Shawn M. Stacy - Hydrodynamical Analysis of Nanometric Aluminum/Teflon Deflagrations

Hydrodynamical Analysis of Nanometric Aluminum/Teflon Deflagrations BY SHAWN C. STACY, B.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 Brandon Weeks Accepted Fred Hartmeister Dean of the Graduate School
May 2008
Texas Tech University, Shawn C. Stacy, May 2008
Acknowledgments
I am exceptionally grateful to everyone that has helped me accomplish so much while at Texas Tech University. Specifically, Im thankful for the opportunities and guidance of Dr. Michelle Pantoya has given me over the last two years. With her help, I have grown much as a researcher and I am more prepared for any challenges ahead of me. I would also like to thank Dr. Mark Grimson at the Texas Tech Imaging Center for helping me with the finer points of electron microscopy. Also, I would like to acknowledge Idaho National Laboratory for technical and financial assistance that was critical to this work.
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Table of Contents
ACKNOWLEDGMENTS ................................................................................... II TABLE OF CONTENTS ................................................................................... III ABSTRACT .......................................................................................................... V LIST OF TABLES .............................................................................................. VI LIST OF FIGURES .......................................................................................... VII I. INTRODUCTION AND BACKGROUND ..................................................... 1 1.1 OVERVIEW ................................................................................................. 1 1.2 ALUMINUM COMPOSITE REACTIVE MATERIALS ............................. 1 1.3 NANO-SCALE COMPOSITES.................................................................... 3 1.4 UNDERWATER TESTING ......................................................................... 5 1.4.1 SEQUENCE FOR UNDERWATER REACTIONS ................................. 5 1.4.2 UNDERWATER TESTING..................................................................... 8 II. EXPERIMENTAL SETUP AND PROCEDURE ....................................... 11 2.1 SAMPLE PREPARATION......................................................................... 11 2.2 EXPERIMENTAL SETUP ......................................................................... 14 2.3 DATA ACQUISITION ............................................................................... 16 2.4 REAL CODE CALCULATIONS ............................................................... 20 III. RESULTS...................................................................................................... 23 3.1 GAS GENERATION .................................................................................. 23 3.2 PRESSURE ................................................................................................. 26 3.3 OBSERVATIONS ...................................................................................... 27
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3.4 TMD RESULTS .......................................................................................... 29 IV. DISCUSSION................................................................................................ 33 4.1 UNDERWATER TESTING OF DEFLAGRATIONS ............................... 33 4.2 HYDROPHOBIC TEFLON ........................................................................ 35 4.3 GAS GENERATION .................................................................................. 37 V. CONCLUSIONS ............................................................................................ 43 VI. FUTURE WORK.......................................................................................... 44 REFERENCES .................................................................................................... 55 APPENDIX .......................................................................................................... 58
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Abstract
The hydrodynamics of deflagrations from reactive materials (RM) submerged underwater can be studied using a modified aquarium test. Normally loose powder RM will disperse after being submerged in water. Introducing hydrophobic materials such as Teflon into the reactant matrix, enables a barrier against permeation of water into the reactants. Also, ignition via resistance heating can be difficult underwater because significant energy is lost by convection off the wire into the water. Nano-Al particles require significantly less energy for ignition than their micron scale counterparts such that underwater ignition via resistance heating can be achieved. The objective of this study is to examine the reaction hydrodynamics from a submerged nano Al-Teflon mixture as a function of mixture composition and bulk density. Submerged Aluminum/Teflon mixtures were ignited and the ensuing reaction was recorded with a high speed camera and a pressure transducer. The resulting bubble shape, size, and pressure histories along with the burn time and rate allow the analysis and comparison of different fuel/oxidizer compositions and powder packing densities. Results show that as the density of the powder decreases the reaction transitions from a slow jet of multiple bubbles to quick single bubble. One observation is that as the percentage of aluminum increases the bubble radius also increases even though there is less of the gas producing Teflon in the mixture. This could imply that the excess aluminum is reacting with water.
List of Tables
1. POWDER SPECIFICATIONS.......................................................................... 12 2. ACTUAL MASS PERCENTS OF AL AND TEFLON FOR MIXTURES ... 13 3. REAL CODE RESULTS FOR INCREASING PRESSURE .......................... 14 4. EXPERIMENTAL RESULTS........................................................................... 23 5. PERCENT TMD AND BUBBLE SHAPE RESULTS..................................... 30 6. REAL CODE RESULTS FOR TEFLON AND 80% PURE ALUMINUM .. 50 7. REAL CODE VOLUME PRODUCT RESULTS FOR AL + TEFLON WITH A MASS PERCENTAGE OF WATER ............................................................ 50 8. REAL CODE ADIABATIC FLAME TEMPERATURE RESULTS FOR AL + TEFLON WITH A MASS PERCENTAGE OF WATER ........................... 61 9. EXPERIMENTAL RESULTS FOR DISPLACEMENT ENERGY, BUBBLE GROWTH RATE, AND PRESSURIZATION RATE .................................... 62 10. PERCENT OF WATER REQUIRED FOR COMPARISON IN REAL CODE RESULTS ................................................................................................ 63
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List of Figures
1. HEAT OF COMBUSTION COMPARISON OF AL/TEFLON, TNT, AND THERMITE MIXTURES CALCULATED USING REAL CODE ................. 2 2. UNDERWATER EXPLOSIVE BEHAVIOR .................................................... 8 3. SEM MICROGRAPH OF ALUMINUM AND TEFLON AT 50% TMD. ... 12 4. TANK SETUP INCLUDING THE SAMPLE BLOCK (A), IGNITION WIRE LEADS (B), AND UNDERWATER BLAST PRESSURE SENSOR (C). ........................................................................................................................ 16 5. OVERALL TEST SETUP WITH THE HIGH SPEED CAMERA, TANK, AND FIBER OPTIC LIGHT GUIDE ............................................................... 17 6. EXAMPLE OF A SINGLE BUBBLE REACTION WITH 14 MILLISECONDS BETWEEN EACH FRAME .............................................. 17 7. LIGHTED CONDITIONS WITH THE HIGH SPEED CAMERA (A), TANK SETUP (B), FIBER OPTIC LIGHT GUIDE (C), AND VARIAC TRANSFORMER (D) ......................................................................................... 18 8. PHANTOM SOFTWARE FOR RADIUS ANALYSIS. .................................. 19 9. THE RADIUS IS OBTAINED FROM TWO POINTS PER FRAME ON THE SURFACE OF THE BUBBLE. THE POINTS ARE AVERAGED FOR THE FINAL RADIUS CURVE. ........................................................................ 20 10. MAXIMUM RADIUS DATA FROM HIGH SPEED VIDEOS SHOWING THE MAXIMUM RADIUS INCREASES WITH POWDER EQUIVALENCE RATIO................................................................................... 25 11. MAXIMUM BUBBLE VOLUME ..................................................................... 26 12. A REPRESENTATIVE PRESSURE PROFILE FOR ONE SECOND ........ 27 13. EXPERIMENTAL PRESSURE RESULTS AT MAXIMUM RADIUS ....... 27 14. EXAMPLES OF UNBURNED MICRON ALUMINUM AND TEFLON REACTIONS ....................................................................................................... 28
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15. ILLUSTRATION SHOWING THE INFLUENCE OF CARBON ON BUBBLE TRANSPARENCY ............................................................................ 29 16. AIR BUBBLE BEFORE REACTION .............................................................. 29 17. %TMD AND BURN TIME ANALYSIS .......................................................... 30 18. FROM LEFT TO RIGHT: THE JET OF BUBBLES, THE BALL OF BUBBLES, THE MUSHROOM SHAPED BUBBLE, AND FINALLY THE SINGLE BUBBLE THAT IS USED FOR THE RADIUS ANALYSIS. ........ 31 19. RADIUS OSCILLATIONS FOR BLOCK RIGHT1....................................... 32 20. DETAILED RADIUS OSCILLATIONS FOR TIME .02 TO .03 SECONDS FOR BLOCK RIGHT1 ...................................................................................... 32 21. PENDULUM ANALOGY .................................................................................. 35 22. REAL CODE CALCULATION FOR THE AL/TEFLON WITHOUT AND WITH 50% WATER. THE EQUIVALENCE RATIO IS ONLY CALCULATED FOR THE AL/TEFLON POWDER..................................... 38 23. REAL CODE CALCULATION OF ADIABATIC FLAME TEMPERATURE FOR DIFFERENT MASS PERCENTS OF WATER ..... 40 24. RESULTS SHOWING GAS PRODUCTION INCREASES WITH FUEL RICH MIXTURES AND MOST OF THE GAS PRODUCTION INCREASE IS FROM HYDROGEN GAS (AOCHI, 2000)................................................. 41 25. HEAT OF COMBUSTION (KJ/MOLE) .......................................................... 58 26. HEAT OF COMBUSTION (KJ/M3) ................................................................. 59 27. HEAT OF COMBUSTION (KJ/KG) ................................................................ 60 28. DATA FROM TABLE 4 PLOTTED TO SHOW THE EFFECT OF SAMPLE MASS .................................................................................................. 64 29. FIRST ATTEMPT NORMALIZING RADIUS DATA .................................. 54 30. SECOND ATTEMPT NORMALIZING RADIUS DATA ............................. 66 31. SECOND ATTEMPT NORMALIZING RADIUS DATA IN TERMS OF VOLUME PER MOLES .................................................................................... 67
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Chapter I Introduction and Background

1.1 Overview
Reactive materials (RM) are of interest in the combustion community. These materials have the adaptability that allows maximum performance and still have the safety required for various applications. Furthermore, nanometer-scale RM offer enhanced performance over their micron-scale counterparts. To better understand how nanometer-scale RM or RM in general behave, hydrodynamic studies can be done. Aquarium tests offer a unique way to hydrodynamically analyze RM and characterize performance. Combustion characteristics that are difficult to obtain under normal burn testing conditions can easily be obtained with underwater burns. It is possible to determine an estimate of the gas generation and kinetic energy released. In addition, aluminum-based RM have a special interest because of the aluminum/water reaction that can produce hydrogen along with large amounts of energy. Hydrogen production is of significant interest for its use in alternative fuels.
1.2 Aluminum Composite Reactive Materials

Aluminum composite RM have a high energy density and the combustion performance that allows them to be used in various applications from new types of propellants to underwater cutting torches. Aluminum reacts very readily and acts as a metal reducing agent in reduction/oxidation reactions (metal combustion). On exposure to air, aluminum forms a passive layer of aluminum oxide that is a barrier preventing the 1
remaining aluminum from reacting. The aluminum oxide shell allows the aluminum RM to be handled safely and also could change the reaction mechanism. Aluminum can be combined with metal oxides (known as Thermites), other metals (known as intermetallics), and other compounds (such as Teflon). Aluminum-based reactions are extremely exothermic (Fischer & Grubelich, 1998). Also, based on the REAL code (Belov, 2004) calculations shown in Figure 1, aluminum/water and aluminum/Teflon reactions have a higher energy density than a conventional explosive (TNT) and common Thermite reactions. Heat of Combustion results in kJ/mole, kJ/m3, and kJ/kg are presented in the appendix.
cal/cc C7H5N3O6 (TNT) cal/g
2Al+Fe2O3
2Al+MoO3
2Al+3H2O
4Al+3C2F4
1000
2000
3000
4000
5000
6000
7000
Figure 1. Heat of Combustion comparison of Al/Teflon, TNT, and Thermite mixtures. The values were calculated using REAL code
1.3 Nano-scale composites

Advances in powder manufacture have allowed particles of aluminum to be commercially available in the nanometer range. Nano-scale particles have one dimension less than 100 nanometers (Son, 2004). RM made with the smaller particles can have improved combustion performance. Combustion performance can be characterized by ignition dynamics and energy propagation. Specifically, parameters such as flame speed, energy generated, energy required for ignition, temperature change, pressure change, and completeness combustion can be used to characterize performance. For example, Nanoscaled reactive materials have a faster flame speed (Bockmon et al., 2005) and lower apparent activation energy (Granier & Pantoya, 2004) than their micron-scaled counterparts. The reaction speed is greatly affected by the smaller particle size. Smaller particle size allows for a larger surface area to volume ratio, decreasing the distance the fuel and oxidizer have to travel to react and increasing the likelihood of contact between the different reactants. Another reason, although not completely based on size of the
particles, is that for loosely packed Thermites, the reaction is convection controlled (Asay et al., 2004). Energy is quickly transferred to the RM in front of the flame faster, allowing the flame to propagate faster with conduction than convection. The change in the mode of heat transfer is only valid for mixtures that have porosity to allow gas to disperse between particles. The mode of heat transfer and the surface area to volume both are influences to increase the nano-scaled RM reaction speed.
Another factor for RM materials is activation energy. Activation energy is the energy required for an energetic material to ignite. Lower activation energy will allow a reaction to occur more easily. For instance, with low activation energy a simple wooden match would be able to ignite the reaction while for higher activation energies a powerful laser is needed. The energy imparted on the sample with the match is much less than the energy from the laser. Particle size plays a large role in the apparent activation energy for aluminum reactions. For example, a composition made from Molybdenum trioxide, MoO3, and nanometric aluminum particles will ignite very readily compared to micron scale aluminum particles (Granier & Pantoya, 2004). The lower apparent activation could allow for more complete burns with smaller aluminum particles. The lower apparent activation energy would allow the flame to propagate to areas of inhomogeneity (excess fuel or oxidizer, inconsistent density, impurities) when they normally would not. Finally, the alumina shell plays a key role in changing how nano-scaled aluminum particles react with an oxidizer. The alumina shell is an oxide layer that forms on the surface of aluminum from exposure to oxygen. The alumina shell might act much like a pressure vessel, containing the molten aluminum under compression until the shell fails. When the shell fails the shell could be violently ejected to the surroundings allowing the molten aluminum core to be completely exposed. The influence of the alumina shell to allow the molten aluminum inside the particles to react unimpeded is called melt dispersion (Levitas et al., 2006). Melt dispersion helps account for the increased reaction
speed that is not explained by the diffusion mechanism and the surface area to volume ratio increase alone.
1.4 Underwater Testing

Underwater explosive testing is an important type of research for reactive materials. Water provides a more dense environment enabling observation of the gasliquid interface. Testing RM underwater allows for monitoring the pressure of the shockwave emanating from the reaction and more importantly for this work, tracking the interface between the gas products and water. The interface can easily be seen underwater, unlike in gas environments were the intermixing of gas from the reaction and the environment is too turbulent and the gas from the reaction diffuses too readily. The interface makes it possible to determine the amount of kinetic energy released and the volume of gas products produced from a reaction. Underwater explosive testing allows for the characterization of RM in a controlled and repeatable setup. 1.4.1 Sequence for underwater reactions To understand underwater testing of RM, underwater explosion/reaction behavior must be understood. Underwater explosions have a sequence of distinct phases starting from the pre-reaction initial conditions to oscillations and collapse (Cole, 1948). Knowing these phases is important because different data can be obtained from each phase.
The initial conditions and setup, particularly depth of the reaction, are important for analysis. The reaction will displace less water at greater depths and also be more unlikely to break the surface of the water. Another important factor is the reflection of acoustic waves based on structures surrounding the explosive sample. Reflected waves can cancel out or provide interference for the initial acoustic wave resulting in erroneous results. The next step in the sequence is ignition and reaction. The activation energy barrier of the sample must be overcome in order for the reactive material to ignite. Once ignited, the reactive material will begin to propagate if the energy generated is greater than the activation energy. The reactants will rapidly transition into products and energy in the form of light, heat and physical expansion. In many cases the intermediate products and final products are gases causing large increases of pressure on the order of tens of thousands of atmospheres (Cole, 1948). After the initial reaction the pressure concentrated at the reactive zone starts to expand spherically. In the water surrounding the gas bubble, there will be an outgoing acoustic pressure wave. The wave will have a sharp, near vertical rise that then will decay from the peak to the center of the reaction. The profile will also drop in amplitude the peak moves away from the center of the reaction. If the velocity of the peak is faster then the speed of sound in water the wave can be called a shockwave, otherwise it is know as an acoustic wave. The compressibility of water has much larger role in mathematical equations for shockwave than acoustic waves. The first oscillation is not 6
used in calculations due to these effects. In contrast, the pressure inside the gas bubble will be isotropic and homogenous but will change with the diameter of the bubble. The pressure inside the bubble will decrease to reach equilibrium with the pressure of the surrounding water forcing the bubble to grow. Once the bubble reaches maximum radius it will start to oscillate (Bocksteiner, 1996; Menon & Mihir, 1997). The gas bubble will oscillate for a reason very similar to why a pendulum will swing back and forth. The pressure is the driving potential in the bubble similar to the height driving the movement in a pendulum. In both cases kinetic and potential energy are exchanged with each other until the energy is completely dissipated and the oscillations stop. For the bubble oscillations, the highest pressure will be when the bubble is at the minimum radius. When the bubble is at its maximum radius it will have the least amount of pressure. These two extremes will be the points of highest potential energy, while the highest kinetic energy will be when the pressure is equal to the hydrostatic pressure outside the bubble. The bubble will oscillate between the maximum and minimum radii until pressure equilibrium is reached with the surrounding water and all the energy is lost from viscous dissipation. These oscillations are illustrated in Figure 2.
Figure 2. Underwater Explosive Behavior
Based on viscosity of water and speed of the bubble rise from buoyancy, the bubble will collapse into smaller bubbles. Depending on the RM and depth of the reaction this could be as soon as it reacts or until it reaches the surface. Once the bubble collapses, radius and bubble pressure data will make it difficult to obtain any useable results, because there are multiple radii to measure and the pressure sensor will not be inside of a bubble. 1.4.2 Underwater Testing Underwater explosive testing is more time consuming and costly than normal reactive material testing but the benefits are well worth while. The main benefit is visualizing the volumetric gas production of the reaction. Underwater testing methods are diverse allowing trade offs based on the data required and resources available.
Underwater explosive testing is often carried out in open areas of water to minimize the effects of acoustic reflections and damage to surroundings while being able to use full sized charges and munitions. These tests can be done destructively with a real munitions and targets or non-destructively with explosives in open water. Open water tests are useful because they allow for repeatable experiments that can be used to compare the characteristics of one explosive to another. Both of these types of tests are time consuming to prepare and difficult to observe underwater. Conversely, there are also aquarium tests which allow for quick setup and comparable results to open water nondestructive tests. Aquarium tests are underwater explosive experiments conducted in a sturdy tank filled with water. Aquarium tests commonly use pressure transducers to measure the pressure wave and/or the bubble pressure. The tank setup also allows for adaptability while still maintaining the ability for positioning the sensors and samples in the same location each experiment. Researchers commonly suspended the RM samples in the center of the tank (Frankel et al., 1982; 1996; Menon & Mihir, 1997; Aochi et al., 1999), but other methods were also used (Goldstein & Johnson, 1982). Suspending the sample reduces the influence of the walls and surface of the water on the pressure waves in the tank. Each experimenter used a different ignition, pressure sensor, and camera setup that suited their samples. The most important advantage aquarium tests have are lighting and camera conditions that are impossible in an open water setup are made trivial in aquarium experiments. With the right lighting conditions, it possible to film the entire sequence of
events of an underwater reaction with a high speed camera. Aquarium testing does have its disadvantages. The wave reflections cause problems for data acquisition and for tank durability. The wave reflections from the tank walls and the water surface will make shockwave analysis difficult but will not strongly influence the bubble radius and pressure (Menon & Mihir, 1997). Finally, the tank must be cleaned after each experiment because of the solid product residue. The advantages of aquarium tests make them an invaluable research tool besides the disadvantages.
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Chapter II Experimental Setup and Procedure

2.1 Sample Preparation
Reactive material samples were obtained by mixing aluminum and Teflon (PTFE) at various fuel/oxidizer balances. The aluminum powder was obtained from Novacentrix (Austin, Tx). The powder is spherical, with an average diameter of 80 nanometers, and covered with thin oxide (alumina) shell roughly 2 nanometers thick. The alumina shell was determined to be 20% of the total particle mass. X-ray diffraction, TEM imaging, and BET surface area analysis was used to find the particle size and purity. The Teflon obtained from Dupont (Zonyl MP1150) particles have an average diameter of 200 nanometers and are also spherical. An SEM micrograph of the mixture is shown in Figure 3.
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Figure 3. SEM micrograph of Aluminum and Teflon at 50% TMD.
In addition to the nanoscale aluminum, micron-scale aluminum was also tested. The micron aluminum (Atlantic Equipment Engineers) was 1-3 microns in diameter, spherical and 99% pure. Molybdenum trioxide, MoO3, (Novacentrix) was also used as an oxidizer for initial experiments. The Molybdenum trioxide particles were rectangular, 44 nanometers in the smallest dimension, and 99% pure. The powders are displayed in Table 1.
Table 1. Powder Specifications Manufacture Novacentrix Dupont Atlantic Equipment Engineers Novacentrix
Powder Aluminum Teflon-PTFE Aluminum MoO3
Particle Size 80nm 200nm 1-3m 44nm
Purity 80% 100% 99% 99%
Form Factor Spherical Spherical Spherical Rectangular
The aluminum and Teflon powders were combined at mass percents shown in Table 2. Mass percents were given by the chemical balance reaction in Equation (1) (Asay et al., 2004) and the equivalence ratio, , Equation (2). The mass percents took into account the difference between active aluminum content the overall mass of the powder. The combined powders were suspended in hexanes to allow for ultrasonic mixing. Ultrasonic mixing improves homogeneity by reducing agglomerates. The
suspended powders were placed under cyclic ultrasonic vibration with a Misonix Sonicator 3000 for 10 seconds on and 10 seconds off for 2 minutes total. Cyclic operation reduces the maximum thermal load on the sample. After mixing the suspended particles are placed in a glass pan inside a fume hood to dry. The final dry powder mixture was removed with an electrically grounded metal brush and placed into a glass vial.
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Table 2. Actual mass percents of Al and Teflon for mixtures
1 1.5 2 4 Al + 3(C2 F4 ) 4 AlF3 + 6C
80% Pure Powder %Al %C2F4 30% 70% 39% 61% 46% 54% (1)
(F O ) = (F O )
Actual
(2)
Balanced
Where: F = Mass of the fuel 0 = Mass of the oxidizer (C2F4) The SEM micrograph, shown in figure 2, was taken of the final aluminum/Teflon reactive material to verify homogeneity and the lack of agglomerates. Micrographs are of an aluminum/Teflon pellet that was pressed to 50% of theoretical maximum density (TMD). TMD (Equation (3)) is the bulk density of a composite material assuming there are no voids. A Hitachi S-570, medium resolution, tungsten filament, scanning electron microscope was used.
TMD =
Al M Al + C F M C F + Al O M Al O
2 4 2 4 2 3
2 3
M total
Where: = bulk density & M = mass
(3)
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REAL code was used to show that the balanced equation was a valid approximation of the actual reaction. In Table 3, as the pressure increases the products approach the assumed and ideal balance reaction. In an underwater reaction, the pressure will increase as a function of depth (hydrostatic pressure), gas production, and reaction rate. Watson (2007) showed that the aluminum/Teflon reaction was shown to have a flame propagation rate of over 700 meters per second for confined burns. The confined burn apparatus that was used consisted of loose powder in polycarbonate tubes (108mm long with a 3.2 mm inner diameter) ignited with nickel/chromium wire. These faster reactions have less time for the gas expansion therefore will build up pressure allowing for reaction to occur at higher pressures.
Table 3. REAL code results for increasing pressure
Pressure, atm 1 10 100 1000 10000 Balanced Equation
AlF3 C Other products Temp, K 62.33% 14.18% 23.49% 3513.3 64.98% 14.10% 20.92% 3835.9 67.68% 14.45% 17.88% 4189.1 70.51% 14.45% 15.04% 4326.2 77.62% 16.81% 5.57% 4726.6 82.34% 17.66% 0.00%
2.2 Experimental Setup

The underwater combustion experiments were conducted inside of an acrylic tank. The tank was 4 inches (~10 cm) long, 4 inches wide and 7 inches (~18 cm) tall as shown in Figure 4. The tank was filled with 1 liter of distilled water to ensure to constant hydrostatic pressure between experiments and to reduce impurities from the water that may influence the reaction chemistry. 1 inch, clear acrylic cubes (Delvies Plastics Inc.)
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were positioned at the bottom of the tank. The cubes had a flat bottomed, 3/16 inch (~0.16 cm) diameter, and 3/16 inch deep hole milled into the top. Approximately 50mg of powder mixture are placed along with a small length of 33-gage Nickel/chromium (Omega engineering, 80% nickel/20% chromium) alloy wire inside the hole. Nickel/chromium wire was used because it has a high melting temperature along with a high electrical resistance. The 33-gage wire was used because the smaller wire will heat the surroundings quicker than a large gage wire. Also by using a smaller wire, which will take up less volume, allows for easier loading of the sample and more accurate TMD calculations. The sample was ignited by supplying 15 volts of AC current to the wire with a variac voltage transformer.
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Figure 4. Tank setup including the sample block (a), ignition wire leads (b), and underwater blast pressure sensor (c).
2.3 Data Acquisition

Data was collected from high-speed video and pressure transducer signals. A schematic of the test setup is shown below in Figure 5.
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Figure 5. Overall test setup with the high speed camera, tank, and fiber optic light guide
The reactions were recorded with a high speed digital camera (Vision Research, Phantom 7) at 5000 frames per second (fps). The optimal camera settings for this analysis were as follows: Resolution at 512x512 pixels, exposure time at 180s, minimum (Extreme Dynamic Range) exposure time at 100s, and the f-stop at the 16 setting on the 55mm Nikon lens. The Extreme Dynamic Range exposure time helps the image from being over saturated during the reaction while still allowing the darker portions of the reaction event to be filmed. Figure 6 shows an example of the video recorded.
Figure 6. Example of a single bubble reaction with 14 milliseconds between each frame
It was difficult to get enough light into the cameras CCD without also oversaturating the image at high frame rates. To alleviate the problem a fiber optic light guide (Cole-Parmer Illuminator 41720) was used to focus intense light where it was needed. The fiber optic light guide enhances the lighting conditions to improve imaging before and after the reaction event was self illuminating. Secondly, it was important for the
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surface of the bubble to be visible during the reaction. A white sheet of paper is used as a background on the side opposite of the camera. The white background improved contrast allowing the interface of the bubble to be monitored more accurately. Figure 7 shows the setup under lighted conditions.
Figure 7. Lighted conditions with the high speed camera (a), tank setup (b), fiber optic light guide (c), and variac transformer (d)
The high speed video was analyzed by using the Phantom software shown in Figure 8. Radius data was collected by using the pressure sensor as a scale (4.2 mm) and clicking on two points on the edge of the bubble. An origin was set at the center of the top of the hole in the acrylic block (the intersection of the two lines in the figure). One point was taken from where the top of the bubble intersects the vertical origin line. This point would give a diameter from the top of the bubble to the top. The vertical radius is 18
the quotient of the diameter is divided by two. The second point was taken from the surface of the bubble at the furthest point to the right. The second point gives the side radius.
Figure 8. Phantom software for radius analysis.
These points were averaged to find the final radius curve used as seen in Figure 9. The maximum radius was defined as the average radius corresponding to when the maximum side radius occurs. The maximum side radius was used because as the bubble migrates upwards the side radius decreases while the top radius continues to increase.
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25 20
Radius, mm
15 10 5 0 0 0.01 0.02 0.03

Time, seconds Avg Side TOP
0.04
0.05
0.06
Figure 9. The radius is obtained from two points per frame on the surface of the bubble. The points are averaged for the final radius curve.
Along with the high speed video, pressure transducer data was collected. The data was recorded with an underwater blast pressure sensor (138A33, PCB Piezotronics Inc.), along with a signal conditioner (483A22, PCB Piezotronics Inc.), and data acquisition board (BNC-2110, National Instruments) at 10 kHz. The sensor was placed at a slight angle, approximately 1cm over the sample cube, and approximately 3/4cm away from the hole. The pressure sensor was 4.2 mm (.17 inch) in diameter allowing it to be placed close to the small sample without being a large obstruction.
2.4 REAL Code Calculations

Estimated values for heat of combustion, adiabatic flame temperature, and gas generation were calculated using the REAL code (Belov, 2005). REAL is a chemical equilibrium modeling program designed for high temperatures (6000K) and high 20
pressures (600-800 MPa) (Belov, 2004). One of three different equations of state (EOS) can be chosen for calculations: Ideal gas, 3 coefficients virial EOS or, an EOS proposed by Nedostup (1979). Virial EOS was used for these calculations because it gave the best results at the temperatures and pressures of these reactions. The heat of combustion is calculated by using the default template provided in REAL and inputting desired composition. The heat of combustion template included options to fine-tune the specific volume and specific internal energy. Iterations of REAL code calculations were done to determine the specific internal energy that will give similar results as Fischer and Grubelich (1998) for a range of various reactions. The specific internal energy was then used to calculate the heat of combustion for the balanced aluminum/Teflon reaction. The heat of combustion was calculated to be 10,709 kJ/kg for aluminum/Teflon mixtures with pure aluminum and 8856 kJ/kg for 80% pure aluminum. Experimental differential thermal analysis (DTA) results presented by Cudzillo and Trxcinski (2001) for aluminum/Teflon at 26.5% aluminum (slightly fuel lean) were lower at 7,540 kJ/kg but only 57% of the aluminum reacted. Their experiment analyzed the mixture of aluminum (50 micron diameter) and Teflon particles (less than 40 microns in diameter) at a heating rate of 10 Kelvin per second. Assuming that only 57% of the Teflon reacted with the 57% of the aluminum, the REAL code heat of combustion would be 6104 kJ/kg. The heat of combustion was calculated 8755 kJ/kg with only 57% aluminum and 100% of the Teflon. Real code gave a close approximate to
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the experimental data as the experimental results fall between the two heat of combustion values. The adiabatic flame temperature and gas generation were calculated by inputting the desired composition and modeling the reaction in a combustion chamber at constant pressure (1 atm). The specific enthalpy of the system was also inputted. The specific enthalpy was determined in the method similar to the specific internal energy for the heat of combustion
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Chapter III Results

3.1 Gas Generation
The modified aquarium test provides a method to measure gas generation. The gas/water interface allows the radius to be tracked and assuming the bubble is spherical, the volume can be calculated. Table 4 shows the experimental results for the burn times and maximum radii for 15 different samples. The equivalence ratios (), sample mass and block numbers are also displayed. Blocks 26-28 were not used for maximum radius calculations. The multiple bubbles would erroneously show the radius values to be estimated lower than they actually were. Multiple bubbles were defined as a stream of 2 or 3 large bubbles. The burn times for those blocks were also shown to be longer than the rest of the samples. Since the radius results are not used for 26-28 blocks and block 29 has no video there are 2, 4, and 5 results for the 1, 1.5, and 2 equivalence ratios, respectively. The largest radius was shown to be 22.6 millimeters for a fuel rich sample.
Table 4. Experimental results
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Block# EqR, % TMD Sample Mass, mg Burntime, sec 18 1 17.3% 31.2 0.132 19 1 16.2% 29.5 0.116 20 1.5 11.5% 27.7 0.065 23 1.5 12.3% 30 0.070 25 2 15.8% 29.2 0.068 31 2 15.1% 28.6 0.072 26 1 14.3% 26.1 0.176 27 1 15.2% 28.3 0.196 28 1 14.9% 27.1 0.170 29 1.5 15.2% 34.3 no video 30 1.5 14.8% 31 0.100 34 1.5 15.2% 29.7 0.067 35 2 14.8% 28.6 0.065 37 2 15.3% 36.7 0.067 38 2 14.1% 26.1 0.119
Max. Radius, mm 18.3 18.0 17.7 19.2 19.4 18.8 Multiple bubbles Multiple bubbles Multiple bubbles no video 16.7 17.6 20.4 22.6 19.5
Feb-08
Oct-07
24
To better understand how aluminum/Teflon stoichiometrically the radius results were plotted in Figure 10. The bubble radius increases with equivalence ratio from the balanced to the most fuel rich samples (=1 to =2). It also seems like there may be a small increase from the balanced samples to the slightly more fuel rich (=1.5) ones.
24 23 Max Radius, mm 22 21 20 19 18 17 16 15 0.5 1 1.5 2 2.5 Powder Equivalence Ratio,

Figure 10. Maximum radius data from high speed videos showing the maximum radius increases with powder equivalence ratio.
The sample mass would increase the bubble radius because there are more reactants to product gas. Calculations in the appendix (
25
A.4 Normalizing Radius Data) normalize the radius data with moles and mass of the sample. The bubble radius was normalized by calculating the volume of the assumed spherical bubble and dividing by mass (Figure 11).
0.0014 Volume of Bubble, m^3/kg 0.0012 0.001 0.0008 0.0006 0.0004 0.0002 0 0.5 1 1.5 Equivalence Ratio,
Figure 11. Maximum bubble volume
2.5
3.2 Pressure
The pressure data was correlated to the visual data by assuming there was no pressure increase at the sensor until the bubble reached it. In detonations there would be an initial shockwave followed by a slow decay until the bubble reached the sensor (Cole, 1948). For the deflagrations there is no shockwave therefore the first pressure increase would be the interface of the bubble. The pressure at the maximum radius is shown in figure 10. It cannot be determined if there is any pressure change at the maximum radius based on this data.
26
5 4.5 4 3.5 Pressure, kPa 3 2.5 2 1.5 1 0.5 0 0 0.2 0.4 Tim e, sec 0.6 0.8 1
Figure 12. A representative pressure profile for one second
1.8 1.6 Bubble Pressure, kPa 1.4 1.2 1 0.8 0.6 0.4 0.2 0 0.5 1 1.5 Equivalence Ratio,
Figure 13. Experimental pressure results at maximum radius
2.5
3.3 Observations
In addition to the radius and pressure data, observations that were more qualitative were made. The first observation was that micron aluminum was difficult to 27
ignite using resistance heating in this setup. A small amount of powder would ignite and quench before completely burning as seen in Figure 14. Figure 14 illustrates small amounts of lightly packed micron aluminum and Teflon powder that did not completely burn. The powder immediately around the wire would ignite then quench.
Figure 14. Examples of unburned micron aluminum and Teflon reactions
A second observation was that fuel rich aluminum and Teflon mixtures intrinsically have less carbon in the final products. The carbon forms a thin layer on the surface of the bubble. This thin layer reduces visibility through the surface of the bubble as can be seen in the balanced mixture for figure 15. In the fuel rich bubble there was less carbon on the surface of the bubble and the bubble is more transparent.
28
Figure 15. Illustration showing the influence of carbon on bubble transparency
Another important observation was that after being submersed a thin layer of air would be visible on the surface of the aluminum and Teflon powder. The thin layer of air can be seen as a small bubble (before the reaction is initiated) in the center of Figure 16. When aluminum and MoO3 powder were placed under the same conditions the powder would completely disperse in the water. The thin layer of air acts as barrier preventing water interacting with the powder sample.
Figure 16. Air bubble before reaction
3.4 TMD Results

Bubble shape was roughly dependent on percent TMD (Theoretic Maximum Density). As the percent TMD decreases the bubble shape becomes less chaotic, as shown in Table 5; the high density samples burned as a series of bubbles and low density ones burned as single bubbles. Furthermore, the mid-ranged TMD samples show a transition where the sample will be either a ball of bubbles or a few large bubbles. In addition, burn times were dependent on bubble shape. For jets of bubbles/multiple bubbles, the burn duration was .260 to .3 seconds while for the single bubble the burn 29
times were more than five times faster at .049 to .052 seconds. The TMD and burn time results are also shown in Figure 17 to better illustrate the increase. Finally, the percent TMD analysis experiments were not used to find the bubble radius because of the large differences between the samples mass.
Table 5. Percent TMD and bubble shape results
Block# Top7 Right1 Top8 Right3 Right5 Right6 Right7 Right8
EqR, % TMD Sample Mass, mg Burntime, sec 1 41.6% 17.3 0.260 1 42.2% 17.1 0.300 1 35.9% 17.2 0.300 1 35.5% 17.4 0.158 1 16.8% 10.2 0.127 1 20.8% 9.1 0.052 1 17.8% 10.6 0.103 1 16.3% 10.6 0.049
Hydrodynamics Jet of Bubbles Jet of Bubbles Multiple Bubbles Ball of Bubbles Mushroom Single Bubble Mushroom Single Bubble
Low TMD Mid. Hi.
0.35 0.3 Burn Time, sec 0.25 0.2 0.15 0.1 0.05 0 0% 10% 20% 30% 40% 50% Percent TMD
Figure 17. %TMD and burn time analysis
30
Figure 18 illustrates the visual difference in percent TMD and bubble shape. Dark clouds of carbon and gas from were previous bubbles have collapsed can be seen for the 40% and 35% TMD pictures. The defining difference between the mushroom and single bubble is that the mushroom bubble would grow separated from the block.
Figure 18. From left to right: the jet of bubbles, the ball of bubbles, the mushroom shaped bubble, and finally the single bubble that is used for the radius analysis.
It should also be noted that for the jet of bubbles in high TMD samples oscillations are visible in bubbles that separate from main column of bubbles. The period of oscillation was shown to be .0028 seconds (2.8 milliseconds) in Figure 19 and Figure 20.
31
8 7 6
Radius, mm
5 4 3 2 1 0 0 0.005 0.01 0.015 0.02

Time, seconds
0.025
0.03
0.035
0.04
Figure 19. Radius oscillations for block right1

8 7 6 Radius, mm 5 4 3 2 1 0 0.02
0.021
0.022
0.023
0.024
0.025
0.026
0.027
0.028
0.029
0.03
Time, seconds
Figure 20. Detailed radius oscillations for time .02 to .03 seconds for block right1
32
Chapter IV Discussion
4.1 Underwater Testing of Deflagrations
Distinct and complete oscillations were difficult to capture in large single bubble reactions produced from deflagrations. In single bubble deflagrations, the bubble would slow its growth rate as it expanded and give the appearance of pausing. Deflagration reactions are defined by a combustion wave that propagates at subsonic speeds while detonations are defined by a combustion wave at supersonic speeds (Kuo, 2005). The key difference for a hydrodynamical analysis is that deflagrations are slower than detonations. In underwater explosives the reactants are quickly converted into a high pressure gas bubble that expands and oscillates. The oscillations occur because of the pressure difference between the ambient surroundings and the inside of the bubble. These oscillations are used to calculate the bubble, potential, kinetic, and energy lost from the damping effects of the water. The equations used to calculate these quantities are all based on the assumptions that the pressure is less than hydrostatic pressure at the maximum radius, the maximum pressure is during the minimum radius and that reaction is complete before the radius reaching its maximum (Cole, 1948; Trilling, 1951; Vokurkal, 1987; Bocksteiner, 1996; Menon & Mihir, 1998). None of the assumptions correlate to the results seen for the aluminum/Teflon deflagrations.
33
However, there was oscillatory behavior captured in high speed videos for some of the small bubbles in high TMD samples. The periods of the oscillation were brief compared to the overall length of the reaction. The period of oscillation was .0028 seconds (2.8 milliseconds) of a 0.3 second total burn time for a high TMD sample. For explosives the burn time is shorter than the period of oscillation. In other research with the detonation of explosives, the time scales of initial oscillation were on the order of 10100 milliseconds, but reaction was finished before end of the first period of oscillation (Cole, 1948; Bocksteiner, 1996; Menon & Mihir, 1998). The difference in the total burn time for detonations and deflagrations implies the reaction is obscuring the oscillations by continued production of gas for deflagrations. Continued gas production could also explain why the pressure at the maximum radius is greater than the hydrostatic pressure as seen in Figure 13. Furthermore, it is possible that the test setup plays a role in the slower gas production. The sample is ignited in a cylindrical hole inside of an acrylic block. The gas products are ejected into the surrounding environment as a jet. In other research (Cole, 1948; Menon & Mihir, 1998; Aochi et al., 2000) the sample charge was suspended in the center of the tank and the gas expands radially outward. Limiting the gas to one direction could slow the gas expansion allowing the oscillations to initiate while the gas is still expanding thereby masking them. An analogy for the difference between the deflagrations and other two classifications of combustion in underwater reactions is the pendulum example suggested 34
in the introduction. An illustration of this analogy can be seen in Figure 21. The detonation or explosion would be similar to releasing the weight of a pendulum from as high as possible. The deflagration on the other hand, would be similar to having the weight hanging freely and continually applying a force (wind for example) in one direction. The oscillations for the explosion example would be very apparent, while in the deflagration the oscillations would be reduced by the continued force.
Figure 21. Pendulum Analogy
4.2 Hydrophobic Teflon

The thin layer of air on the aluminum/Teflon shows that it is hydrophobic (little to no water affinity) while aluminum/MoO3 is not. To quantify the water affinity of Teflon, the sessile drop technique can be used (McHale et al., 2001; Blossey, 2003; Mao et al., 2005; Van Der Wal & Steiner, 2007). A water drop is placed on the surface of the material and the contact angle between the surface and the water drop is measured. The maximum contact angle (180) for a spherical drop will form for super-hydrophobic.
35
Conversely, for a super-hydrophilic material the drop would completely spread out with no contact angle. The contact angle of smooth Teflon and water was reported as 110-118 (Van Der Wal & Steiner, 2007). Van Der Wal and Steiner (2007) have shown it is possible form a superhydrophobic surface made of Teflon. They sintered a thin layer of 200 nm Teflon particles and micron scale polystyrene beads together on a glass surface. The polystyrene was removed with chloroform leaving a porous Teflon matrix. Van Der Walm et al. reported that their porous Teflon surface is more hydrophobic than a smooth Teflon surface; they reported a maximum contact angle with the porous Teflon as approximately 171. They also prepared a sample without polystyrene to have a solid surface that had a contact angle of 125. Having a rough, porous surface increases the contact angle for Teflon, therefore a Teflon powder may also increase contact angle. To understand the implication of the sessile drop results on underwater surfaces the hydrophobic phenomena must be understood. For rough surfaces it could be assumed that air is forming a thin layer on the surface of the material so the water only touches the peaks of the Teflon. There are two main forces to be taken in to account, the surface tension of the water and the water/solid interaction. The water/solid interaction can be thought of as the surface friction or surface adhesion between the water and Teflon. Having little contact with the solid means there is less surface area to provide friction to the water. Teflon is also a low fiction surface further decreasing the water/solid interaction, thereby ensuring the surface tension of the water the dominate force in the 36
droplet. The surface tension holds the water together to keep water from permeating and air from escaping the material. Marmur (2006) used similar assumptions to these to theoretically show that underwater surfaces can be super-hydrophobic if the surface was rough enough. He used Gibbs surface energy analysis to show that the rougher surfaces would keep water from touching less of the material therefore provide a more hydrophobic surface.
4.3 Gas Generation

The results presented in Figure 10 and Figure 11 show the experiment is repeatable and can be correlated with theoretical REAL code results. Gas production REAL code results for aluminum/Teflon without and with water (50% of the mass) are shown in Figure 22. The reactive mixture produces more gas with water than the without. Also as the reactive material becomes more fuel rich the amount of gas produced increases.
37
8 Product Volume, m^3/kg 7 6 5 4 3 2 1 0 0

With 50% Water Without Water
Powder Equivalence Ratio,

Figure 22. REAL code calculation for the Al/Teflon without and with 50% water. The equivalence ratio is only calculated for the Al/Teflon powder.
To estimate the percentage of water reacting with the powder mixture the stoichiometric reactions for aluminum/Teflon and aluminum/water are used (Equation (1) and Equation (3), respectively). First the excess aluminum in the fuel rich aluminum/Teflon mixtures was determined, and then the water necessary to react stoichiometrically with that excess aluminum. The percentage of water for total reaction mass was determined to be less than 10% for the samples in this experiment. 50% water was chosen for REAL code calculations to give improved contrast between the volume increase with and without water gas generation. These calculations are shown in appendix (
38
A.3 Calculations for Excess Water).
2 Al + 3H 2 O Al 2 O3 + 3H 2
(4)
The excess aluminum in the fuel rich mixtures is likely reacting with water producing hydrogen gas (among other gases), thereby increasing the volume of gas produced from the reaction. To validate this hypothesis, the thermodynamic properties of the gas products must be understood. The volume is a function of the moles of gas produced, temperature, and the inverse of pressure. The ideal gas law can be used to estimate these relationships. To begin with, a possible reason for an increase in volume is an increase in temperature. REAL code calculations (Figure 23) were done to show adiabatic flame temperature for various mixtures of aluminum, Teflon, and water at constant pressure (1atm). To help determine how to model the reaction the videos were studied. Based on the video evidence, aluminum and Teflon began reacting inside the block and the reacting mixture is forced upwards by the expanding gas. In the bubble of expanding gas, excess aluminum fuel has a chance to react with water. Two extremes and a transition condition were modeled to determine the flame temperature/equivalence ratio gradient. One of the extremes was where the aluminum/Teflon mixture reacts alone without the influence of water. Without the influence of water the flame temperature decays (2126 to 1315K) over the range of equivalence ratios used in the experiments (=1, 1.5, and 2). For the second extreme, the mixture reacts with 50% by mass o f water and increases (1088 to 1717K)
39
over the same range. Finally, the temperature was approximately constant over the range of the experiments for powder mixed with 25% water. In the tank setup, aluminum and Teflon can be treated as a premixed reaction and those products are able to react with the water as a diffusion controlled reaction. The flame temperature decreases with increasing equivalence ratio (Figure 23). Therefore, temperature is not increasing the volume of reaction.
Adiabatic Flame Temperature, K
4000 3500 3000 2500 2000 1500 1000 500 0 0.5 1.5 2.5 3.5 4.5 Powder Equivalence Ratio,
Al+Teflon (without water) Al+Teflon (with 25% water) Al+Teflon (with 50% water)
Figure 23. REAL code calculation of adiabatic flame temperature for different mass percents of water
Secondly, pressure can account for the volume change. There was a large pressure range for the fuel rich mixtures and the there are only two data points for the balanced mixtures. From the results there was no pressure decrease, but it cannot be stated that there was a pressure increase for fuel rich mixtures. The pressure was not decreasing,
40
therefore pressure cannot be a reason for the increased volume of the bubble for fuel rich mixtures. Finally, the excess gas for fuel rich mixtures may be hydrogen gas released when the extra aluminum fuel reacts with surrounding water. Aochi et al. (2000) reacted aluminum and potassium chlorate KClO3 mixtures underwater and collected the products. Products were analyzed with gas chromatography. Figure 24 was produced using their table of results. The total gas volume increases for the fuel rich mixture, while it remains constant for fuel lean and balanced mixtures. Also, the amount of hydrogen gas produced increases with aluminum content. In addition other gases can be produced such as CO, CO2, and methane from the reaction with the carbon and liberated oxygen.
700 600 Volume x10^-6 m^3 500 400 300 200 100 0 0
Total Gas Hydrogen Gas
0.5
1.5
2.5
Sample Equivalence Ratio,

Figure 24. Results showing gas production increases with fuel rich mixtures and most of the gas production increase is from hydrogen gas (Aochi, 2000).
41
The temperature, pressure, and gas results together show that the volume changes are likely from excess gas production. The volume should be decrease with temperature and stoichiometry. Also, the pressure was not decreasing, so it can not account for the volume increase. Finally, the only property that can increase the volume is that there are more moles of gas in the bubble. Maximum radius was used to find the energy required to displace the water around the bubble. This energy, shown in Equation (5), is based on the hydrostatic pressure at the depth of reaction and volume of the bubble (Cole, 1948). The equation assumes that the bubble pressure is less than the hydrostatic pressure at the maximum radius. The bubble volume was approximated as spherical. To compare the energy between different samples, the energy was divided by the sample mass. Determining displacement energy has an advantage of being able to predict the size of the bubble at different depths by solving for maximum radius at different hydrostatic pressures. 4 P R3 3 hydrostatic max = M sample mass
Edisplacement
(5)
42
Chapter V Conclusions
The modified aquarium test provides a unique diagnostic technique to study the hydrodynamics of reactive material deflagrations underwater. The hydrophobic and gas generation properties of Teflon particles and the combustion properties of nano-scale aluminum powder allow for the aluminum/Teflon mixture to be studied in this method. Bubble radius and pressure were recorded and analyzed to show that gas production increases with fuel rich mixtures. Excess aluminum for fuel rich reactions reacts with the surrounding water and produces more gas. Product analysis has shown that there is hydrogen produced in the reaction and the only hydrogen available is in surrounding water. The results were validated with the REAL thermal equilibrium code and results from other researchers. There was also a correlation between the percent theoretical maximum density of the sample and the hydrodynamics of the bubble. The gas production dynamics transition with increasing density from a quick single bubble burn to a longer duration of small bubbles.
43
Chapter VI Future Work

There are some improvements that could be made for this experimental setup. First, having the pressure sensor outside of the bubble and having the bubble grow into the sensor can cause problems. There is the effect of the water/gas interface on the surface of the sensor and the pressure concentrations due to jet of products in the center of the bubble both erroneously influence the pressure data. A better way to find the pressure inside the bubble would be to have multiple pressure sensors outside of the bubble. The data from the pressure sensors could be plotted on a pressure versus distance plot. The data curve fitted and the bubble pressure at zero distance can be determined. Future work would also include expanding the experiment. One change that could be made is to find other materials to use in place of Teflon. The hydrophobic feasibility of new materials could be determined by the sessile drop technique. Also it may be interesting to reproduce bubble energy experiments by igniting hanging pellets from within. Hanging pellets were tried initially for this work but the pellet would travel away from the initial position. If the pellets were stationary the bubble would also be more spherical. The spherical assumption would be more valid in that case than in this work. Also by hanging the pellets it will eliminate the effect of the surface of the block on the shape of the bubble.
44
References
Aochi, T., Matsunaga, T., Nakayama, Y., Iida, M., Myake, A., & Ogawa T. (2000). Analysis of Underwater Explosion Gas Products of Aluminum/Potassium Chlorate Mixtures. Kayaku Gakkaishi, 61(4), 167-175. Asay, B.W., Son, S.F., Busse, J.R., & Oschwald, D.M. (2004). Ignition Characteristics of Metastable Intermolecular Composites. Propellants, Explosives, Pyrotechnics, 29(4), 216-219. Bates, L. R. (2004). Underwater Explosive Behaviour of Compositions Containing Nanometric Aluminium Powder. Proceedings of the Materials Research Society Symposium (p257-263). Boston, MA: Materials Research Society. Belov, B.V. (2004). REAL for windows, Moscow. Blossey, R. (2003). Self-Cleaning Surfaces Virtual Realities. Nature Materials, 2(5) 301-305. Bockmon, B. S., Pantoya, M.L., Son, S.F., Asay, B.W., & Mang, J.T. (2005). Combustion Velocities and Propagation Mechanisms of Metastable Interstitial Composites. Journal of Applied Physics, 98(6), 064903. Bocksteiner, G. (1996). Evaluation of Underwater Explosive Performance of PBXW-115 (AUST) (DSTO-TR-0297). Melbourne, Victoria, Australia: Aeronautical and Maritime Research Laboratory. Cole R. H. (1948). Underwater explosions. Princeton, New Jersey: Princeton University Press. Cudzillo, S. & Trzcinski, W.A. (2001). Metal/Polytetrafluoroethylene Pyrolants, Polish Journal of Applied Chemistry, XLIV(1-2), 25-32. Fischer, S.H. & Grubelich, M.C. (1998). Theoretical Energy Release of Thermites, Intermetallics, and Combustible Metals. Proceedings of the 24th International Pyrotechnics Seminar. Monterey, CA. Frankel, M.J., Liddiard, T.P., & Forbes, J.W. (1982). Low-Level Shock Reaction Thresholds in High Explosives and Propellants. Combustion and Flame, 45(1), 31-37.
45
Goldstein, S. & Johnson, J.N. (1982). Aquarium Tests on Aluminized ANFO. Proceedings of the 7th Symposium (International) on Detonation (p1016-1023). Annapolis, MD: US Naval Surface Weapons Center. Granier, J.J. & Pantoya, M.L. (2004). Laser Ignition of Nanocomposite Thermites. Combustion and Flame, 138(4), 373-383. Kuo, K. K. (2005). Principles of combustion (2nd ed.). Hoboken, New Jersey: John Wiley & Sons. Levitas, V. I., Asay, B. W., Son, S. F., & Pantoya, M. (2006). Melt Dispersion Mechanism for Fast Reaction of Nanothermites. Applied Physics Letters 89, 071909. Mao, Z., Yang, C., & Chen, J. (2005). Simple Hydrostatic Model of Contact Angle Hysteresis of a Sessile Drop on Rough Surface. Chinese Journal of Chemical Engineering, 13(1), 118-123. Marmur, A. (2006). Underwater Superhyrdrophobicity: Theoretical Feasibility. Langmuir, 22(4), 1400-1402. McHale, G., Erbil, H.Y., Newton, M.I., & Natterer, S. (2001). Analysis of Shape Distortions in Sessile Drops. Langmuir, 17(22), 6995-6998. Menon, S. & Mihir, L. (1998). On the Dynamics and Instability of Bubbles Formed During Underwater Explosions. Experimental Thermal and Fluid Science, 16(4), 305-321. Nedostup V.I. & Gal'kevich E.P. (1979). Generalized Form of the Equation of State of Real Gases. Journal of Engineering Physics, 37(4), 1213-1217. Pittaluga, F. & Nascetti D. (1981). A New Method for Propulsive Applications of the Aluminum-Water Reaction. La Thermotecnica, 35(6), 334-342. Son, S.F. (2004) Performance and Characterization of Nanoenergetic Materials at Los Alamos. Proceedings of Materials Research Society Symposium 800 (p161-172). Boston, MA: Materials Research Society. Trilling, L. (1951). The Collapse and Rebound of a Gas Bubble. Journal of Applied Physics, 23(1), 14-18. Van Der Wal, P. & Steiner, U. (2007). Super-Hydrophobic Surfaces Made from Teflon. Soft Matter, 3(4), 426-429.
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Vokurka, K. (1987). Oscillations of Gas Bubbles Generated by Underwater Explosions. Acta Technica CSAV, 32(2), 162-172. Watson, K.W. (2007). Fast reaction of nano-aluminum: A study on fluorination versus oxidation. Masters Thesis, Texas Tech University, Lubbock, TX.
47
Appendix A Supplementary Results and Calculations

A.1 Supplemental REAL Results
C7H5N3O6 (TNT) 2Al+Fe2O3
2Al+MoO3
2Al+3H2O
4Al+3C2F4
0 200 400 600
kJ/mole
800
1,000
1,200
Figure 25. Heat of Combustion (kJ/mole)
48
2Al+MoO3
2Al+3H2O
4Al+3C2F4
0 5,000,000 10,000,000 15,000,000 20,000,000 25,000,000 30,000,000
kJ/m^3
Figure 26. Heat of Combustion (kJ/m3)
2Al+MoO3
2Al+3H2O
4Al+3C2F4
0 2,000 4,000 6,000
kJ/kg
8,000
10,000
12,000
Figure 27. Heat of Combustion (kJ/kg)
49

Table 6. REAL code results for Teflon and 80% pure aluminum
Heat of Comb., kJ/kg 0.5 5628 1 8856 1.5 8045 2 7404 2.5 6885
Gas Gen., %mass 88.56% 85.82% 86.14% 86.12% 87.35%
Temp, K 2583.3 3513.3 3473.5 3126.4 2383.8
Table 7. REAL code volume product results for Al + Teflon with a mass percentage of water
No Water 0.5 2.56 1 3.77 1.5 3.98 2 3.97 2.5 3.41 3 2.78 4 2.40 5 2.07
Gas Generation, m^3/kg 50% Water 25% Water 10% Water 3.10 4.46 4.47 3.77 5.15 5.07 4.79 4.77 4.58 5.51 4.69 3.86 6.03 4.61 3.75 6.40 4.54 3.66 6.84 4.51 3.24 6.65 4.17 2.62
Table 8. REAL code adiabatic flame temperature results for Al + Teflon with a mass percentage of water
0.5 1 1.5 2 2.5 3 4 5
Adiabatic Flame Temperature, K No Water 50% Water 25% Water 10% Water 2583 941 1634 2441 3513 1088 2027 2749 3474 1442 1902 2429 3126 1717 1925 1952 2384 1931 1940 1953 1860 2099 1951 1956 1871 2326 2065 2013 1800 2327 2122 2028
50
A.2 Supplemental Experimental Results

Table 9. Experimental results for displacement energy, bubble growth rate, and pressurization rate Initial Bubble Displacement Avg Bubble Pressurization Energy Growth Rate Rate Block# kJ/kg m/s kPa/s 18 83.75 0.89 54.36 19 83.77 1.06 118.79 20 85.58 1.15 84.08 23 99.90 1.91 130.25 25 105.92 1.45 86.65 31 98.26 1.58 69.65 26 N/A N/A 19.84 27 N/A N/A 16.47 28 N/A N/A 26.76 29 N/A N/A 13.04 30 63.42 0.43 49.89 34 77.88 1.65 80.73 35 125.85 1.84 103.12 37 133.98 1.41 134.37 38 120.35 0.92 54.62
51
A.3 Calculations for Excess Water

Water required = Alexcess F O Balanced Al + H 2O
(A1)
Alexcess = Al + Al =1
Table 10. Percent of water required for comparison in REAL code results
(A2)
1 1.5 2 2.5
Al excess Water Req. 0% 0% 25% 6% 50% 10% 75% 14%
52
A.4 Normalizing Radius Data

The radius data was normalized to reduce the influence of radius. To understand the how the radius increases with increasing mass, maximum radius and sample mass were plotted in Figure 28. For the most fuel rich (=2) and the balanced (=1) reactions it can be seen that the radius increases with the sample mass.
24 23 Max Radius, mm 22 21 20 19 18 17 16 15 20 25 30 Sample Mass, mg

Figure 28. Data from Table 4 plotted to show the effect of sample mass
=1 =1.5 =2 35 40
To reduce the effect of sample mass, the radius divided by the sample mass and was plotted in Figure 29. The influence of the sample mass was overcompensated as the largest sample radius (fuel rich sample) is now as low as the fuel balanced reactants.
53
800 Specific Radius, m/kg 750 700 650 600 550 500 20 25 30
Sample Mass, mg
Figure 29. First attempt normalizing radius data
=1 =1.5 =2
35
40
By calculating the volume (assuming the bubble is spherical) and dividing by the mass the radius can be normalized (Figure 30). There is still a slight trend for the volume increasing with mass, but it is less than the experimental error of the data. The volume was also multiplied by the molar weight to get the volume per moles (Figure 31).
54
Specific Volume, m^3/kg
1.4 1.2 1 0.8 0.6 0.4 0.2 0 20 25 30

Sample Mass, mg
Figure 30. Second attempt normalizing radius data
=1 =1.5 =2
35
40
0.09 0.08 0.07 0.06 0.05 0.04 0.03 0.02 0.01 0 0.0004 0.00045 0.0005 0.00055 0.0006
Moles of Reactant
Volume, m^3/mole
=1 =1.5 =2
0.00065
Figure 31. Second attempt normalizing radius data in terms of volume per moles
55
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Hydrodynamical Analysis of Nanometric Aluminum/Teflon Deflagrations BY SHAWN C. STACY, B.S.M.E.

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

Chapter I Introduction and Background

1.2 Aluminum Composite Reactive Materials

Texas Tech University, Shawn C. Stacy, May 2008

cal/cc C7H5N3O6 (TNT) cal/g

Texas Tech University, Shawn C. Stacy, May 2008

1.3 Nano-scale composites

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

1.4 Underwater Testing

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

Figure 2. Underwater Explosive Behavior

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

Chapter II Experimental Setup and Procedure

Texas Tech University, Shawn C. Stacy, May 2008

Powder Aluminum Teflon-PTFE Aluminum MoO3

Particle Size 80nm 200nm 1-3m 44nm

Purity 80% 100% 99% 99%

Form Factor Spherical Spherical Spherical Rectangular

Texas Tech University, Shawn C. Stacy, May 2008

Table 2. Actual mass percents of Al and Teflon for mixtures

1 1.5 2 4 Al + 3(C2 F4 ) 4 AlF3 + 6C

Texas Tech University, Shawn C. Stacy, May 2008

Pressure, atm 1 10 100 1000 10000 Balanced Equation

2.2 Experimental Setup

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

2.3 Data Acquisition

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

Figure 8. Phantom software for radius analysis.

Texas Tech University, Shawn C. Stacy, May 2008

15 10 5 0 0 0.01 0.02 0.03

2.4 REAL Code Calculations

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

Chapter III Results

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

24 23 Max Radius, mm 22 21 20 19 18 17 16 15 0.5 1 1.5 2 2.5 Powder Equivalence Ratio,

Texas Tech University, Shawn C. Stacy, May 2008

Texas Tech University, Shawn C. Stacy, May 2008

Figure 12. A representative pressure profile for one second

Texas Tech University, Shawn C. Stacy, May 2008

Figure 14. Examples of unburned micron aluminum and Teflon reactions

Texas Tech University, Shawn C. Stacy, May 2008

Figure 15. Illustration showing the influence of carbon on bubble transparency

Figure 16. Air bubble before reaction

_Shawn Christopher Stacy_____________________ Student Signature