lower gas production in these micron Al reactions, there is not enough build-up of gases to increase the pressure wave propagation the extent that the flame speed is increased. Therefore, in the micron Al reactions, the effects of confining the gases has a greater effect on increasing the optical propagation rate due to convection than it does at increasing the pressure propagation rate, and the difference between the optical and pressure propagation rates broadens. This implies that using oxidizing agents that produce large quantities of gas can bring a reaction closer to detonation if it is confined and utilizes nanoscale particulates. However, a balanced medium in which enough gas is introduced to accelerate the reaction rate and draw the pressure wave propagation rate closer to the optical wave propagation rate without exceeding the pressure at which the reaction rates begin to diminish is needed and may result in very fast reactions with the potential to achieve detonation.
52
Table 7: Difference between optical and acoustical wave propagation rates Mass % Pure Al 40 50 nm Al 40 40 50 1 - 3 m Al 60 40 Optical Minus Acoustical Propagation Rate (m/s) 75.498 110.549 137.086 162.012 105.341 3.916
Al Size
Composition
Another interesting result is the Mach number achieved by these reactions. The Mach number was calculated assuming a combination of proceeding through the gas that comprised the largest percentage of the gaseous byproducts of the reactions or proceeding through air along with proceeding at the adiabatic flame temperature or proceeding at room temperature. The gas medium, when not assumed to be air, for use in this calculation was found using the REAL Code (Tim Tec, LLC.) chemical equilibrium software to be AlF in the Al/Teflon reaction and CO in the Al/MoO3/Teflon and Al/MoO3 reactions. The adiabatic flame temperatures were also found using the REAL Code (Tim Tec, LLC.) chemical equilibrium software and are displayed in Table 6. The Mach number was calculated using Equation 2.7 and the results are displayed in Table 8.
53
Table 8: Mach number calculations for the flame speed of the reactions. Al Size 50 nm Al 1-3 m Al Mass % Pure Al 40 40 40 50 60 40 Composition Ma in gas medium at reaction temp 1.18 0.90 0.87 0.49 0.15 0.22 Ma in air at reaction temp 0.79 0.91 0.88 0.33 0.16 0.22 Ma in gas medium at room temp 3.61 2.74 2.75 1.50 0.47 0.70 Ma in air at room temp 2.42 2.76 2.77 1.01 0.47 0.70
Initially looking at the flame speeds, the reactions appear to approach Mach 3 as shown by the Mach number calculation at room temperature shown in Table 8. If this was the case acoustical effects may play a huge role and detonation in the reaction would be imminent. However, considering the reaction occurs in air at the reaction temperature yields Mach numbers on the subsonic regime and would be more consistent with a deflagration. The actual Mach number will most likely be somewhere in between and may be best represented by the Mach number calculation in the gas byproduct medium at the reaction temperature. This number is probably slightly high as the gas will not be at the adiabatic flame temperature but it will be much higher than that of room temperature. These Mach numbers are on the order of Mach 1 and would suggest a reaction that is still a deflagration but may be nearing detonation. This is consistent with the comparison of the optical and acoustical propagation rates from above.
3.2.4 Implications
For confined burning environments, the addition of Teflon and associated increase in gas enhances the convective heat transfer in the reaction. The confining of 54
these gases allows more of the fluorine to remain in the reaction zone increasing the amount of energy applied to the reaction resulting in more complete combustion and faster propagation rates. The addition of the Teflon to the nano Al reactions narrowed the difference between the optical and pressure propagation rates bringing the reactions closer to detonation. However, despite the significant enhancements in flame speed seen by initially increasing the pressure due to the high convective heat transfer rates and confining of the oxide gases, there appears to be a point at which the increasing pressure begins to retard the flame speed. This implies that using an oxidizer that produces a large amount of gas can significantly increase flame rates as well as bringing the reaction closer to achieving or possibly achieving detonation as long as the pressure generated is not sufficient enough to pass the threshold at which it will begin hindering the reaction. Therefore, to achieve the fastest possible flame speeds and to achieve detonations a medium must be found that produces just enough gas to create high pressures that approach but dont exceed the pressure threshold.
3.3 Effects of Confinement

To better illustrate the effects of confining the reactions, Figure 20 shows the burn rates for each composite containing 50nm Al under both open and confined states (Error bars are provided but may be smaller than the point marker. For error values see detailed Tables in Appendices).
55
1200 Flame Propagation Rate (m/s) 1000 800 600 400 200 0 0% 20%
Al/Teflon Confined Al/Teflon Open Al/MoO3/Teflon Confined Al/MoO3/Teflon Open Al/MoO3 Confined Al/MoO3 Open
40% 60% Mass Percent Aluminum
80%
100%
Figure 20: 50 nm Al open and confined burn results for all composites.
It is obvious that confinement has a profound effect on combustion characteristics in these composites, as expected. All three composites showed substantial increases in flame speed when going from the open to confined configuration. These increases are likely a result of increased convective heat transfer due to the retaining of hot gases. This enhances the convective heat transfer and the rate of heating of the composite. To evaluate the potential combustion mechanism in these reactions diffusive distances were estimated using Equation 2.5. The approximate diffusive distances were calculated as a function of the pressure rise time and displayed in Table 9.
56
Table 9: Approximate maximum diffusive distance for the reactions.
Al Size 50 nm Al 1-3 m Al
Mass % Pure Al 40 40 40 50 60 40
Composition
Ld (nm)
5.80E-05 5.59E-05 5.03E-05 1.77E-04 2.90E-04 9.90E-05
These results suggest that the maximum distance that the oxidizing gas is able to diffuse through is < 1nm. The oxide layers of the Al powders used are ~ 2nm. This implies that the reactions under confinement cannot be diffusion controlled as the oxidizing gas will not diffuse far enough to penetrate the aluminum particles oxide shell. The melt dispersion mechanism proposed by Levitas, Asay, Son, and Pantoya (2005) may be the dominant mechanism in these reactions as the heating rates and flame speeds are fast enough to promote spallation of the Al particles. Another significant observation was the factor by which each composite increased. Table 10 displays the amount of increase in each composite.
57

Table 10: The factor of increase due to confinement in each 50 nm Al composite. Mass % Pure Al Increases by a multiple of
10 20 30 40 50 60 70 80 90 10 20 30 40 50 60 70 80 90 10 20 30 40 50 60 70 80 90
N/A 0.1 180.3 260.7 177.0 214.6 167.3 57.7 N/A N/A 30.0 1.9 2.3 3.5 3.6 7.3 7.2 0.0 32.3 23.3 2.1 2.1 3.7 12.7 40.2 0.0 0.0
All of the composites showed an increase in flame speed when confining the reaction. This is a direct effect of the enhanced convective heat transfer as a result of the confinement of the intermediate and product gases as well as the more complete combustion associated with the retaining of oxidizer gases. The Al/Teflon composite would see the most effect from the confining of these gases due to the abundance of gas produced in that reactive system. The increases in Al/ MoO3 and Al/ MoO3/Teflon were small in comparison to those achieved by the Al/Teflon composite. The higher level of 58
Al/MoO3
Al/MoO3/Teflon
Al/Teflon
gaseous production in the Al/Teflon reaction would account for a part of the difference in the amount of increase seen when confining the Al/Teflon reaction compared to the reactions containing MoO3. However a significant part of this difference may be owed to the mechanism controlling the reactions. The combustion mechanism may be responsible for much of the large factor of increase in flame speed exhibited when confining the Al/Teflon reaction. The Al/MoO3/Teflon and Al/MoO3 composites, when using the nanometer Al particles, achieved heating rates fast enough to promote the melt dispersion mechanism in both the open and confined states. The Al/Teflon was most likely still diffusion controlled in the open configuration burns; whereas, it had likely made a switch to the melt dispersion mechanism in the confined state burns. Therefore the increases in flame speed when confining the Al/MoO3/Teflon and Al/MoO3 reaction can be mainly contributed to the increased convective heat transfer and more complete combustion when under confinement as the reaction mechanism remained the same for both configurations. A large portion of the increase seen when confining the Al/Teflon reaction may be a result of a shift in reaction mechanism from diffusion to the melt dispersion. Even though confining of the gaseous Al/Teflon reaction had much larger effects than the confining of the less gaseous Al/MoO3/Teflon and Al/MoO3 reactions, there was a negative side effect. As discussed in the earlier section, the large pressure associated with confining such a gaseous reaction plays a dual role. On one hand it serves to increase the convective heat transfer increasing the flame speed. On the other at some point it becomes a hindrance and begins to retard the flame speed. The Al/Teflon reaction could have experience an even larger factor of increase due to confinement had 59
the pressure not started to negatively effect its flame speed. Therefore, for confining a reaction to have the most impact the reacting species must produce enough gas to create pressures large enough to promote high levels of convective heat transfer without exceeding the pressure threshold at which the flame speeds begin to reduce.
60
Chapter IV Conclusions
The use of fluorine as an oxidizing agent in thermite reactions yields higher heats of combustion as well as increased gas content. In open burn configurations the increased gas content reduces flame propagation speeds because gas liberated during the reaction escapes the reaction zone. In the confined state these gases are contained promoting enhanced convection as well as more complete burning. Confining the reaction also leads to increases in pressure. The increased pressure promotes convection and accelerates flame speeds. It also causes the pressure wave propagation rate to draw closer to the optical propagation rate; however, both reaction configurations result in deflagrations with Ma numbers less than 1. At a critical threshold, beyond 5 MPa but less than 10 MPa, further increases in pressure beyond 5 MPa but less than 10 MPa begin to suppress flame propagation. This is evident in the Al/Teflon reaction as it has more reactive power and more gas production than the other composites yet it exhibits lower optical and acoustic propagation rates. The pressures achieved by the nano Al/Teflon reaction in confined burning configuration crossed the pressure threshold such that propagation rates are reduced. These results imply that in open configurations faster flame speeds will be achieved by using oxidizers that result in low gas output reactions as less energy is lost to the surrounding in the form of escaping gases. In the confined configuration the fastest flames speeds will be achieved by using oxidizers that produce enough gas to increase the peak pressure just below its critical threshold. Too high a peak pressure begins to suppress the reaction and reduce the flame speed. 61
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Appendix A Detailed high-speed camera data
66
Table 11: 50 nm Al composite open burn flame speed results.
Open Burns
Al/Teflon
% Al 10% 20% 30% 40% 50% 60% 70% 80% 90% Velocity 1 (m/s) 0.000 0.152 1.480 3.042 3.540 2.731 2.037 1.337 0.000 Avg. Vel. (m/s) 0.000 0.141 1.662 3.213 4.249 2.620 2.311 1.332 0.000 St. Dev. 0.000 0.012 0.203 0.172 0.681 0.116 0.238 0.073 0.000 Velocity 2 (m/s) 0.000 0.128 1.625 3.210 4.309 2.500 2.459 1.402 0.000 Velocity 3 (m/s) 0.000 0.143 1.880 3.386 4.898 2.630 2.437 1.257 0.000
Mass (mg) Result 203.300 no ign. 206.200 ign. 200.200 ign. 201.200 ign. 203.900 ign. 200.800 ign. 203.000 ign. 200.300 ign. 202.300 no ign.
St. Error 0.000 0.007 0.117 0.099 0.393 0.067 0.137 0.042 0.000
Al/MoO3/Teflon
Al/MoO3
67
ign. ign. ign. ign. ign. ign. ign. ign. ign. 2.551 26.177 419.841 432.317 208.335 31.048 3.852 0.845 0.061 2.711 22.446 453.463 440.398 192.305 32.486 3.837 0.821 0.012 2.982 22.995 431.812 496.962 205.131 29.461 4.290 0.863 0.095
10% 20% 30% 40% 50% 60% 70% 80% 90%
249.000 249.600 250.400 250.800 250.100 249.800 250.500 249.700 250.700
no ign. ign. ign. ign. ign. ign. ign. ign. ign.
0.000 12.714 380.001 418.183 221.303 73.691 9.323 1.131 0.310
0.000 11.333 320.001 400.097 231.639 74.498 9.766 1.197 0.289
0.000 11.049 370.136 413.629 237.904 80.702 10.529 1.225 0.297
0.000 11.699 356.713 410.636 230.282 76.297 9.873 1.184 0.299 2.748 23.873 435.039 456.559 201.924 30.998 3.993 0.843 0.056
0.000 0.891 32.174 9.407 8.383 3.836 0.610 0.048 0.011 0.218 2.014 17.042 35.223 8.483 1.513 0.257 0.021 0.042
0.000 0.514 18.575 5.431 4.840 2.215 0.352 0.028 0.006 0.126 1.163 9.839 20.336 4.897 0.874 0.149 0.012 0.024
10% 20% 30% 40% 50% 60% 70% 80% 90%
249.800 249.600 250.400 251.200 249.600 250.300 250.500 249.900 250.800
Table 12: 1-3 m Al composite open burn flame speed results.
Open Burns
Al/Teflon
% Al Mass (mg) 10% 401.6 20% 404.1 30% 402.3 40% 403.4 50% 403.0 60% 400.8 70% 408.0 80% 403.8 90% 401.9 Result no ign. no ign. ign. ign. ign. ign. ign. no ign. no ign. Velocity 1 (m/s) 0.000 0.000 0.548 0.802 1.352 0.646 0.113 0 0 Velocity 2 (m/s) 0.000 0.000 0.488 0.829 1.327 0.628 0.109 0 0 Velocity 3 (m/s) 0.000 0.000 0.486 0.793 1.466 0.563 0.094 0 0 Avg. Vel. (m/s) 0.000 0.000 0.507 0.808 1.382 0.612 0.105 0.000 0.000 St. Dev. 0.000 0.000 0.035 0.019 0.074 0.044 0.010 0.000 0.000
St. Error 0.000 0.000 0.020 0.011 0.043 0.025 0.006 0.000 0.000
Al/MoO3/Teflon
Al/MoO3
68
no ign. no ign. ign. ign. ign. ign. no ign. no ign. no ign. 0.000 0.000 2.228 2.771 3.769 1.294 0.000 0.000 0.000 0.000 0.000 1.546 3.183 4.570 1.310 0.000 0.000 0.000 0.000 0.000 1.443 2.905 4.009 1.465 0.000 0.000 0.000
10% 20% 30% 40% 50% 60% 70% 80% 90%
450.700 450.200 449.800 450.100 450.300 449.300 449.600 450.500 449.500
no ign. no ign. ign. ign. ign. ign. ign. ign. ign.
0.000 0.000 0.072 0.127 0.334 0.338 0.204 0.050 0.001
0.000 0.000 0.079 0.129 0.315 0.321 0.239 0.052 0.001
0.000 0.000 0.068 0.126 0.300 0.342 0.220 0.050 0.001
0.000 0.000 0.073 0.127 0.316 0.334 0.221 0.051 0.001 0.000 0.000 1.739 2.953 4.116 1.356 0.000 0.000 0.000
0.000 0.000 0.006 0.002 0.017 0.011 0.018 0.001 0.000 0.000 0.000 0.427 0.210 0.411 0.094 0.000 0.000 0.000
0.000 0.000 0.003 0.001 0.010 0.006 0.010 0.001 0.000 0.000 0.000 0.246 0.121 0.237 0.055 0.000 0.000 0.000
10% 20% 30% 40% 50% 60% 70% 80% 90%
450.600 450.200 449.500 450.300 449.800 448.900 450.400 450.600 449.600
Al/Teflon
% Al 10% 20% 30% 40% 50% 60% 70% 80% 90%
Mass (mg) Result 200.800 no ign. 202.600 ign. 204.100 ign. 201.200 ign. 203.200 ign. 201.500 ign. 202.800 ign. 201.000 ign. 201.600 no ign.
Table 13: 50 nm Al composite confined burn flame speed results. Velocity 1 (m/s) Velocity 2 (m/s) Velocity 3 (m/s) Avg. Vel. (m/s) 0.000 0.000 0.000 0.000 0.014 0.013 0.016 0.014 304.967 272.959 320.962 299.629 821.538 853.594 837.362 837.498 779.282 730.404 746.458 752.048 632.121 574.230 480.496 562.282 380.716 363.689 415.583 386.663 77.241 82.380 71.125 76.915 0.000 0.000 0.000 0.000 St. Dev. 0.000 0.002 24.443 16.028 24.914 76.515 26.453 5.635 0.000
St. Error 0.000 0.001 14.112 9.254 14.384 44.176 15.273 3.253 0.000
Al/MoO3/Teflon
Al/MoO3
69
ign. ign. ign. ign. ign. ign. ign. no ign. no ign. 84.259 526.895 897.302 931.044 734.958 415.838 162.991 0.000 0.000 88.039 593.093 876.656 979.549 760.721 386.231 185.955 0.000 0.000 94.279 551.758 930.695 970.109 773.521 378.099 132.935 0.000 0.000
10% 20% 30% 40% 50% 60% 70% 80% 90%
249.600 235.400 213.800 211.800 193.200 166.800 142.100 137.200 127.800
no ign. ign. ign. ign. ign. ign. ign. ign. no ign.
0.000 336.765 736.235 994.030 787.859 272.056 71.628 8.778 0.000
0.000 367.853 650.780 909.065 852.913 296.812 78.573 7.559 0.000
0.000 349.790 684.639 968.553 808.535 248.472 66.040 9.239 0.000
0.000 351.469 690.551 957.216 816.436 272.447 72.080 8.525 0.000 88.859 557.249 901.551 960.234 756.400 393.389 160.627 0.000 0.000
0.000 15.612 43.033 43.602 33.239 24.172 6.279 0.868 0.000 5.060 33.439 27.269 25.716 19.641 19.862 26.589 0.000 0.000
0.000 9.014 24.845 25.174 19.190 13.956 3.625 0.501 0.000 2.921 19.306 15.744 14.847 11.340 11.467 15.351 0.000 0.000
10% 20% 30% 40% 50% 60% 70% 80% 90%
223.600 218.700 209.500 196.600 189.300 181.800 174.100 166.600 160.300
Table 14: 1-3 m Al composite confined burn flame speed results.
Confined Burns
Al/Teflon
% Al 10% 20% 30% 40% 50% 60% 70% 80% 90% Result no ign. no ign. ign. ign. ign. ign. ign. no ign. no ign. Velocity 1 (m/s) 0.000 0.000 139.3328 291.817 338.993 316.204 298.955 0 0 Velocity 2 (m/s) 0.000 0.000 126.837 301.542 351.007 306.216 277.703 0 0 Velocity 3 (m/s) 0.000 0.000 133.578 294.184 354.838 310.242 253.619 0 0 Avg. Vel. (m/s) 0.000 0.000 133.249 295.848 348.279 310.887 276.759 0.000 0.000 St. Dev. 0.000 0.000 6.254 5.071 8.267 5.025 22.683 0.000 0.000
Mass (mg) 401.5 402.9 405.2 400.6 403.1 402.3 404.2 400.3 403.2
St. Error 0.000 0.000 3.611 2.928 4.773 2.901 13.096 0.000 0.000
Al/MoO3/Teflon
Al/MoO3
70
no ign. ign. ign. ign. ign. ign. no ign. no ign. no ign. 115.045 230.343 76.607 11.831 0.000 0.000 0.000 0.000 79.209 0.000 81.804 126.184 258.588 71.462 10.595 0.000 0.000 0.000 0.000 87.253 118.981 243.126 94.684 10.883 0.000 0.000 0.000
10% 20% 30% 40% 50% 60% 70% 80% 90%
338.300 353.200 363.900 384.200 400.300 420.000 455.200 472.500 483.200
no ign. no ign. ign. ign. ign. ign. ign. no ign. no ign.
0.000 0.000 61.982 115.627 142.854 172.959 93.255 0.000 0.000
0.000 0.000 59.771 113.377 136.365 160.164 83.930 0.000 0.000
0.000 0.000 64.934 129.866 144.831 158.584 90.603 0.000 0.000
0.000 0.000 62.229 119.623 141.350 163.902 89.263 0.000 0.000 0.000 82.755 120.070 244.019 80.918 11.103 0.000 0.000 0.000
0.000 0.000 2.590 8.941 4.429 7.883 4.805 0.000 0.000 0.000 4.106 5.649 14.144 12.196 0.647 0.000 0.000 0.000
0.000 0.000 1.496 5.162 2.557 4.551 2.774 0.000 0.000 0.000 2.370 3.261 8.166 7.042 0.373 0.000 0.000 0.000
10% 20%
303.500 321.700
30% 40% 50% 60% 70% 80% 90%
346.800 362.700 380.200 396.300 414.600 437.300 453.500
Appendix B Detailed pressure transducer data
71
Sample Rate (pps)
100 k
Al/Teflon
Test # Test 1 Test 2 Test 3 Test 4 Test 5 Test 6 Test 7 Test 8 Test 9 AVG St. Dev. St. Error
Peak Pressure (psi) 1187.729 1496.69 1481.496 2084.223 1344.742 1440.976 1755.003 1119.353 2124.743 1559.439444 359.7215905 119.9071968
Table 15: 50nm Al composite pressure tests results. Peak Pressure Rise Time Rise Time Rise Rate Rise Rate (MPa) (sec) ( sec) (psi/sec) (MPa/sec) 8.189102837 0.00014 140 13073883 90141.2463 10.31931385 0.00007 70 26590926.17 183337.974 10.21455492 0.00006 60 32837702.37 226407.978 14.37021112 0.00007 70 33529913.21 231180.604 9.271669318 0.00008 80 25767906.42 177663.453 9.935179363 N/A N/A N/A N/A 12.10031922 N/A N/A N/A N/A 7.717666932 N/A N/A N/A N/A 14.64958667 N/A N/A N/A N/A 10.75195603 0.000084 84 26360066.23 181746.251 2.480192954 3.2094E-05 32.0936131 8220296.376 56676.946 0.826730985 1.4353E-05 14.3527001 3676228.298 25346.7008 Propagation Rate (m/s) 846.667 846.667 635 635 846.667 N/A N/A N/A N/A 762.0002 115.9347906 51.84761454
10k
100k
Al/MoO3/Teflon
Al/MoO3
72
154.481 192.468 162.078 215.26 164.61 238.052 230.445 205.13 349.481 212.445 59.58601444 19.86200481 1.065108956 1.32702009 1.117488425 1.484165392 1.13494595 1.641310693 1.588862277 1.414321503 2.409586571 1.464756651 0.41083109 0.136943697 0.00004 0.00004 0.00004 0.00004 0.00022 0.00005 0.00007 0.00004 0.00003 6.3333E-05 5.9791E-05 1.993E-05 40 40 40 40 220 50 70 40 30 63.3333333 59.7913037 19.9304346
Test 1 Test 2 Test 3 Test 4 Test 5 Test 6 Test 7 Test 8 Test 6 AVG St. Dev. St. Error
716.689 704.027 600.195 916.754 739.482 1061.105 724.286 1000.325 653.378 790.6934444 161.2934212 53.76447374
4.9413965 4.854095086 4.138198678 6.320796059 5.098548696 7.316061126 4.993775969 6.896997796 4.504882539 5.451639161 1.112078945 0.370692982
0.00007 0.00009 0.00008 0.00007 0.00008 N/A N/A N/A N/A 0.000078 8.3666E-06 3.7417E-06
70 90 80 70 80 N/A N/A N/A N/A 78 8.36660027 3.74165739
13738649.5 11598715.2 10509742.1 18909115 14772742.53 N/A N/A N/A N/A 13905792.87 3266057.99 1460625.537
94724.6498 79970.3228 72462.1179 130373.753 101854.47 N/A N/A N/A N/A 95877.0627 22518.6762 10070.6581
846.667 846.667 846.667 846.667 846.667 N/A N/A N/A N/A 846.667 0 0
10k
Test 1 Test 2 Test 3 Test 4 Test 5 Test 6 Test 7 Test 8 Test 9 AVG St. Dev. St. Error
4558415 6711020 6331161 9496793 746413.8 6331195 3950661 6711072 13801951 6515409.089 3636891.497 1212297.166
31429.1637 46270.8521 43651.8166 65478.08 5146.34177 43652.051 27238.8476 46271.2106 95161.0983 44922.1624 25075.4831 8358.49437
635 846.667 846.667 846.667 423.33 846.667 846.667 846.667 1270 823.148 223.1170301 74.37234338
100k
Table 16: 1-3 m Al composite pressure test results.
Test # 1119.353 678.702 567.273 268.442 397.598 606.2736 326.9912409 146.2349286 27.857 58.246 58.246 73.442 54.44775 19.11982326 9.559911631 164.61 98.767 96.233 55.714 144.351 157.013 119.448 42.66042105 17.41604396 0.823564934 0.294133237 0.120079391 0.995265068 1.082566481 0.384134491 0.66350315 0.680974465 0.00031 0.00024 0.00016 0.00031 0.00024 0.000245 1.13494595 0.00021 0.131826535 0.065913268 0.00069 0.000345 690 345 210 310 240 160 310 240 245 0.375404005 0.002105 2105 0.401592016 0.506364744 0.0029 0.0024 2900 2400 0.401592016 0.0018 1800 70907.75 32921.83 13813.06 0.192067246 0.00132 1320 22611.29 2.254525147 1.008254297 0.00067177 671.773771 5377592.9 37077.196 0.00030043 300.426364 2404932.66 16581.426 155.89935 488.89171 226.98802 95.237692 35063.4825 241.75419 25139.8471 173.33314 12569.9236 86.666569 830087.8 289425.2 430521 337667.1 468974.9 546482.4 5723.2537 1995.5164 2968.3377 2328.1326 3233.468 3767.8634 483859.733 3336.0953 5.8224E-05 58.2237065 192893.3 1329.9524 2.377E-05 23.7697286 78748.3598 542.9508 4.180109148 0.000784 784 4346561.95 29968.488 1.850842359 2.741341594 0.0019 0.0009 1900 900 2532474.59 17460.797 861038.526 5936.6514 3.911209488 0.0004 400 2570455.33 17722.665 254 84.667 254 186.2668 76.90223642 34.39172565 35.27778 50.8 84.667 63.5 58.561195 20.88267553 10.44133776 254 230.9091 282.222 230.9091 211.6667 230.9091 240.1026667 24.61439952 10.04878652 4.679485365 0.0005 500 1882471.29 12979.182 127 7.717666932 0.00022 220 13886370 95743.147 211.667
Peak Pressure (psi)
Peak Pressure (MPa)
Rise Time ( sec)
Rise Time (sec)
Rise Rate (psi/sec)
Rise Rate (MPa/sec)
Propagation Rate (m/s)
Sample Rate (pps) 50 k
Test 1
Test 2
Test 3
Al/Teflon
Test 4 Test 5
10k
AVG
St. Dev. St. Error
Test 1
50k 10k
Test 2
Al/MoO3/Teflon
Al/MoO3
73
Test 3 Test 4
AVG
St. Dev. St. Error
Test 1
Test 2
Test 3
Test 4
50k
Test 5 Test 6
AVG
St. Dev. St. Error
Appendix C Additional Figures
74
1200.000
Al/Teflon
Al/MoO3/Teflon Al/MoO3
1000.000
800.000
600.000
Flame Propagation Rate (m/s)
75
400.000
200.000
0.000 0% 20% 40% 60% Mass Percent Aluminum

Figure 21: Confined burn results of composites containing 50 nm Al
80%
100%
400.000
350.000
Al/Teflon Al/MoO3/Teflon Al/MoO3
300.000
250.000
200.000
150.000
76
100.000
50.000
0.000 0% 20% 40% 60% Mass Percent Aluminum

Figure 22: Confined burn results of composites containing 1-3 m Al
80%
100%
600.000
500.000
400.000
300.000
77
200.000
100.000
0.000 20% 40% 60% Mass Percent Aluminum

Figure 23: Open burn results of composites containing 50 nm Al
0%
80%
100%
5.000
4.500
4.000
3.500
3.000
2.500
2.000
78
1.500
1.000
0.500
0.000 20% 40% 60% Mass Percent Aluminum

Figure 24: Open burn results of composites containing 1-3 m Al
0%
80%
100%
PERMISSION TO COPY
In presenting this thesis in partial fulfillment of the requirements for a masters degree at Texas Tech University or Texas Tech University Health Sciences Center, I agree that the Library and my major department shall make it freely available for research purposes. Permission to copy this thesis for scholarly purposes may be granted by the Director of the Library or my major professor. It is understood that any copying or publication of this thesis for financial gain shall not be allowed without my further written permission and that any user may be liable for copyright infringement.
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June 12, 2007____ Date
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Kyle Watson - Fast Reaction of Nano-Aluminum: A Study On Fluorination Versus Oxidation

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Kyle Watson - Fast Reaction of Nano-Aluminum: A Study On Fluorination Versus Oxidation

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FAST REACTION OF NANO-ALUMINUM: A STUDY ON FLUORINATION VERSUS OXIDATION BY KYLE WATSON, M.S.M.E.

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

1.2 Aluminum as a Fuel

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

1.3 Teflon vs. Metallic Oxide as an Oxidizer

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Surface Morphology Area

39.8 m2/g 510 m2/g >50 m2/g

Spherical Spherical Rectangular

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

6 Al + 3(C 2 F4 ) + MoO3 4( AlF3 ) + ( Al 2 O3 ) + 6C + Mo

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Where: F= Mass of the fuel A = Mass of the oxidizer

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

2.2 Open Burn Setup

Texas Tech University, Kyle Watson, August 2007

2.3 Confined Burn Setup

Texas Tech University, Kyle Watson, August 2007

Figure 5: Picture of prepared burn tube.

Figure 6: Picture of instrumented confined burn apparatus.

2.4 Data Acquisition

Texas Tech University, Kyle Watson, August 2007

Figure 7: Schematic illustrating the test setup.

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Pressurization Rate (dp/dt)

Initial Pressure Rise (used to

Sensor 1 Sensor 2 Sensor 3 Sensor 4

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

Chapter III Results and Discussion

Texas Tech University, Kyle Watson, August 2007

Texas Tech University, Kyle Watson, August 2007

3.1.2 The Effects of Particle Size and the Addition of Teflon

Texas Tech University, Kyle Watson, August 2007