COMBUSTION BEHAVIOR OF SOL-GEL SYNTHESIZED ALUMINUM AND TUNGSTEN TRIOXIDE by DANIEL PRENTICE, 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 Darryl James

Jordan M. Berg Accepted John Borrelli Dean of the Graduate School May, 200

ACKNOWLEDGEMENTS

I would like to thank my advisor Dr. Michelle Pantoya for introducing me to this exciting field of nanotechnology research. Thank you for being so generous in your advice and in allowing me to be a part of the growing literature on nano-composite energetic materials. I would like to acknowledge Dr. Alex Gash from Lawrence Livermore National Laboratory for providing the aerogel materials studied as well as the SEM micrographs and XRD analysis. Thank you to Dr. John Granier and Mr. Keith Plantier for help in setting up and conducting experiments. Without your help, I would not have known where to start. I would also like to acknowledge Mr. Dustin Osborne for conducting the TGA work and Dr. Mark Grimson and Mr. Peter Jung for their help and advice with the SEM work. Thank you to my wife Sara for your support during this exciting but stressful time in our lives. And finally, thank you to my parents for encouraging me to always do my best and for supporting me in whatever I chose to do.

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TABLE OF CONTENTS

ACKNOWLEDGEMENTS.............................................................................................ii ABSTRACT...................................................................................................................vi LIST OF TABLES ........................................................................................................vii LIST OF FIGURES......................................................................................................viii CHAPTER I. INTRODUCTION ......................................................................................... 1 1.1 Traditional Thermites ......................................................................... 1 1.2 Nano-composite Thermites................................................................. 2 1.3 Advantages of Tungsten Trioxide....................................................... 3 II. EXPERIMENTAL......................................................................................... 5 2.1 Sample Preparation ............................................................................ 5 2.1.1 Aerogel Tungsten Trioxide Properties........................................ 5 2.1.2 Commercial Tungsten Trioxide Properties ................................. 9 2.1.3 Thermite Synthesis .................................................................. 10 2.1.4 Pellet Synthesis........................................................................ 11 2.3 Open Channel Burn Testing Apparatus............................................. 11 2.4 Pellet Combustion Rate Testing Apparatus....................................... 12 III. THEORY..................................................................................................... 15 3.1 Motivation to Research Aerogel Composites .................................... 15 iii

3.2 Aerogel Synthesis............................................................................. 16 3.3 Advantages of Aerogels.................................................................... 17 IV. RESULTS.................................................................................................... 19 4.1 Open-Channel Combustion Wave Speed .......................................... 19 4.2 Pellet Combustion Wave Speed........................................................ 20 4.3 Pellet Ignition Sensitivity ................................................................. 21 V. DISCUSSION.............................................................................................. 23 5.1 Open-Channel Combustion Wave Speed .......................................... 23 5.1.1 Optimum Equivalence Ratio .................................................... 23 5.1.2 Optimum Oxidizer Composition .............................................. 24 5.2 Pellet Combustion Wave Speed and Sensitivity ................................ 26 5.2.1 Combustion Wave Speed as a Function of Bulk Density .......... 26 5.2.3 Combustion Wave Speed as a Function of Composition .......... 27 5.3 Aerogel Combustion Dominant Mechanism Transition..................... 36 VI. VII. CONCLUSIONS ......................................................................................... 39 ALUMINUM AND TUNGSTEN TRIOXIDE AGING EFFECTS............... 41 7.1 Aluminum and Tungsten Trioxide Aging Study................................ 41 7.1.1 Introduction ............................................................................. 41 7.1.2 Experimental Setup.................................................................. 44 7.1.3 Results..................................................................................... 50 7.1.4 Discussion ............................................................................... 51 7.1.4 Conclusions ............................................................................. 54 iv

7.2 Long Term Aerogel Aging ............................................................... 55 REFERENCES ............................................................................................................. 57

ABSTRACT

Calcined (to remove impurities) and non-calcined tungsten trioxide (WO3) aerogels as well as micron-scale and nano-scale commercial WO3 powders were mixed with nano-scale aluminum (Al) and their combustion performance in the form of combustion wave speeds was compared in loose powder and pressed pellet configurations. Results show that both the calcined and non-calcined, aerogel based mixtures outperformed the commercial based mixtures in both configurations. Combustion wave speed was also found as a function of mixture bulk density. Results show that conduction is the dominant energy transfer mechanism in pressed pellets while convection is the dominant mechanism in loose powder form. This causes material purity to be the most important factor for pressed pellets and oxidizer particle size to be the most important factor for loose powders. A preliminary aging study was conducted which showed a 7% performance reduction after 4 days of laboratory air exposure and 91-98% performance reduction after 22 months of exposure.

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LIST OF TABLES

1. 2. 3. 4.

Oxidizer Properties.................................................................................................. 5 Calculated Andreev numbers and physical parameters for Al+WO3 composites at 31.7-34% TMD ............................................................................... 29 Normalized Andreev number for Aerogel 120 and Aerogel 400 in pellet and powder configuration............................................................................. 30 Combustion Wave Speeds ..................................................................................... 50

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LIST OF FIGURES

1. 2. 3. 4. 5. 6. 7. 8. 9.

X-ray diffraction analysis of Aerogel 120 and Aerogel 400...................................... 7 Thermal gravimetric plots of Aerogel 120 and Aerogel 400 ..................................... 8 SEM micrographs of Aerogel 120 and Aerogel 400 ................................................. 9 Photograph of the open channel burn testing apparatus .......................................... 12 Schematic of the laser ignition and flame propagation diagnostic system ................................................................................................................... 14 Plot of open-channel combustion wave speed as a function of equivalence ratio for Aerogel 120 and Aerogel 400................................................ 19 Plot of combustion wave speed as a function of pellet density ............................... 21 Plot of ignition delay time as a function of pellet density ....................................... 22 Photograph of an Aerogel 400 pellet at 49.6% TMD.............................................. 27

10. Andreev number as a function of pellet oxidizer composition at a TMD range of 31.7-34%........................................................................................ 29 11. Calculated adiabatic flame temperature as a function of mass percent water in the oxidizer .............................................................................................. 32 12. Estimated drop in combustion wave speed as a function of mass percent water in the oxidizer.................................................................................. 33 13. Combustion wave speed as a function of oxidizer surface area and pellet density................................................................................................... 34 14. Semi-Log plot of combustion wave speed as a function of TMD for Aerogel 120 and Aerogel 400 ........................................................................... 37 15. Photograph of sample storage containers ............................................................... 46 16. Schematic of flame propagation apparatus............................................................. 48 17. Photograph of burn channel ................................................................................... 49 viii

18. Plot of combustion wave speed as a function of days aged..................................... 51 19. Thermal gravimetric plot of original and aged Aerogel 120 and Aerogel 400 ........................................................................................................... 56

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CHAPTER I INTRODUCTION

1.1 Traditional Thermites Thermite reactions are characterized by an oxidation-reduction reaction between a metal and a metallic oxide. The reactions are highly exothermic and typically selfsustaining. Wang et al. [1] conducted a thorough literature review on typical thermite applications ranging from welding [2, 3] to the synthesis of metals and alloys [4] or ceramic and composite materials [5-7]. Other applications include a cost-effective method for storing radioactive wastes [8], using gas-generating additives to create thermites that could be used for the demolition of concrete [9] or in self-destruct electrical components [10]. Because thermites are a mixture, an ideal balance of fuel and oxidizer components can be attained resulting in high energy densities. The energy density is typically higher than that of explosives because monomolecular energetic materials often have an imperfect fuel-oxidizer balance. The reaction rate for a thermite is limited by the mass transport between the reactants. In monomolecular energetic materials such as explosives, the reaction rate is governed by chemical kinetics and thus explosives have a faster energy release rate or greater power than thermites.

1.2 Nano-composite Thermites Because thermite reactions are mass diffusion limited, decreasing the reactant particle size decreases the diffusion distances and increases the reaction rate [11]. By reducing the size of the reactants from micron-scale to nano-scale, flame propagation rates (i.e. speeds) have been measured up to 1000 times faster than traditional thermites [12]. Other studies have similarly confirmed that nanocomposite thermites exhibit greater speeds than their micron scale counterparts [13-16]. In light of the increased speeds found in nanocomposite thermites, researchers are beginning to develop materials that have very high energy densities like traditional thermites but also have high energy release rates (power) like explosives or other monomolecular energetic materials. Researchers at Lawrence Livermore National Laboratory (LLNL) created a new class of energetic materials using sol-gel chemistry [17-23]. Their method allows for not only nanocomposite but actually nanostructured thermite production. They are able to create a nano-scale structure with a skeletal sol-gel matrix composed of the oxidizer with the fuel imbedded in the voids between the matrix [22]. The nanostructure allows for a level of homogeneity and intimate mixing that is otherwise not easily achieved by simply mixing nano particles. The sol-gel method offers the possibility to control the composition, morphology and reactivity of the thermite at the nanometer scale [17]. LLNL researchers first synthesized Fe2O3 aerogel and xerogels [17]; then synthesized composites such as Fe2O3+Al aerogel and xerogel thermites [18]; and further expanded the technique to synthesize other oxides (Cr2O3, Al2O3, In2O3, Ga2O3, SnO2, ZrO2, HfO2, Nb2O5, and WO3) [20, 21] and included silicon gas generators into the 2

thermites [24-26]. One result was that water or hydroxyl groups are an inherent component in the sol-gel synthesis of these thermites [17, 20]. Plantier et al. conducted combustion experiments using LLNL sol-gel derived Fe2O3 aerogel and xerogel and compared it to commercially available nanoscale Fe2O3 [27]. They measured the combustion wave speeds in open and confined burning experiments and showed relatively poor burning performance of the aerogel and xerogel Fe2O3 compared to the commercially available nanopowder. This was attributed to the high amount of impurities (hydroxyl groups and organic contamination) found in the solids. New aerogel and xerogel powders were then calcined to 410 C to remove impurities and results showed the largest improvement in combustion wave speed from ~10 m/s to over 900 m/s in confined burning conditions.

1.3 Advantages of Tungsten Trioxide For ordnance applications, desirable properties for the mixture include a high adiabatic flame temperature and large enthalpy of reaction [28]. Tungsten trioxide (WO3) combined with aluminum has a high adiabatic flame temperature (5544 K [41]) and large enthalpy of reaction (3801 cal/cc [41]). Another important property when high energy density is desired is high material density. Tungsten trioxide has high material density (7.20 g/cc compared with 5.25 g/cc for Fe2O3). Furthermore, oxidizers such as WO3 and MoO3 sublime at relatively low temperatures unlike Fe2O3 which remains in the solid phase. The gas generated during sublimation could facilitate a diffusion limited reaction. Also, Balakir et al. found that oxidizers with high vapor pressure such as WO3 gave the 3

fastest rates of combustion [30]. For these reasons, this study focused on characterizing the combustion behavior of Al and WO3. There were three objectives in this study of nano-Al and WO3 combustion. The first objective was to determine the optimum stoichiometry. Because it has been shown that varying the bulk density of the thermite has a significant affect on the combustion behavior of Al and MoO3 [29], the second objective was to determine how the bulk density affects the combustion wave speed of nano-Al and WO3. The final objective was to identify the dominant mechanisms controlling the combustion behaviors corresponding to the different thermite mixes in loose powder and pressed form. Optimum stoichiometry was determined by varying the fuel/oxidizer ratio of the mixtures where the ratio that exhibits the fastest combustion wave speed is deemed optimum. The thermites were composed of nano-scale aluminum powder mixed with four types of WO3 oxidizers. The oxidizers were calcined and non-calcined WO3 aerogels prepared at LLNL, and commercially available nano and micron-scale WO3 powders. These experiments were performed by burning loose powders of various fuel/oxidizer ratios in an open channel and measuring the combustion wave speed and flame propagation behavior via high-speed photography and imaging diagnostics. Bulk density combustion behaviors were determined by preparing samples of various densities and examining flame propagation behavior also using high-speed imaging diagnostics. Identifying the dominant mechanisms controlling the combustion behaviors was accomplished by using an Andreev numerical analysis and by analyzing the visual data recorded for the combustion wave speed experiments. 4

CHAPTER II EXPERIMENTAL

2.1 Sample Preparation The WO3 oxidizers vary according to manufacturing methods and physical properties described in Table 1. The Al fuel particles were 80 nm average diameter supplied by Nanotechnologies Inc. (Austin, Texas) and consistently used for all mixtures in this study. An alumina shell that is roughly 4 nm thick encapsulates the core Al particle such that this powder has an active Al content of 84 %. Active Al is defined as the portion of powder not in the form of Al2O3. Table 1. Oxidizer Properties
Oxidizer Name Aerogel 120 Aerogel 400 nm WO3 Oxidizer Description (WO3) Nano-Scale,Cubic Tungsten Trioxide (Calcined to 120 C) Nano-Scale, Orthohombic Tungsten Trioxide (Calcined to 400 C) Nano-Scale Tungsten Trioxide Micron-Scale Tungsten Trioxide Particle Surface Area 77.1 m2/g (BET) 28.2 m2/g (BET) 16.9 m2/g (Manufacturer Provided) 0.026 m2/g (Calculated by Visual Method) % WO3 91 96 100 (Assumed) 100 (Assumed)

2.1.1 Aerogel Tungsten Trioxide Properties Both of the WO3 aerogels were synthesized at Lawrence Livermore National Laboratories (LLNL). The Aerogel 120 was calcined to 120C and the Aerogel 400 was calcined to 400C to remove hydroxyl groups (OH) and impurities that have been shown to be present during the sol-gel synthesis process [17, 20, 27]. Chemical analysis of the

aerogel derived oxidizers was performed at LLNL and the purity is recorded in Table 1. Aerogel 120 has 1.2% carbon and 1.0% hydrogen impurities by weight. Aerogel 400 has trace carbon and hydrogen impurities (<0.5 wt.%). Surface area measurements were made using a gas adsorption analyzer and using BET (Brauner, Emmett, and Teller) theory. Crystalline structure was determined by x-ray diffraction (XRD) performed at LLNL as seen in Fig. 1. The Aerogel 120 is highly disordered and is classified as cubic tungsten oxide as determined from Fig. 1a. The Aerogel 400 is highly crystalline and is classified as orthorhombic tungsten oxide as determined from Fig. 1b. To confirm the presence of bonded water, thermal analysis of the Aerogel 120 and Aerogel 400 oxidizers was conducted using a thermal gravimetric (TG) analyzer (Netzsch, STA 409 PC). The TG curves for the Aerogel 120 and Aerogel 400 are shown in Fig. 2. A decrease in the TG curve as temperature increases represents a weight loss of the sample as it is heated. The TG curve shows that the Aerogel 120 sample had a weight loss at about 150 C. This confirms the presence of bonded water in the Aerogel 120. The TG curve for Aerogel 400 was nearly constant which shows there was little to no bonded water in the sample. The presence of water in the Aerogel 120 but not in the Aerogel 400 was expected because Plantier et al. observed a similar phenomena in sol-gel synthesized Fe2O3 [27].

a.

b. Figure 1. X-ray diffraction analysis of a. Aerogel 120 and b. Aerogel 400 (Courtesy LLNL) 7

Figure 2. Thermal gravimetric plots of Aerogel 120 and Aerogel 400

Figure 3 shows scanning electron microscope (SEM) micrographs of the Aerogel 120 and Aerogel 400 oxidizers. As seen in Fig. 3b, the Aerogel 400 particles sintered together upon heating to form large agglomerates.

a.

b.

Figure 3. SEM micrographs of a. Aerogel 120 and b. Aerogel 400 (Courtesy LLNL)

2.1.2 Commercial Tungsten Trioxide Properties The commercial nano-scale WO3 was donated by Nanomat (North Huntingdon, PA) and will be referred to as nm WO3. The commercial micron-scale WO3 was purchased from Acros Organics (Morris Plains, NJ) and will be referred to as m WO3. The surface area measurement for the nm WO3 was determined using a gas adsorption analyzer and BET theory. The mass percent WO3 content was assumed to be 100 % for both of these materials. The surface area measurement for the m WO3 was estimated by calculating the surface area of representative single particles viewed from SEM micrographs. The surface areas and purities of the WO3 oxidizers can be found in Table 1. 9

2.1.3 Thermite Synthesis The mixtures were prepared by combining the powders in pre-specified proportions in a suspension solution of isopropanol. The stoichiometric fuel/oxidizer mass ratio for the Al+WO3 reaction is 0.2327 (Eq. (2.1)).
2 Al + WO3 ! W + Al 2 O3

(2.1)

The equivalence ratio () was calculated according to Eq. (2.2).

# MF & % ( MOx ' act $ "= # MF & % ( MOx ' st $

(2.22)

The subscripts F and Ox represent fuel and oxidizer respectively. The M represents mass

! and act is actual while st is stoichiometric. For the fuel, only the active Al content was
considered. For the oxidizer, only the pure WO3 was considered. An equivalence ratio of 1.4 was shown to be optimum (slightly fuel rich). The powders and solution were mechanically mixed using an ultrasonification process. This process allowed for a more homogeneous mixture by breaking up large agglomerates. The mixture and solution were heated at a low temperature, approximately 70 C, in a glass dish to evaporate the isopropanol. The composite dried powder was recovered from the dish and stored in a vial until tested in open channel burn experiments or immediately cold-pressed using a hydraulic press and uni-axial die if the thermite was to be tested in pellet form. Care was taken to perform the combustion experiment for the particular composition within 24 hours of their creation to minimize any aging effects of the Al from oxidation in air.

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2.1.4 Pellet Synthesis Using a standard axial press, the dried powder mixtures of =1.4 were pressed into a solid cylindrical pellet with a constant diameter of 6.5 mm and varying length, dependent on the pellet density desired, on the order of 3 mm. The theoretical maximum density (TMD) was calculated as a weighted average of the pure solid densities of the three reactants (Al, WO3, and Al2O3). The pellets were pressed to various percentages of the TMD ranging from 20 to 50 % for each mixture. All of the pellets had a mass of approximately 250 mg.

2.3 Open Channel Burn Testing Apparatus Figure 4 shows the open burn channel used to determine the loose powder combustion wave speeds. A 10 x 0.3175 x 0.3175 cm square channel cut into an acrylic block was filled with 250 mg of thermite to be tested. The top of the channel was open to ambient air. The composites were ignited using a spark ignition system of which the terminals for the spark gap can be seen in Fig. 4. A Phantom IV high-speed camera from Vision Research (Wayne, NJ) captured images of the reacting thermite perpendicular to the open burn channel and at frames rates of 32,000 frames per second (fps) with a resolution of 128 x 32 pixels. The camera interfaced with a computer that used Vision Research software to post process the photographic data. By establishing a reference length, the software determines speed based on a distance between sequential time frames.

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Figure 4. Photograph of the open channel burn testing apparatus

2.4 Pellet Combustion Rate Testing Apparatus Figure 5 shows a schematic of the apparatus used to ignite the pellets and measure the combustion wave speed. The energetic pellet is housed in a reaction chamber with various ports for the laser beam and viewing not shown in the schematic. The flat end of the cylindrical pellet was carefully aligned with the beam path of a 50-W CO2 laser (10.6 m wavelength). The beam delivery was controlled by a pushbutton operated, electromechanical shutter. The laser output was measured with a thermal power meter that adjusts in and out of the beam path. The laser output was kept at 50 W continuous wave. A triggering device was used to simultaneously open the shutter and start recording from the high-speed camera. The same high-speed camera and image analysis software used in the open channel burn experiments was used to measure the pellet burn speeds. Because

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the trigger is a human controlled pushbutton without any electronic timing device and because the pellets burn very quickly, it is probable that some laser radiation is imparted onto the pellet after ignition. By using the enthalpy of reaction, the laser power and an average pellet burn time, it was calculated that no more than 0.35% of the total pellet energy released could come from laser exposure. This value assumes a worst-case scenario where the shutter remained open for the entire pellet burn. Further information regarding the testing apparatus can be found elsewhere [13].

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Figure 5. Schematic of the laser ignition and flame propagation diagnostic system 14

CHAPTER III THEORY

3.1 Motivation to Research Aerogel Composites Monomolecular energetic materials are only able to achieve approximately half of the energy density of energetic composites due to chemical stability issues and because modern synthesis procedures limit the oxidizer-fuel balance and the physical density obtainable [19]. Micron-scale energetic composites are only able to achieve reaction rates on the order of meters per second compared to kilometers per second for monomolecular energetic materials. It has been shown that for a given bulk density, decreasing the reactant particle sizes increases the combustion rate [11, 30, 35]. Synthesizing the oxidizer using sol-gel chemistry, to form an aerogel, is one way to decrease reactant particle sizes from the micron-scale to the nano-scale. Tillotson et al. showed that aerogel composites are very sensitive to thermal ignition [18]. They theorized that because of the very low thermal conductivity of an aerogel based composite, there is the rapid formation of hot spots or localized high temperature regions that ignite the composite. The high sensitivity of aerogel composites would be an advantage in terms of performance but possibly a disadvantage in terms of safety.

15

3.2 Aerogel Synthesis Gash et al. describe an aerogel as a highly porous lightweight solid [17]. They explain that aerogels are created using sol-gel chemistry. Furthermore, they describe the sol-gel chemistry process where hydrolysis and condensation of molecular chemical precursors, in solution, is used to produce nanometer-sized primary particles called sols [36] which are linked through further condensation to form a three dimensional solid network, or a gel, with the solvent liquid in its pores. An aerogel is formed when the solvent is removed by supercritical extraction [17]. This leaves a three dimensional porous structure made up of nano-scale particles. Tungsten trioxide aerogels are formed by the dissolution of the metal salt, WCl6 in this case [21], in a solvent followed by the addition of an epoxide which induces gel formation in a timely manner [17]. A more indepth review of sol-gel chemistry and aerogels is found elsewhere [17-21]. One problem with this method of aerogel synthesis was that hydroxyl groups or bonded water was found in the aerogel. Water in the form of either hydration of the precursor salt or as the solvent was found to be a necessary component in the synthesis of the aerogels [17]. Because the water is so detrimental to combustion performance, calcination of the aerogel was used to remove the hydroxyl groups. Fourier Transform Infrared Spectroscopy (FTIR) confirmed that a large percentage of the hydroxyl groups were removed when the aerogel was calcined to 200 C under a dynamic vacuum [17]. The downside to calcining the aerogels is that the surface areas and pore volumes were found to decrease while the pore diameters increase with increasing drying temperatures [17]. Because the hydroxyl groups are surface bound, heating induces condensation of the 16

groups which pulls together the small particles that make up the microstructure of the gel [17].

3.3 Advantages of Aerogels Aerogels composites have some distinct advantages over micron-scale composites or even nano-scale composites not based on aerogels. One of which is the possibility to precisely control the composition, morphology and reactivity of the composite at the nanometer scale [17]. Sol-gel chemistry can produce material with variable and uniform densities [18]. A major advantage of aerogel composites over both micron-scale and other types of nano-scale composites is its level of homogenous mixing. The aerogels feature intimate mixing of components at the nano-meter scale [18]. Tillotson et al. [18] explained that in conventional mixing, domains of either fuel or oxidizer can exist which limit the mass transport which decreases the efficiency of the reaction. Sol-gel derived nanocomposites such as aerogels should be more uniformly mixed thereby increasing the reaction efficiency. A long-term goal is to create aerogel based nanocomposites where the aluminum is integrated into the oxidizer during the aerogel creation. This would produce a lattice structure in which the fuel (Al) resides within the pores of the solid oxidizer (WO3) matrix [18]. The nanocomposites featured in this study were not constructed this way, but fundamental knowledge gained here will allow the creation of an integrated nanocomposite aerogel as described above. 17

Finally, the production of aerogels can allow for the materials to be synthesized in the final desired shape and density. Gash et al. [17] created monolithic materials in a variety of shapes and sizes. They recognized that this might eventually eliminate the need for the time-consuming, expensive and potentially dangerous pressing and machining of energetic solids.

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CHAPTER IV RESULTS

Because the same nano-aluminum was mixed with all of the oxidizers studied, the thermite mixes will be referred to by their representative oxidizer (e.g. an Al+Aerogel 120 sample will simply be called Aerogel 120).

4.1 Open-Channel Combustion Wave Speed Figure 6 shows the open-channel combustion wave speed plotted as a function of thermite equivalence ratio for the Aerogel 120 and Aerogel 400 samples. Maximum speeds of 490 and 310 m/s were seen at an equivalence ratio of 1.4 for the Aerogel 120 and Aerogel 400 samples respectively.

Figure 6. Plot of open-channel combustion wave speed as a function of equivalence ratio for Aerogel 120 and Aerogel 400 19

4.2 Pellet Combustion Wave Speed Figure 7 shows the combustion wave speed as a function of pellet density for all four thermite mixtures investigated. The error bars do not represent experiment repeatability but rather measurement errors that occur while using the Phantom imaging software. Due to the relatively fast burn speeds of the pellets and the limited data acquisition rate of the high-speed camera, 32,000 frames per second allowed roughly 15 frames of data for each experiment. Furthermore, the resolution of each frame was 128 x 32 pixels which made it difficult to visually observe the combustion wave. Therefore, five speed measurements were made for each mixture using the Vision Research imaging software. The speed was measured as an average speed between first light and the completion of the self-propagating wave. The standard deviation was plotted as error bars for each experiment. As the speed became faster, as in the Aerogel 400 experiments, the measurement error increased. This was because fewer frames were captured for successively higher speeds.

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Figure 7. Plot of combustion wave speed as a function of pellet density As seen in Fig. 7, the Aerogel 400 exhibited the fastest combustion wave speeds for all densities. The combustion wave speed slightly increased with an increase in pellet density from 20-30% TMD for the Aerogel 400 samples while staying constant or slightly decreasing for the other samples. The increased speeds of the Aerogel 400 over the Aerogel 120 is the opposite result of that seen in the open burn experiments. As a loose powder, the Aerogel 120 produced consistently higher speeds by 58% over the Aerogel 400 at an optimum stoichiometric ratio of 1.4. For pellets, the Aerogel 400 produced consistently higher speeds by at least 376% over the Aerogel 120.

4.3 Pellet Ignition Sensitivity One important factor to consider before analyzing trends in the pellet combustion wave speed data is the initial condition of the pellet before combustion. Figure 8 shows

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the ignition time as a function of pellet density for all of the same data points seen in Fig. 7. The ignition time dramatically increased for all samples above a theoretical maximum density of 35%. Above this critical density, the pellets are highly reflective. No attempt was made to reduce reflectivity (i.e. by coating the front face to enhance absorption). Therefore, only combustion behaviors below 35% TMD were further analyzed.

Figure 8. Plot of ignition delay time as a function of pellet density

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CHAPER V DISCUSSION

5.1 Open-Channel Combustion Wave Speed

5.1.1 Optimum Equivalence Ratio The slightly fuel rich optimum equivalence ratio shown in Fig. 6 is similar to results for nano-Al+MoO3 [13, 29] and nano-Al+Fe2O3 combustion [27]. Pantoya et al. [29] attributed higher combustion wave speeds for nano-particles at slightly fuel rich equivalence ratios to possible Al oxidation with the ambient air that is not taken into account in the stoichiometric calculations. A slightly fuel rich composition may enhance the thermal transport properties of the mixture because the Al has a higher thermal diffusivity and conductivity than WO3 or air. Plantier et al. [27] attributed the slightly fuel rich optimum equivalence ratios to enhanced thermal properties; namely, increased thermal conductivity. They concluded that for highly compacted composites, a higher thermal conductivity will enhance heat transfer in the diffusive dominant reaction thereby increasing combustion wave speeds. The Aerogel 120 and Aerogel 400 samples in this study likely experienced a similar phenomena as in the nano-scale MoO3 and Fe2O3 studies [13, 29 and 27]. Namely the thermal transport properties are enhanced for a slightly fuel rich thermite mixture. Beyond this critical mixture ratio, too little solid oxidizer is available to further increase speed. Because nano-scale thermites experience diffusion controlled reactions, the 23

enhanced heat transfer contributes towards pre-heating the reactants which increases the combustion wave speed.

5.1.2 Optimum Oxidizer Composition The Aerogel 120 and Aerogel 400 both exhibit higher combustion wave speeds than traditional micron-scale Al+WO3 composites. Maximum combustion wave speeds of 490 and 310 were seen for the Aerogel 120 and Aerogel 400 samples respectively while similar open burn experiments using m WO3 produced a maximum combustion wave speed on the order of 40 m/s. The aerogel derived oxidizers react faster because the smaller particle diameters of the aerogels decrease the diffusion distances thereby increasing the combustion wave speed. Also, the smaller particle sizes lead to increased surface area and increased contact between the Al fuel and the WO3 oxidizer which also promotes faster combustion wave speeds. Bockmon et al. found that strong convective mechanisms likely control the combustion wave speed for loose powders of nano-Al+MoO3 thermites burning in confined geometries [14]. When convective processes are significant, a pressure gradient propels the combustion wave forward. This was found in nano-Al+MoO3 thermites because the molybdenum trioxide sublimes at a lower temperature than the adiabatic flame temperature for the reaction. Therefore, the MoO3 expels gas during combustion. Tungsten trioxide, like MoO3, sublimes below the adiabatic flame temperature of the reaction (sublimation temperature of 3680 K [1], reaction adiabatic flame temperature. of 24

4280 K [1]). This causes WO3 to also expel gas during the combustion reaction. Balakir et al. concluded that the Al+WO3 reaction proceeds primarily in the oxide gas phase [30]. The gaseous intermediate products cause the reacting particles to be violently propelled in all directions. Some of these particles are ejected in the direction of the unburned thermite in the channel. This ignites the unburned thermite much sooner than if the reaction was not violent and only conductively driven. Therefore, the Al+WO3 reaction is diffusion controlled and convection dominant in a loose powder form. The Aerogel 120 has the highest combustion wave speed because it has the smallest particle diameter therefore the smallest diffusion distance. Even though the Aerogel 400 has fewer impurities than the Aerogel 120, it is limited by a larger particle diameter due to sintering during calcination. Because convection is dominant in the loose powder thermite, the small particle diameter of Aerogel 120 outweighs the benefit of higher purity with larger particle diameters found in the Aerogel 400. The faster the reactants diffuse, the faster gas is produced. In summary, the Aerogel 120 has faster combustion wave speeds than the Aerogel 400 due to a faster reaction rate which causes a greater rate of ejected particles (convection) that advance the combustion wave. It should be noted that the products of the Al+WO3 reaction are solids. The tungsten is only in a gaseous form during combustion but the products (i.e. W and Al2O3) condense back into solids as they cool. The reaction is classified as gasless combustion. The highly energetic nature of the reaction carried nearly all of the residue away such that products were not available for further analysis.

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5.2 Pellet Combustion Wave Speed and Sensitivity

5.2.1 Combustion Wave Speed as a Function of Bulk Density The combustion wave speed increases as pellet density increases for Aerogel 400 as seen in Fig. 7. It also appears that the Aerogel 120, nm WO3, and m WO3 samples speeds either stay constant or slightly decrease as pellet density increases. Combustion wave speed data is valid up to pellet densities of 35% TMD. After which, the initial conditions are not constant due to differing heating rates from laser ignition as seen in Fig. 8. As the pellets were pressed to higher densities, the surface finish became much more reflective. Figure 9 shows the surface finish for an Aerogel 400 pellet at 49.6 % TMD. The increasing sheen found at higher pellet densities could reflect some of the laser radiation. Although some radiation would be reflected, the remaining radiation would continue to heat the pellet at a slower rate. The goal is to only heat a thin planar surface of the pellet but the long laser exposure times cause the entire pellet to pre-heat. This slower heating rate effect can increase the combustion wave speed and at the very least causes the initial conditions to be different for pellets with greatly varying ignition delay times.

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Figure 9. Photograph of an Aerogel 400 pellet at 49.6% TMD The remaining combustion wave speed data below 35% TMD shows an apparent trend of increasing wave speed as density increases for Aerogel 400 and no definitive trends for Aerogel 120, m WO3 and nm WO3 as seen in Fig. 7. The increasing trend in Aerogel 400 cannot be confirmed because it only involves two data points without experimental repeatability. If the trend is valid, it can be explained by the fact that pellets of higher densities have higher thermal conductivity. As explained earlier, higher thermal conductivity leads to higher combustion wave speeds. Based on previous unpublished research, it appears that the pellet pressing process does not affect parameters such as particle size. More densely pressed pellets have fewer voids as expected but the particles are not sintered together.

5.2.3 Combustion Wave Speed as a Function of Composition Because the ignition delay times were similar for the four different sample compositions at a given pellet density, the combustion wave speed as a function of 27

thermite composition can be studied. The combustion wave speeds for the Aerogel 400 were dramatically higher than the Aerogel 120, nm WO3, and m WO3 at all pellet densities. Strictly focusing on the aerogels, this is the opposite trend observed for the open channel burns. To explain the reverse trend, the dominant mechanism for the reaction must first be determined. To quantify whether each reaction was conduction or convection dominant, a stability criterion known as the Andreev number was used. The Andreev number is a non-dimensional parameter similar to the Peclet number but tailored to reacting flow through porous media at constant pressure as seen in these thermite pellets [32]. Equation 5.1 shows the calculation used to find the Andreev number (An).

An =

" bUdh c p = const. kg

(5.1)

In this equation, b is the bulk density of the composite, U is the combustion wave speed,

! d is the hydraulic pore diameter, c is the specific heat of the composite and k is the h p g
thermal conductivity of the gas. The hydraulic pore diameter was estimated using Eq. (5.2) [33].
dh = 4" Ao (1# ")

(5.2)

In this equation, is the void volume, Ao is the specific surface area, calculated as the
! solid surface area divided by the solid volume (A /V ), and (1-) is the solid volume
s s

fraction. The Andreev number is relative so it is useful for comparing convection and conduction dominance between two samples. Larger Andreev numbers indicate convection dominance while smaller numbers indicate conduction dominance. 28

Because the pellets corresponding to different composites were not all produced at the exact same density, the Andreev number was found for the narrowest range of densities from 31.7 to 34% TMD. The Andreev number corresponding to the previous range is plotted as a function of oxidizer composition in Fig. 10 with the corresponding values used in calculation shown in Table 2.

Figure 10. Andreev number as a function of pellet oxidizer composition at a TMD range of 31.7-34% Table 2. Calculated Andreev numbers and physical parameters for Al+WO3 composites at 31.7-34% TMD
Avg. Bulk Density (kg/m^3) 2012.31 1923.2 2015.28 1850 Combustion Surface Area Velocity of WO3 (m/s) (m^2/g) 0.1018 0.026 2.1988 15.7 7.1642 28.2 2.309 77.1 Total Surface area in Pellet (m^2) 1.242709043 3.863403864 5.923260903 14.02803719 Total Volume in Pellet (m^3) 1.2648E-07 1.2418E-07 1.1627E-07 1.2319E-07 Total Heat Capacity Cp (J/kg K) 472.6271 471.49765 468.05365 462.18209 Potential Volume (m^3) 4.244E-08 3.992E-08 3.953E-08 3.917E-08 Void Volume (m^3) 8.404E-08 8.425E-08 7.674E-08 8.402E-08 Hydraulic Diameter, dh (m) 3.4216E-14 1.0833E-14 6.0255E-15 2.9514E-15 Andreev Number 2.418E-08 1.577E-07 2.972E-07 4.253E-08

nm WO3 Aerogel 400 Aerogel 120

The Andreev analysis showed that the combustion reactions were strongly conduction dominant for all of the oxidizers at all densities. Moreover, any hot particles 29

ejected by gaseous intermediate products were propelled away from the pellet due to planar burning as confirmed by high-speed photography. Similar Andreev analysis performed on the Aerogel 120 and Aerogel 400 powders found is shown in Table 3. The Aerogel 120 is nearly 2600 times as convective in powder configuration as it is in pellet configuration. Similarly, the Aerogel 400 is nearly 600 times as convective in powder configuration as it is in pellet configuration. Table 3 Normalized Andreev number for Aerogel 120 and Aerogel 400 in pellet and powder configuration Normalized Thermite Andreev Number Aerogel 120 (Pellet) 1 Aerogel 400 (Pellet) 7 Aerogel 120 (Powder) 2583 Aerogel 400 (Powder) 3965 It should be noted that the Andreev analysis only focuses on physical parameters such as particle size, surface area, density, etc., and not on chemical composition. This causes the Andreev analysis performed above to not fully account for the phenomena taking place in Al+WO3 reactions; namely the gaseous intermediate products created from WO3 sublimation. Nonetheless, it is still a useful tool to provide insight into the thermal transport mechanisms occurring. Focusing on the aerogel based pellets specifically, it now becomes clear why the Aerogel 400 outperformed the Aerogel 120. Because conduction is the dominant mechanism for the pellet combustion, the bonded water impurities found in the Aerogel 120 hinder the reaction. The bonded water acts as a heat sink. No large-scale effects such as convection are present in the pellet combustion to outweigh the impurity effects as was 30

seen in the open channel burn experiments. Removing impurities to improve combustion performance was the initial reasoning for calcining the aerogel. Equation 5.3 was used to model the combustion occurring in the Al+WO3 reactions.
1.4 Al + 0.0706Al2O3 + 1/2WO3 + x H 2O "1/2W + 0.4 Al + 0.5706Al2O3 + x H 2O

(5.3)

The subscript x represents the appropriate moles of water for the oxidizer considered.
! This equation accounts for the alumina inherent in nano-Al as well as the bonded water

impurities found in the aerogels. It was assumed that all of the impurities in the aerogels are bonded water. Flame temperatures of 2530 K and 2847 K were calculated for the Aerogel 120 and Aerogel 400 samples respectively using Eq. 5.3. A flame temperature of 3078 K was calculated for an ideal, water-free reaction. The effect of water content on adiabatic flame temperatures is plotted in Fig. 11 for a range or water content of 0-25% oxidizer mass. This shows that the adiabatic flame temperature decreases rapidly as the water content is increased.

31

Figure 11 Calculated adiabatic flame temperature as a function of mass percent water in the oxidizer To estimate the effect adiabatic flame temperature and therefore bonded water content would have on the pellet combustion wave speed, a model derived by Armstrong [42] was used and is shown in Eq. 5.4.
A* exp("E A /RTf )(RTf / E A )# 2 u = 12 d 2 ((Tf " T0 ) /Tf )
2

(5.4)

In this equation, u is the combustion wave speed, A* is a constant based on the inverse
! Lewis number, E is the activation energy, R is the gas constant, T is the adiabatic flame A f

temperature, is the thermal diffusivity, d is the particle diameter and T0 is the initial temperature. Because the adiabatic flame temperature was the only parameter to be varied, Eq. 5.4 can be reduced to the proportion seen in Eq. 5.5.

32

u2 ~

Tf exp("E A /RTf ) # (T " T & 0 % f % T ( ( $ f '

(5.5)

Using this proportion, the adiabatic flame temperatures calculated previously and an
! estimated activation energy of 250 kJ/mol [43], the effect of bonded water content on

combustion wave speed was approximated as seen in Fig. 12. This shows that as the water content in the oxidizer is increased, there is a dramatic drop in combustion wave speed. This analysis predicted that the just a 5% mass water content in the oxidizer would result in a 41% decrease in the combustion wave speed compared with no water content. This verifies why the Aerogel 400 with low water content, greatly outperformed the Aerogel 120 with higher water content, in the pellet configuration.

Figure 12 Estimated drop in combustion wave speed as a function of mass percent water in the oxidizer

33

The reason the Aerogel 400 had a higher combustion wave speed than the m WO3 and nm WO3 can be clearly seen in Fig. 13. By definition, diffusion distance again plays the dominant role for oxidizer performance. The Aerogel 400 oxidizer had the largest surface area (i.e. smallest particle diameter) which causes it to have the highest combustion wave speeds.

Figure 13. Combustion wave speed as a function of oxidizer surface area and pellet density One aspect that has not been analyzed is radiative transport mechanisms. Plantier et al. observed that the flame is highly luminescent in nano-scale Al+Fe2O3 thermites [27]. Because of the high luminescence, they claim that radiation transport may be a significant factor. These nano-scale Al+WO3 thermites also exhibit extremely luminescent combustion properties. To achieve high-speed photographs that are not

34

overexposed, a NDx2 filter, NDx4 filter or a series of both are commonly needed at a fstop value of 32 even with 1/32000 second exposure times. Yang et al. measured absorption coefficients for nano and micron-scale aluminum particles in the UV and VIS spectrum [31]. They found that nano-scale Al particles have significantly higher absorption coefficients than micron-scale particles. To the authors knowledge, similar experiments have not been performed on nano and micron-scale WO3 particles. Pantoya and Granier also recognized that absorption properties of nano-scale particles might be an important contributing factor to the increased ignition sensitivity of Al+MoO3 nanocomposites [29]. They stated that the high flame temperatures coupled with the solid products would provide an intense source for radiation transport. They further explained that because the nano-scale Al particles are smaller than the wavelength of light in the thermal radiation wavelength regime, dependent scattering may increase the effective penetration depth of radiative transport. They claim that this increased penetration depth may cause a larger pre-heat zone to be formed preceding the reaction zone during pellet combustion. They concluded that this enhanced pre-heating of unreacted material would affect the combustion wave speed but not necessarily the ignition sensitivity. Alternatively, an initial study of Al+MoO3 nanothermites conducted by Son et al. concluded that radiation is of little importance and that convective heat transfer is the dominant mechanism during combustion[34]. Therefore, radiative transport mechanisms may or may not play an important role in Al+WO3 thermites. 35

At the very least, radiation transport mechanisms may be important in understanding ignition sensitivity of these pellets because laser radiation was used to ignite the thermites. Different oxidizer and thermite absorption coefficients could affect ignition characteristics such as pre-heating and hot spot formation. Further research is needed before a conclusion can be reached about radiation transports role in nanocomposite thermites.

5.3 Aerogel Combustion Dominant Mechanism Transition The most interesting and important finding from this study is the observed transition from convection based heat transfer to conduction based heat transfer as density increases for the aerogel samples. Figure 14 is a semi-logarithmic plot of the combustion wave speed of the Aerogel 120 and Aerogel 400 as a function of theoretical maximum density. It was formed by combining the open burn data found in Fig. 6 and the pellet burn data for the aerogels found in Fig. 7.

36

Figure 14 Semi-Log plot of combustion wave speed as a function of TMD for Aerogel 120 and Aerogel 400 The Aerogel 120 produced a higher combustion wave speed than the Aerogel 400 in the low-density, open channel configuration. Conversely, in high-density, pressed pellet configuration, the Aerogel 400 consistently produced higher combustion wave speeds than the Aerogel 120. In the open channel configuration, convection heat transfer is the dominant mechanism as confirmed by Andreev analysis as seen in Table 3. Low normalized Andreev numbers correspond to conduction while high numbers correspond to convection. When convection is the dominant mechanism, the most important parameter affecting the combustion wave speed is the particle diameter. Aerogel 120 is composed of smaller particles than Aerogel 400, therefore the Aerogel 120 produces faster combustion wave speeds. As density is increased, the air pockets found in the material are removed which lowers the convective effects. Andreev analysis confirms that conduction is the dominant heat transfer mechanism for the thermites in pellet form (Table 3). The bonded water 37

found in Aerogel 120 impedes the energy transport through conductive mechanisms. For this reason, the Aerogel 400, which does not contain bonded water impurities, outperforms the Aerogel 120 in pellet form. The transition from convection to conduction as density is increased causes the important material parameters to be different depending on the material density. In essence, at the low densities found in powders, convection is dominant and the particle diameter is the most important parameter. At high densities found in pellets, the purity of the oxidizer outweighs the benefits of smaller particle diameter because conduction is the dominant mechanism. Unfortunately, Fig. 14 merely suggests the previous trends. The original set of experiments did not test the aerogels at densities other than the natural density produced through mixing. It would be desirable to find the combustion wave speed for several densities slightly above the natural powder density of each aerogel Also, repeatability was not conducted due to the limited amount of Aerogel 120 and Aerogel 400 available and the uncertainty in the total number of experiments that would eventually be conducted. At the end of this study, when it was apparent that more data would be beneficial for low-density combustion data, new experiments were conducted. Even though new nano-Al was used, the aerogels had aged over a period of 22 months which greatly decreased the performance of the Aerogel 120 and Aerogel 400 (see Chapter VII). Therefore, new data was unable to be obtained for low-density combustion of Aerogel 120 and Aerogel 400. This causes the transition phenomenon to be suggested but not proven. 38

CHAPTER VI CONCLUSIONS

An optimum equivalence ratio of 1.4 was found for thermites composed of nanoAl and Aerogel 120 or Aerogel 400 oxidizer. The slightly fuel rich composition is explained by the increased thermal transport properties found when more nano-Al is used. This pre-heats the reactants and increases the combustion wave speed. Because thermite reactions are diffusion limited, both the Aerogel 120 and Aerogel 400 exhibit higher combustion wave speeds than m WO3 in an open-channel burning configuration. Convection was determined to be the dominant mechanism for the advance of the combustion wave in the loose powder open-channel burn experiments. This was explained by the fact that WO3 sublimes below the adiabatic flame temperature of the combustion reaction. This causes gas to be expelled during the reaction creating convection in the form of the violent ejection of burning particulate in all directions. Andreev analysis further suggests convection dominance. This convection causes the Aerogel 120 to burn faster than the Aerogel 400 even though the Aerogel 400 has fewer impurities. The large-scale effect of convection combined with the smaller particle diameter of Aerogel 120 outweighs the purity benefits of Aerogel 400 in loose powder form. The increase in Aerogel 400 combustion wave speed observed as density increases was attributed to the associated increase in thermal conductivity. Aerogel 400 composites exhibited faster combustion wave speeds at all pellet densities than the 39

Aerogel 120, nm WO3 or m WO3. Andreev analysis showed that conduction is the dominant mechanism for combustion in pellet form. This explains why the Aerogel 400 outperformed the Aerogel 120 which is the opposite trend seen in loose powder form. Bonded water impurities act as a heat sink and impede thermal transport through conduction. Therefore, even though the Aerogel 400 had larger a particle diameter than Aerogel 120, its lack of bonded water causes it to perform better. The Aerogel 400 outperformed the nm WO3 and m WO3 because of its smaller particle diameter and therefore reduced diffusion distance over the other oxidizers. It was noted that radiation effects might play a role in the ignition sensitivity and combustion wave speed of these materials. To date, little research has focused on the radiation effects.

40

CHAPTER VII ALUMINUM AND TUNGSTEN TRIOXIDE AGING EFFECTS

A preliminary study was conducted to quantify aging effects (i.e. decreased combustion wave speeds) that had been observed qualitatively. It was know that aluminum oxidizes in air over time but the length of time and associated environmental factors were unknown or not quantified. The goal was to obtain a length of time for which a mixed thermite could be stored before its performance was significantly reduced.

7.1 Aluminum and Tungsten Trioxide Aging Study

7.1.1 Introduction One of the unique properties of aluminum is that its surface will naturally oxidize with air to form a layer of alumina (Al2O3). There are a few studies that investigate the oxidation of nanosized aluminum powders [12 and 37]. Aumann et al. [12] showed that nano-Al powder consists of an aluminum core with a shell of amorphous alumina. They said that the shell of alumina is what keeps the mixed thermite from reacting until an external energy source stimulates the reaction. They exposed the nano-Al to a controlled amount of oxygen gas at various temperatures for a short time. This showed that the oxide growth was temperature dependent for time periods on the scale of hours. They observed no growth in the alumina shell for temperatures less than 350C. Pesiri et al. [37] also showed that the oxide shell thickness can be controlled by carefully introducing 41

oxygen gas to the aluminum nanopowder during production. They showed that the nanoAl powder would still react with the oxygen in the atmosphere even with the protective alumina layer. This reaction was claimed to increase the thickness of the alumina shell for 3 months of continuous exposure at which point it stabilizes. Finally, they showed that the nano-Al powder is very sensitive to any water vapor in the air and will absorb 5% wt. water from the atmosphere within minutes. Therefore, they recommend handling and storing the nano-Al powder under dry Nitrogen gas. Because of the nano-Als sensitivity to air and water exposure, aging studies have been conducted to quantify the effects of exposure to the atmosphere [38-40]. Walter et al. [38] not only studied the effect of aging on nano-Al, but also on the oxidizers nanoMoO3 and nano-CuO. They showed that the surface area of nano-MoO3 decreased twofold from 10-12 days exposure to light and air. The nano-CuO showed only a slight decrease in particle size with exposure to light and air. The nano-Al metal content decreased by 50% wt. from two years of exposure to air. This showed that for a thermite of Al and MoO3, the aging effects of the MoO3 would have a greater impact sooner than the aging effects of the aluminum. Bulian et al. [39] and Puszynski [40] investigated the aging of nano-Al powder exposed to air with high moisture content. Bulian not only looked at the physical properties of the aluminum, but also the effect on the open burn rate of the exposed aluminum mixed with CuO. Bulian showed very large speed decreases when the aluminum was exposed to 97% relative humidity air for less than 3 days. After 3 days, the thermite wouldnt react at all. The major decrease in speed was even observed when the decreasing reactive aluminum content of the exposed nano-Al 42

was accounted for by increasing the nano-Al mixed with CuO. Bulian attributed the decrease in speed to two factors: the increase in the Al2O3 thickness and the increase in the water content in the aluminum. Puszynski further showed that a large reduction in the percent reactive aluminum content was seen in nano-Al exposed to air with as low as 43% R.H. The time for aluminum content reduction of 50% or greater was on the order of 5-40 days. Finally, both Bulian and Puszynski showed that the effect of water vapor on nano-Al powder could be stopped by coating the aluminum with oleic acid or Dow Corning Z-6124 silane. Additionally, the coatings increased the open burn speeds when the coating weight percent was five or less due to the coating increasing the mixing of the aluminum and the oxidizer. Walter et al. [38] only studied the effect of aging on the nano-Al, nano-MoO3 and nano-CuO separately. The effect of aging on an already mixed thermite was not investigated. Furthermore, there are other relevant oxidizers, such as WO3, which need to be investigated. Bulian et al. [39] and Puszynski [40] also chose to study the aging of the nano-Al and not the thermite itself. Bulian only investigated the effect of very high relative humidity air exposure and Puszynski didnt conduct burn speed measurements on the thermites containing aluminum exposed to lower relative humidity air. Often times, in a lab environment, it is impractical to test a thermite immediately after it has been mixed. The thermites are stored in non-airtight plastic or glass containers. Because of the unknown effect of the exposure of the thermite to the atmosphere, there is no fixed rule for how long the thermite is good after it has been mixed. This study will focus specifically on the effect of atmospheric air exposure on 43

thermites consisting of nano-Al mixed with nano-WO3. Separate mixes will be exposed to the air in an indoor lab environment and sealed in a container for a period of four days. Combustion wave speed measurements of the loose powders will be made from samples of the mixes at various times of exposure by using a high-speed camera. This will extend previous studies by being the first study, to the authors knowledge, to investigate the effect of aging on the mixed thermite itself. Furthermore, it will investigate mixes that include the commonly used oxidizer WO3. Finally, it will quantify the change in performance of thermites exposed to atmospheric conditions common to a lab environment and explain the relevant phenomena using previously published studies.

7.1.2 Experimental Setup The aluminum powder was obtained from Nanotechnologies (Austin, TX) and has a 120 nm average particle diameter. The average particle diameter is calculated by the manufacturer using a gas adsorption analyzer using Brauner, Emmett, and Teller (BET) theory to measure the surface area. The diameter is calculated by assuming the particles are spherical. These Al particles are passivated with an alumina (Al2O3) shell that is roughly 4 nm thick and encapsulates the core Al particle. Based on thermal analysis (Base Hydrolysis Method), the manufacturer determined that this powder has an active Al content of 81%. Active Al is defined as the portion of powder not in the form of Al2O3. The previous material specifications were measured on June 25, 2004 for the particular batch of Al used in this study. Also, the Al used was originally opened on July 14, 2004 after being received from the manufacturer packed in argon gas. After being 44

opened, it was sealed in an airtight container until mixed with the oxidizer on October 18, 2004. The tungsten trioxide (WO3) powder was purchased from Aldrich (St. Louis, MO) and has an average particle diameter of 49.6 nm. The manufacturer supplied the particle diameter data using an unspecified method. Also, because no purity data was provided, it was assumed that the WO3 was 100% pure. This assumption was valid because the WO3, unlike the Al, doesnt have a passivation shell or any other characteristic which would cause a loss of purity. The WO3 used in this study was originally opened from the manufacturer on September 9, 2004 and again stored in an airtight container until mixed with the fuel on October 18, 2004. It was calculated that approximately 6 grams of Al+WO3 mixture was needed. Due to safety considerations, three separate but chemically equivalent batches of 2 grams each were prepared as described below. Each batch was prepared by combining the powders in controlled proportions in a suspension solution of isopropanol. The powders and solution were mechanically mixed using an ultra-sonification process. This process allowed for a more homogeneous mixture by breaking up large agglomerates. The mixture and solution was heated at a low temperature in a glass dish to evaporate the isopropanol solution. After all of the isopropanol had evaporated, the composite powder was scraped from the dish and placed into a vial to be immediately combined with the other batches. The three batches were mechanically mixed and then separated into two equal amounts. One half was placed into a 4 oz. polypropylene vial with a lid from Tyco

45

Healthcare Group LP. (Mansfield, MA) and the other half was placed into a glass dish open to the ambient laboratory environment. Both of the thermite samples, one open to the air and one enclosed in the vial, were stored next to each other in the ambient lab environment as seen in Fig. 15. The temperature and relative humidity was measured and recorded every 24 hours using a digital hygro-thermometer calibrated by Control Company (Friendswood, TX) on June 4, 2001. The temperature and relative humidity measurements were averaged for the five days of aging to get an overall average temperature of 23.6C, and an overall average relative humidity of 38%.

Figure 15 Photograph of sample storage containers 46

The performance of the thermite was quantified by measuring the combustion wave speed of loose powder burning in a channel exposed to an ambient air environment. The schematic of the full apparatus used to measure the combustion wave speed is found in Fig. 16. A square channel 0.3175 cm wide and 10 cm long was used to burn the loose powders in as seen in Fig. 17. The channel was made of acrylic so that the light from the thermite combustion could pass through. The powder was ignited by a spark gap that passed through the channel. A trigger fired the spark gap ignition and triggered the camera at the same time. A Phantom IV high-speed camera from Vision Research (Wayne, NJ) was used to record the flame propagation. The camera interfaced with a computer that used Vision Research software to post process the videos. By establishing a reference length, the software determines speed based on a distance between sequential time frames.

47

PC with Imaging Software

Open Burn Channel High Speed Camera Spark Gap Ignition

Trigger

Figure 16 Schematic of flame propagation apparatus 48

Figure 17 Photograph of burn channel Every day for five days, two samples from the vial and two samples from the tray were burned and the combustion wave speeds were recorded. Each sample was 250 mg. Two samples were burned daily to obtain repeatability data. It was observed that the combustion wave speeds were not constant throughout the burn. Because the speed was not constant, either the measurement time or the measurement length was required to be kept constant to achieve comparable speed measurements. It was impractical to keep the length viewed in the videos constant because the camera was moved daily for other experiments so the time was held constant. The average speed was measured between the frame where first light was visible and 40 frames later. Because the camera ran at 32000 49

frames/sec, 40 frames is equal to 1.25 ms. The standard deviation was calculated for all of the repeated tests.

7.1.3 Results Table 4 presents the combustion wave speeds recorded over the four-day period. It shows the individual and average speeds starting on day 0 until day 4. It can be seen that one repeatability test was conducted for each sample. Table 4 Combustion Wave Speeds Velocities (m/s) 0 1 2 3 36.176 33.591 30.843 31.168 31.734 30.305 33.260 31.751 33.955 31.948 32.052 31.460 3.141 2.324 1.709 0.412

Days Aged Vial Burn 1 Vial Burn 2 Avg. Std. Dev. Tray Burn 1 Tray Burn 2 Avg. Std. Dev.

4 31.446 31.445 31.446 0.001 27.936 32.893 30.415 3.505

37.446 33.878 35.662 2.523

33.042 36.073 34.558 2.143

30.842 33.829 32.336 2.112

29.951 33.242 31.597 2.327

In Fig. 18, the average combustion wave speed for the tray and vial mixes is plotted as a function of the number of days the mix has aged. The error bars represent a standard deviation between the repeated tests for each sample. The points on the plot were slightly separated for each day to show the error bars more clearly. All tests were actually conducted within 30 minutes of each other on each day so the daily points would truly be on top of one another.

50

40
Combustion Wave Speed (m/s)

38 36 34 32 30 28 26 -0.5

Vial Contained Tray Contained

0.0

0.5

1.0

1.5 2.0 2.5 Days Aged

3.0

3.5

4.0

4.5

Figure 18 Plot of combustion wave speed as a function of days aged

7.1.4 Discussion Figure 18 shows that there is a decrease in the combustion wave speed for thermites that have aged for a period of four days. This result was expected because it was already known that Al particles form thicker alumina shells the longer they are exposed to air [12 and 37] which reduces the amount of active aluminum or fuel. Using the data from Table 4, it was calculated that over a period of 4 days, the sample stored in the vial had a reduction in combustion wave speed of 7.4% and the sample stored in the tray open to the air had a reduction in combustion wave speed of 14.7%. This shows that it is certainly better to place a mixed thermite in some type of container than to allow it to

51

be exposed to air freely. Even though the vial was not advertised as air tight, it did have enough benefit to reduce the speed degradation by half. Bulian et al. [39] showed a reduction in the combustion wave speed of over 50% within two days exposure to air at 40C and 97% relative humidity. This study shows that samples exposed to air at a lower temperature and a lower relative humidity experience a much smaller reduction in the combustion wave speed performance. Bulian et al. [39] also theorized that the decrease in combustion wave speed was due to the increase in the alumina barrier on the aluminum particles and increase in the physisorbed and chemisorbed water. This study shows that the increase in the water content in the aluminum plays a greater role than the increase in the alumina shell. Far less reduction in wave speed was seen at double the exposure time at similar dry air exposures but reduced water vapor exposures. Of course, Bulian et al. [39] also used copper oxide as the oxidizer and mixed the thermite after the aluminum exposure. This suggests that a thermite that is already mixed is less susceptible to environmental exposure. This could be due to the fact that the oxidizer blocks some of the aluminum particles contact with the environment. Tungsten trioxide doesnt experience an effect like the alumina shell formation when exposed to air so the air exposure by itself would not affect the WO3 as severely as the aluminum. Further study is needed to prove this theory. Chemical analysis to determine the chemical composition of the thermite at different stages of exposure would show whether the alumina formation is hindered in a premixed thermite.

52

There were several problems encountered with this study. The greatest problem encountered was in measuring an accurate combustion wave speed. Because the wave speeds did not vary by a large degree, very accurate measurements were needed to find a trend in the data. Because the combustion wave was identified by visual methods, problems arose from the brightness of the thermite when burnt. The brightness can be reduced mechanically and electronically by filters and image processing but reflections off of the burning channel and the smoke from the combustion made finding the combustion wave difficult. Other difficulties came from the combustion waves being so fast in a Al+WO3 thermite. There was only a limited amount of data that could be recorded with the equipment on hand. The camera recorded at 32,000 frames/sec which was not ideally fast enough for these very high-speed thermites. Finally, the Al+WO3 thermite exhibited non-constant combustion wave speeds. Other thermites such as Al+Fe2O3 exhibit much more constant combustion wave speeds when they are burnt in loose powder form. All of these factors, which would be minor if examining greater speed variations, become large sources of error when such accuracy is needed. This is represented by the relatively large error bars seen in Fig. 18. This study showed that there is a reduction in the degradation of a thermites performance when it is mixed before being exposed to the environment and when the ambient conditions have low relative humidity. This produces a need for further investigation into these phenomena. Besides combustion wave speeds, data about the thermites surface area is also needed. This would more directly compare to the work that Bulian et al. [39] and Puszynski [40] have completed. Also, conducting chemical analysis 53

on the thermites at different levels of environmental exposure would show whether or not the oxidizer impedes the alumina growth. Scanning electron microscope (SEM) pictures might also provide some insight to the oxidizer protecting factor. Finally, studies which are conducted for longer time periods with more accurate measurement techniques such as photo diodes could be conducted.

7.1.4 Conclusions It has been shown that Al+WO3 thermites exposed to ambient laboratory air found in an arid climate will reduce the combustion wave speed of the loose powder by 15% within four days. If the thermite is stored in a standard laboratory vial, the combustion wave speed is reduced by 7% within four days. This shows that even an imperfect, or not airtight, vial should be used to store mixed thermites. Also, if the study being conducted with the thermite requires high accuracy, it is necessary to burn the thermite on the same day as it is mixed. It has also been shown that a mixed thermite exposed to relatively dry air experiences a far smaller amount of performance degradation compared to an unmixed thermite exposed to high humidity air. Therefore, the amount of water vapor in the air plays a very important role in the rate of decreasing performance. Further study is needed to show if the mixed thermite may resist environmental exposure to a greater degree than an unmixed thermite.

54

7.2 Long Term Aerogel Aging In an effort to obtain new data to reinforce the trends seen in Fig. 14, a new batch of Aerogel 120 and Aerogel 400 was mixed 22 months after the initial batch. New nanoAl was used in the mixes but it was required to use the original supply of both aerogel oxidizers. Open-channel combustion burns for the new Aerogel 120 and Aerogel 400 were conducted using the same procedures described in Section 2.1.3 and 2.3. Both thermites were mixed at =1.4 as before. The original Aerogel 120 had a combustion wave speed of 490 m/s. The new Aerogel 120 sample had a combustion wave speed of 8 m/s, a decrease of 98%. The original Aerogel 400 sample had a combustion wave speed of 310 m/s. The new Aerogel 400 sample had a combustion wave speed of 29 m/s, a decrease of 91%. Because the aluminum was new, this shows that the aerogels had almost totally degraded over a period of less than two years. Considering the preliminary aging study mentioned previously, the most likely degrading factor was the absorption of water through water vapor in the atmosphere. An aging study of Al and MoO3 showed that the aging effects of MoO3 were greater than the aging effects of Al [38]. Thermal gravimetric analysis was conducted on the aged aerogel samples as shown in Fig. 19. The original TG analysis is plotted along with the new analysis. It can be clearly seen that the aged oxidizers experience a greater reduction in mass as they are heated. This confirms the presence of additional water in the aged samples.

55

Figure 19 Thermal gravimetric plot of original and aged Aerogel 120 and Aerogel 400

56

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