COMBUSTION BEHAVIORS OF BIMODAL ALUMINUM SIZE DISTRIBUTIONS IN THERMITES by KEVIN MOORE, 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 Brandon Weeks Louisa Hope-Weeks Accepted John Borrelli Dean of the Graduate School May, 2005

ACKNOWLEDGMENTS

First of all, I would like to thank my masters supervisor Dr. Michelle Pantoya for all of the hard work she has dedicated to me reaching this point in my academic career. I am so very grateful that she took a chance on me entering her research program, which has been integral in my development as a student. Her positive attitude and optimistic approach to life were crucial to my success. I would also like to thank my supervisor and mentor at Los Alamos National Laboratory, Dr. Steve Son. I am grateful for the opportunity to work with him and gain so much experience from his guidance. He was always willing to take time out to talk with me about whatever is on my mind, for which I am very thankful. I would like to gratefully acknowledge the support of the Army Research Office (Contract Number DAAD19-02-1-0214) and our program manager, Dr. David Mann. I would also like to acknowledge support by the Los Alamos National Laboratory through the Advanced Energetics Initiative, the Defense Threat Reduction Agency (DTRA), and the Seaborg Institute. I would like to thank the Texas Tech University Honors College for their support through the Undergraduate Research Fellowship Program. I would like to thank my wife, Lindsay, for the love and support she has given me through this trying period. I would like to also acknowledge my family for their loving support and always motivating me to put my best foot forward. I would also like to thank several co-workers that I have had during my work towards this point. Bryan Bockmon was an excellent mentor, during the Texas Tech ii

Mechanical Engineering Mentoring Program in the spring of 2002, and first introduced me to the world of energetic materials. I learned so much from Jim Busse and Eric Sanders, co-workers and lab mentors at Los Alamos National Laboratory, and were an immense help in performing my summer experiments. Also, I would like to thank John Granier for all of his help developing experiments here at Texas Tech.

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TABLE OF CONTENTS

ACKNOWLEDGMENTS .................................................................................................. ii ABSTRACT....................................................................................................................... vi LIST OF TABLES............................................................................................................ vii LIST OF FIGURES ......................................................................................................... viii NOMENCLATURE ........................................................................................................... x CHAPTER I. INTRODUCTION ............................................................................................. 1 1.1 Thermites ................................................................................................ 1 1.2 Nano-composite Thermites..................................................................... 2 1.3 Aluminum Combustion........................................................................... 4 II. EXPERIMENTAL ............................................................................................ 7 2.1 Sample Preparation ................................................................................ 7 2.2 Laser Ignition of Pellets ....................................................................... 10 2.3 Laser Ignition of Loose Powders ......................................................... 11 2.4 Combustion Velocities of Loose Powders........................................... 12 2.5 Pressure Cell Tests............................................................................... 13 III. THEORY ........................................................................................................ 14 3.1 Flame Structure..................................................................................... 14 3.2 Diffusion vs. Chemical Kinetics .......................................................... 15 IV. RESULTS ....................................................................................................... 18 4.1 Ignition Sensitivity............................................................................... 18 iv

4.2 Combustion Velocity ........................................................................... 21 V. DISCUSSION ................................................................................................. 24 5.1 Ignition Sensitivity............................................................................... 24 5.2 Combustion Velocity ........................................................................... 26 VI. VII. CONCLUSIONS ............................................................................................ 36 IMPLICATIONS AND FUTURE RESEARCH............................................ 38 7.1 Nano-scale Aluminum Properties ........................................................ 38 7.2 Mixing Techniques .............................................................................. 39 7.3 Preliminary Molybdenum Trioxide Study ........................................... 40 REFERENCES ................................................................................................................. 47

ABSTRACT

In recent years many studies that incorporated nano-scale or ultrafine aluminum (Al) as part of an energetic formulation demonstrated significant performance enhancement. Decreasing the fuel particle size from the micron to nanometer range alters the materials chemical and thermal-physical properties. The result is increased particle reactivity that translates to an increase in the combustion velocity and ignition sensitivity. Little is known, however, about the critical level of nano-sized fuel particles needed to enhance the performance of the energetic composite. Ignition sensitivity and combustion velocity experiments were performed using a thermite composite of Al and molybdenum trioxide (MoO3) at the theoretical maximum density (TMD) of a loose power (5% TMD) and a compressed pellet (50% TMD). A bimodal Al particle size distribution was prepared using 4 or 20 m Al fuel particles that were replaced in 10% increments by 80 nm Al particles until the fuel was 100% 80 nm Al. These bimodal distributions allow the unique characteristics of nano-scale materials and their interactions with micron scale Al particles to be better understood.

vi

LIST OF TABLES

1. Reactant Particle Description................................................................................................7 2. Calculated thermal and physical parameters for all Al-MoO3 composites ........................28

vii

LIST OF FIGURES

1. A SEM micrograph of an 80 nm and 4 m Al mixture ..................................................8 2. Schematic diagram illustrating aluminum distribubimodal mixture ratios.....................9 3. Schematic diagram of the unconfined loose powder ignition sensitivity test apparatus. .....................................................................................................................12 4. Schematic diagram of the combustion velocity test apparatus for loose powders. .....12 5. Typical thermite flame structure diagram.....................................................................14 6. Still frame images of ignition and flame propagation of an Al-MoO3 pellet with an Al distribution of 60 wt % 80 nm and 40 wt % 4 m.. ...........................................18 7. Ignition time for pellets as a function of percent 80 nm Al content mixed with MoO3 and 4 m Al at 50 W laser power ....................................................................19 8. Ignition time for pellets as a function of percent 80 nm Al content mixed with MoO3 and 20 m Al at 50 W laser power ..................................................................20 9. Ignition time for loose powders as a function of percent 80 nm Al content mixed with MoO3 and 4 or 20 m Al at 50 or 100 W laser power.........................................20 10. Combustion velocity as a function of weight percent 80nm Al content for pellets with 4 m Al and MoO3 .............................................................................................22 11. Combustion velocity as a function of weight percent 80nm Al content for pellets with 20 m Al and MoO3 ...........................................................................................22 12. Combustion velocity as a function of weight percent 80nm Al content for loose powder with 4 or 20 m Al and MoO3.......................................................................23 13. Pressure output as a function of percent nano-Al content for loose powder Al-MoO3 mixtures with 4m and 20m Al. ..............................................................29 14. Combustion of 100% 80nm Al and MoO3 loose powder mixture..............................31 15. Combustion of loose powder Al and MoO3 mixture with 10% 80nm Al and 90% 20m Al .............................................................................................................32 16. Combustion of 100% 4m Al and MoO3 loose powder mixture................................33 viii

17. SEM images of products of 50% 80 nm Al and 50% 20 m Al pellet mixtures with MoO3....................................................................................................................34

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NOMENCLATURE

Variable A B C D Ea k
& m"

Arrhenius pre-exponential factor Mass transfer number Species concentration Mass diffusivity Activation energy Surface reaction rate constant Mass flux Radial dimension Gas constant Spherical fuel particle outer radius Temperature Mass fraction

r R R T Y

Greek Pure fuel density Reaction rate

CHAPTER I INTRODUCTION

1.1 Thermites A thermite reaction is often described as a reaction between a metal and a metallic or non-metallic oxide, which results in a more stable metallic oxide and the corresponding metal or non-metal of the reactant oxide [1]. An important product of these reactions is a high heat of reaction, commonly referred to as energy density [1]. Once ignited, the thermite reaction is self-sustaining due to this highly exothermic heat release. Thermite reactions are typically thought to be conductively driven reactions. Most solid energetic materials, including explosives like trinitrotoluene (TNT) and nitroglycerine, are composed of many molecules of the same engineered material. These materials are referred to as monomolecular energetic materials. Within each of these molecules are fuel, typically carbon, and oxidizing molecules which allow the reaction to occur without the presence of additional oxygen from the environment. Monomolecular energetics have kinetically controlled reactions which can produce very high deflagrations or even detonations. Unlike monomolecular energetics, thermites are mixtures of fuel and oxidizing particles, typically ranging from 1 to 100 microns in size. Due to the inherent separation of the fuel and oxidizing particles, the reaction is diffusion controlled, which usually translates to much slower deflagrations. Although thermites have relatively high energy densities, the slow burning rate causes the energy release rate to be much slower than that of monomolecular energetics.

This slow energy release rate has limited the utility of thermite materials mostly to areas outside of explosives. Welding underwater or in hard to reach places is often solved by the use of thermites; molten metals from the reaction can seep between the metal pieces and form a bead during the cooling process [1]. Self propagating high temperature synthesis (SHS) is another important application of thermite-type materials [3-6]. SHS, which often involves the intermetallic reaction between two or more metals, allows the development of materials with more mechanically favorable microstructures for specific applications [3]. One-such application is the formation of a ceramic layer on the inside of metal piping induced by the reaction of a thermite on the inner surface of the pipe [1].

1.2 Nano-composite Thermites Particle size reduction of fuel and oxidizing particles within the micron range in thermite systems has resulted in significantly improved combustion performance. Shimizu and Saitou [7] have experimentally shown that the reaction rate of the Fe2O3V2O5 system increased as the number of contact points between the fuel and oxidizing particles increased. Brown et al. [8] have seen similar results in the Sb-KMnO4 system. As the calculated number of contact points in this system doubled due to smaller particle sizes, the burning rate of the mixtures tripled [8]. Tomasi and Munir [9] have shown that as the particle size of the Nb2O5-Al2Zr system decreased from 25 to 2 microns, the reaction burn rate increased by a factor of five. Drennan and Brown [10] have shown burn rates double as the molybdenum particle size of MoBaO2 and MoSrO2 systems is reduced from 35 microns to 15 microns. It is apparent that the particle size of the mixture 2

plays a significant role in the combustion performance for all of these systems. The increase in reactivity for these cases is attributed to a better mixing between fuel and oxidizing particles. Smaller particle sizes allow the fuel and oxidizing particles to

effectively be closer together, creating smaller diffusion distances that must be overcome during the reaction. Recent developments in particle formation technology have created the cost efficient production of nano-scale particles [11]. One potential for nano-particles to increase combustion performance is due to diffusion distances decreasing for particles of this size. In addition to new particle formation technologies, new characterization

technologies, like small angle neutron scattering, have been developed to determine particle size distributions more accurately for particles in the micron range [12-13]. The reduction of aluminum particle size to the nano-scale in the Al-MoO3 system has shown promising results. An initial study by Son et al. [14] shows increased burning rates in nano-sized aluminum thermite mixtures; an important finding of their experiments shows that radiation is of little importance and that convective heat transfer during the reaction process is a more prominent factor. Bockmon et al. [15] have shown that burning rates of Al-MoO3 nano-powder mixtures can reach confined burning rates of up to 1 km/s. These speeds, which are attributed to a prominent convective burning, are much faster than thermites are traditionally known to burn. Traditional thermites burn on the order of 1 m/s [1]. Direct comparison of nano and micron aluminum particle sizes in Al-MoO3 mixtures by Granier and Pantoya [16] yields very dramatic results. Granier and Pantoya [16] examined the ignition and combustion velocity of Al-MoO3 pressed composites as a 3

function of Al particle size. Their work showed that reducing the Al particle size from micron to nanometer dimensions decreased the ignition delay time by two orders of magnitude (from 10 s to 10 ms). The significantly enhanced ignition sensitivity was attributed to the increased reactivity of the nanometer particles [17]. Pantoya and Granier [17] showed through thermal analysis that the nano-Al and MoO3 reaction is initiated at temperatures below the melting of Al (660 C) and sublimation of MoO3 (770 C) and that the reaction takes place in the solid-solid phase. They also showed that for micron Al reacting with MoO3, the reaction is initiated after Al melting and MoO3 sublimation such that ignition is controlled by a liquid-gas diffusion mechanism. These results indicate that the nano-Al particles are more reactive because they react in the solid phase and at lower temperatures than the micron-Al particles.

1.3 Aluminum Combustion An important part of the study of Al-MoO3 combustion is the behavior of aluminum during the ignition process. Much work has been done related to the reactivity of aluminum, both on the micron and nano scale, over the past 20 years [18-31]. In a study by Popenko et al. [18], a mixture of ultrafine Al powder was combined with micron Al powder for an examination of the bimodal Al distribution combustion behavior in air. They analyzed the presence of bound nitrogen in the products of bimodal Al and air combustion and found that for mixtures consisting of less than 70 % micron Al powder the percent of bound nitrogen remained constant. The interesting finding was that the bound nitrogen content in the combustion products of these mixtures decreases considerably if the ultrafine Al concentration in the mixture is less than 20 % and this 4

behavior is attributed to the concurrent processes of sintering and incomplete combustion [18]. In a study by Trunov et al. [23], differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to analyze micron sized aluminum behavior at increased temperatures. A focus of this study was on the phase changes of the alumina oxide layer that covers the outside of each aluminum particle. Trunov determined the initial oxide layer to be amorphous and between two to three nanometers thick for his samples. During the TGA analysis, a weight gain was observed between 550-650 C. During this temperature range, the alumina layer reportedly underwent a phase change from amorphous to -phase. The -phase has a density that is 20% higher than the amorphous phase and after this transition the outer surface of the aluminum particle may not be completely surrounded by an oxide layer. Exposed aluminum would oxidize as oxygen from the atmosphere diffuses to the particle surface, which could account for the weight gain observed. Other factors may also contribute to the enhanced ignition sensitivity, such as altered absorption properties which enable nano-Al particles to more readily absorbed energy than their micron scale counterparts. In fact, Yang et al. [32] showed that the absorption coefficient of 30-nm Al particles is significantly greater than micron scale particles and a strong function of particle size (see Fig. 5 of Ref. 32). Using nanometer combined with micron scale Al particles in rocket propellant applications has strong advantages. For example, all Al particles are pyrophoric and therefore passivated with an unreactive oxide shell (e.g., Al2O3). As the particle surface area to volume ratio increases the presence of Al2O3 increases and becomes a significant 5

portion of the overall mixture. Because propellant payloads can be restrictive, the unwanted levels of an unreactive oxide that may add weight and reduce energy density are undesirable [11, 35]. For this reason, adding small amounts of nanometer to micronscale Al particles may facilitate increased reactivity without the unwanted burdens of excessive amounts of Al2O3. In a study by Dokhan et al. [36] the burning behavior of ammonium perchlorate (AP) solid propellant with bimodal aluminum particle size distributions was examined. They showed a significant increase in burn rate with only a 20% addition of nanometer Al. At this level, Dokhan et al. [36] showed Al combustion takes place closer to the propellant burning surface allowing increased radiative and conductive heat feed back that increases the temperature at the burning surface and correspondingly increases the burn rate. Due to the increased ignition sensitivity and burning rates of the nano-composite thermites, a recent surge of interest is focused on developing thermites that may replace traditional lead-based compounds in gun primers [37, 38]. Reducing the presence of toxins such as lead in firearms will not only reduce health risks to personnel but will also improve the environment. In particular, nanometer Al mixed with MoO3 and acetylene black (a form of carbon) is being studied as a replacement for lead compounds [37]. This study will examine the ignition sensitivity and combustion velocity of Al and MoO3 composites as a function of the Al particle size distribution. Mixtures are prepared using 4 or 20 micron combined with 80 nm diameter Al particles in discrete mixture ratios. Both powder and compressed pellet combustion was studied. The goal is to investigate the influence of nanometer Al on the ignition sensitivity and combustion velocity of thermites. 6

CHAPTER II EXPERIMENTAL

2.1 Sample Preparation Table 1 shows physical data for the Al particles and the material supplier for the Al and MoO3. The Al particles are encapsulated within a protective Al2O3 shell. The active Al content is the percent of Al powder that is not in the form of Al2O3. As can be seen with the 80 nm diameter Al powder, the Al2O3 shell becomes an appreciable portion of the total powder, causing the active Al content to reduce to only 73 % (Table 1). The active Al content is reported by the manufacturer. The particle diameters listed in Table 1 are an average value reported by the manufacturer. Micrographs, one of which is shown in Figure 1, reveal that the reported average particle diameter is consistent with the particles observed using scanning electron microscopy (SEM). The average oxide shell thickness is calculated assuming that the oxide layer is uniformly surrounding spherical particles and all particles are of the average particle size. Based on these assumptions and the reported active Al content and the average particle diameter, the thickness of the shell is calculated and tabulated in Table 1. Table 1. Reactant Particle Description
Particle 80 nm Al 4 um Al 20 um Al MoO3 % Active Al Content 73 91 99 Al2O3 Layer Thickness 4.3 nm 70 nm 30 nm Supplier Nanotechnologies Alfa Aesar Sigma Aldrich Technanogy/Climax

Aluminum was mixed with MoO3 in a 40/60 wt % ratio which corresponds to a fuel rich equivalence ratio of 1.3, based on active Al content. This mixture ratio was shown to be an optimal composition for achieving the highest combustion velocity and shortest ignition delay time [16]. The mixtures used to make pellets were dispersed in a hexane solution and sonicated to break up agglomerates and ensure a homogeneous mixture. The wet solution was poured into a tray and slightly heated to allow hexane evaporation.

Figure 1. A SEM micrograph of an 80 nm and 4 m Al mixture. For pellet tests, a well-mixed, dried powder was separated into 230-270 mg quantities and cold pressed with a hydraulic press (0.5 1.5 MPa) and a uniaxial die. All final pellets were 6.51 mm in diameter and 3.9 mm in length. Higher pressures (1.5 8

MPa) were needed to form the less dense nano-powder formulations to the same dimensions of the micron-powder formulations. Theoretical maximum density (TMD) calculations are based on the weighted average of Al, MoO3, and Al2O3 present in the mixture. For pellets, the powders were pressed to a TMD of 50 % ( 2 g/cc) while the pour density of powders was 5 % TMD ( 0.2 g/cc). Eleven mixtures of Al/MoO3 were prepared, each with a varying distribution of Al particle size ranging from 100 % 80 nm to 100 % 4 or 20 m diameter. The distribution of active aluminum by particle size for each of the samples is illustrated in Fig. 2.

Distribution of Active Aluminum

100

Percent Active Aluminum

90 80 70 60 50 40 30 20 10 0 1 2 3 4 5 6 Mixture 7 8 9 10 11

Nano Al
Micron Al

Figure 2. Schematic diagram illustrating aluminum distribubimodal mixture ratios.

In all experiments, the thermite mixtures were burned in an ambient environment. A study by Asay et al. [39] has experimentally shown that burning rates of Al/MoO3 powders were the same when in ambient and vacuum environments.

2.2 Laser Ignition of Pellets The pellets were ignited using a 50-W CO2 laser (Universal Laser Systems Inc, Scottsdale, AZ), power meter and associated optics. Ignition and flame propagation were recorded using a Phantom IV (Vision Research, Wayne, NJ) high-speed camera which captured images at 32,000 frames per second (fps). Details of this experimental apparatus are discussed elsewhere [16]. Ignition is defined in the context of thermite combustion as the onset of a fully sustained self-propagating reaction. There are several techniques for measuring an ignition delay time [16]. The technique applied here is based on the first-light approach in which ignition time is determined as the time lapse between sample exposure to laser beam and detection of the first light. This may not guarantee ignition but is a commonly used technique for experimentally determining ignition times [40]. The high-speed

camera is synchronized with the CO2 laser and detects light intensity. In this way, the reaction light is used as the illuminating source to visualize the ignition process. Burn rate is a measure of the burning solid surface of an energetic material and often is used in reference to a single particle. Propellant combustion studies typically refer to a mass burning rate which characterizes the regression rate of the combusting solid propellant. In this thermite combustion, the flame consumes and spreads through discrete particles packed in a highly porous matrix. The physics of flame propagation in 10

this arrangement entails flame spreading and is a strong function of the packing arrangement of particles and the porous structure of the material. The term combustion velocity will be used to characterize the speed of the leading edge of the reaction zone identified by visible light emission recorded from the high-speed photographic data.

2.3 Laser Ignition of Loose Powders A schematic of the setup used in the laser ignition of powders is shown in Figure 3. A Coherent 250-W CO2 laser (Santa Clara, CA) was used to ignite the samples. A NaCl beam splitter (Vigo Photovoltaic, Warsaw, Poland) diverted 8% of the laser beam to a tri-metal detector used to determine the time of the start of the laser pulse. A Thorlabs DET210 photo-diode (Newton, NJ) with a response time of 1 nanosecond, measured light intensity of the reaction and determined the ignition time, based on a Tektronix (Richardson, TX) oscilloscope with a response time of 1 nanosecond. The ignition time was defined as the time at which the photo-diode trace reached 3% of its peak voltage.

11

Figure 3. Schematic diagram of the unconfined loose powder ignition sensitivity test apparatus.

2.4 Combustion Velocities of Loose Powders The unconfined loose powder tests were completed using an apparatus schematically shown in Figure 4. A piezo-electric starter ignited the powder mixture (120 mg) poured into the tray. A profiling glide leveled a consistent cross section

Figure 4. Schematic diagram of the combustion velocity test apparatus for loose powders. 12

throughout the sample.

The pour density of the powder was about 0.02 g/cc

corresponding to a TMD of 5 %. As the reaction progressed inside the tray, two holes, 1 mm in diameter, in the bottom of the tray, which were 2 cm apart, allowed light from the reaction to be emitted into fiber-optic cables. Photo-diodes were used to convert this light pulse to a voltage that was displayed on an oscilloscope. The average velocity of the unconfined burn was determined from the two voltage pulses on the oscilloscope. The time of reaction propagation between the holes was determined by the time delay between the two voltage pulses. Due to the small size of the hole, the voltage pulses did not occur until the reaction passed directly over the pinholes. The average velocity was calculated by dividing the distance between the holes by the time of reaction propagation between the holes. Previous tests have shown through high speed photography that the reaction reaches its steady state velocity after a very short distance, which supports the accuracy of this average velocity measurement.

2.5 Pressure Cell Tests For the pressure cell experiments, a YAG Continuum MiniLite 100mJ laser (Santa Clara, CA), by way of a Thorlabs fiber-optic cable, was used to ignite the samples inside a parr-bomb type chamber. An aluminum cup contained the mixture at a constant volume of 0.151 cm3. The aluminum cup did not react with the samples and was weighed after each test to ensure this. A PCB Piezotronics (Depew, NY) pressure transducer, with a response time of 1 microsecond, was used to determine maximum pressure output for each test.

13

CHAPTER III THEORY 3.1 Flame Structure Ignition of the thermite reaction is traditionally thought to be due to a phase change in one or more reactants. Due to the diffusive nature of the reaction, melting and sublimation are common phase changes that allow elevated temperature fuel and oxidizing particles to come in better contact, which then facilitates ignition of the reaction. The Al/MoO3 reaction occurs according to the following chemical equation: 2Al + MoO3 Al2O3 + Mo. Hcomb=4279cal/cm3

The phase changes of this reaction could be the melt of aluminum at 660 C and/or the sublimation of MoO3 at 700 C. A simplified diagram of the flame structure is shown in Figure 5.

Figure 5. Typical thermite flame structure diagram

14

As the reaction occurs, molten products spew away from the pellet or powder specimen. Some of the energy from the reaction convectively heats a region of the reactants before ignition of those particles. The thickness of the pre-heat zone is

determined by the porosity and thermal characteristics of the sample material.

3.2 Diffusion vs. Chemical Kinetics The combustion behavior of these reactants can be explained by describing the rate at which reactants (Al and MoO3) convert to products (Al2O3 and Mo) [41]. The reaction can be reduced to considering a single small sphere of fuel (Al) and surrounding oxidizer. First assume that the reaction occurs at the surface of the solid Al sphere and the reaction is either limited by the chemical reaction rate or the oxidizer diffusion rate. The reaction rate () can be expressed as shown in Eq. (3.1) [41] assuming the following global reaction.
2 = kC Al C Al O
2 3

(3.1) Al2O3 + Mo

2Al + MoO3

In Eq. (3.1) C Al and C Al2O3 are the concentrations of the reacting chemical species Al and Al2O3 respectively. Each concentration is raised to the power equal to the corresponding stoichiometric coefficient. The specific reaction-rate constant, k, can be expressed as an Arrhenius law according to Eq. (3.2) [41], where A is the pre-exponential factor and E a is the activation energy of the reaction.

k = A exp(

Ea ) RT

(3.2)

15

Assuming that the spherical nano-scale particles burn on the surface as oxidizer
& diffuses to the surface, the mass-burning rate ( m ) of the sphere is given by Eq. (3.3) [41],

& where mR " is the mass flux at the surface, D, is the mass diffusivity and B is the mass

transfer number. & & m = 4R 2 mR " = 4RD ln(1 + B) (3.3)

The mass flux from the particle surface would equal the fuel reaction rate. The reaction rate is first order in oxygen concentration and second order in fuel concentration as in Eq. (3.1).
& m R " = = kYox , RYF2, R

(3.4)

Assuming that the reaction rate occurs at the particle surface, the fuel mass fraction ( YF , R ) in the gas phase is small compared to oxygen such that:

YF , 0 YF , R = 1 Yox , R << 1 .
The mass transfer number can be expressed as

B = Yox , Yox , R
and

(3.5)

Yox , R < Yox , < 1 .

The small number approximation can replace the natural log function in the mass flux term.

& mR " =

D
R

ln(1 + B)

D
R

(Yox , Yox , R )

(3.6)

16

Solving for Yox , R in Eq. (3.4) and substituting into Eq. (3.6), the mass flux at the particle surface is given in Eq. (3.7). k

D
(3.7)

& m R " = Yox , (

R ) D k+ R

In diffusion controlled reactions, the reaction rates are fast compared to the oxygen diffusion rates. Here k >> D/R and the mass flux is a function of the particle radius according to Eq. (3.8).

& mR " = Yox ,

D
R

(3.8)

If the reaction rates are comparable to or slower than the oxygen diffusion rate, then the chemistry controls the reaction. In this case, k << D/R and the mass flux is independent of particle radius (Eq. (3.9)).

& mR " = kYox ,

(3.9)

For diffusion controlled reactions, the mass flux (Eq. (3.8)) and subsequent reaction rates are inversely proportional to particle radius and directly proportional to oxygen concentration. Eq. (3.8) suggests that smaller particles (nano-regime) will

produce higher mass flux rates than larger particles (micron regime) and thus produce increased burn rates.

17

CHAPTER IV RESULTS

4.1 Ignition Sensitivity Figure 6 is a sequence of still frame images illustrating ignition and flame propagation of a pellet composed of 60 wt % 80 nm and 40 wt % 4 m Al particles combined with MoO3. The sequence of images was captured with the high-speed camera at 32,000 fps (corresponding to 31 ms intervals). Ignition occurs at the pellet center front face and the reaction propagates radially then axially through the pellet. The flame front is stable and planar and fully self-sustained.

1 11.762 ms 111.792 ms

111.823 ms 111.855 ms

1 11.886 ms 111.916 ms 111.947 ms

Figure 6. Still frame images of ignition and flame propagation of an Al-MoO3 pellet with an Al distribution of 60 wt % 80 nm and 40 wt % 4 m. The time from trigger is given.

18

Figures 7 and 8 show the ignition delay time as a function of percent nano-Al within the pellet mixture. The standard deviation bars represent the range of measurements for 4-6 pellets from each of the 11 mixtures, the data symbol corresponds to the average ignition delay time. The ignition times reported here for all mixtures containing nano-Al are consistent with previous ignition time measurements made by Granier and Pantoya [16] for 100 % nano-Al MoO3 mixtures. Figure 9 shows the ignition delay time as a function of percent nano-Al for a loose powder mixture. Both mixtures containing either 4 or 20 m Al are shown for laser powers set at 50 or 100 W.

250 Ignition Delay Time, ms 200 150 100 50 0 0 20 40 60 Percent 80nm Al 80 100

Figure 7. Ignition time for pellets as a function of percent 80 nm Al content mixed with MoO3 and 4 m Al at 50 W laser power

19

3000 2500 2000 1500 1000 500 0 0 20 40 60 80 100

Ignition Delay Time, ms

Percent 80nm Al

Figure 8. Ignition time for pellets as a function of percent 80 nm Al content mixed with MoO3 and 20 m Al at 50 W laser power
10000
20m and 80nm at 100W

4m and 80nm Al at 100W

Ignition Delay Time, ms

1000

20m and 80nm Al at 50W

4m and 80nm Al at 50W

100

10

1 0 20 40 60 80 100
Percent 80nm Al

Figure 9. Ignition time for loose powders as a function of percent 80 nm Al content mixed with MoO3 and 4 or 20 m Al at 50 or 100 W laser power. 20

4.2 Combustion Velocity The Phantom imaging software uses a designated light intensity transition and the elapsed time between frames to calculate the combustion velocity. The combustion velocity as a function of 80 nm Al content is plotted in Fig. 10 for the 4 m mixture pellet, in Fig. 11 for the 20 m mixture pellet and Fig. 12 for the 4 and 20 m mixture powders. In Figure 11, the data for 0 and 10 % 80-nm Al content are not shown. In the case of 0% nm Al, the pellet was exposed to the laser for a relatively long period of time before ignition. The exposure to this heat flux volumetrically heated the pellet, igniting the pellet under different initial thermal conditions than for the pellet mixtures containing nano-Al. For this reason, this data was not included. For the 10 % 80 nm Al sample, the pellet could not sustain a self propagating wave and velocity measurements could not be made.

21

40 35 Combustion Velocity, m/s 30 25 20 15 10 5 0 0 20 40 60 80 100 Percent 80nm Al

Figure 10. Combustion velocity as a function of weight percent 80nm Al content for pellets with 4 m Al and MoO3
45 40 Combustion Velocity, m/s 35 30 25 20 15 10 5 0 0 20 40 60 80 100 Percent 80nm Al

Figure 11. Combustion velocity as a function of weight percent 80nm Al content for pellets with 20 m Al and MoO3

22

The unconfined loose powder combustion velocities for both micron-scale mixtures are plotted versus the percent nano Al content in Fig. 12. The piezo-electric starter was not able to ignite mixtures with 0% or 10% nano Al content, therefore no data are shown for these mixtures.
450

Combustion Velocity, m/s

400 350 300 250 200 150 100 50 0 0

20m and 80nm Al 4m and 80nm Al

20

40

60

80

100

Percent 80nm Al
Figure 12. Combustion velocity as a function of weight percent 80nm Al content for loose powder with 4 or 20 m Al and MoO3.

23

CHAPTER V DISCUSSION

5.1 Ignition Sensitivity The increased ignition sensitivity of mixtures with nanometer scale Al may be explained by the increased reactivity of nano-sized metal particles. Pantoya and Granier [16] showed through thermal analysis on nano and micron Al combined with MoO3 mixtures that the initiation mechanisms for the two particle length scales are very different. They showed that for micron composites, Al oxidation occurs after Al melting (660 C) and MoO3 sublimation (770 C) and in the solid-solid phase [16]. Ignition temperatures corresponding to micron composites were measured at roughly 1000 C and the diffusion mechanism is in the liquid-gas state [16]. Figures 7-9 show that only 10 wt % nano-Al content is required to reduce ignition delay times by two orders of magnitude. Enough energy is generated from the localized reaction between nano-Al and MoO3 to ignite neighboring particles. However, if the micron scale particles are too large (20 m) and only 10 % nano Al is within the matrix, enough heat is lost to the larger scale particles to prevent a self-sustained reaction. In this case, shortly after a localized ignition spot is formed, the reaction is extinguished. It is noted that Popenko et al. [18] similarly observed that if the nano-Al concentration in a mixture with micron scale Al powder is less than 10 %, combustion is difficult to initiate. The effective thermal conductivity of the composite may also influence ignition sensitivity. The effective thermal conductivity is a function of the thermal conductivity values of each component within the matrix, the volume fraction, and the 24

distribution of the matrix and dispersed phases(s). Hasselman and Donaldson [42] theoretically investigated the role of material distribution in the effective thermal conductivity of composites and found that the presence of an interfacial thermal barrier could have a significant effect on composite thermal conductivity. In this system, the Al2O3 shell encapsulating nano-Al particles could represent an interfacial thermal barrier. As localized Al oxidation reactions occur, the Al2O3 may provide enough thermal insulation to facilitate localized energy build up. When energy is constrained, heat losses associated with thermal diffusion away from the localized reaction are reduced. This reduction in heat losses effectively causes localized hot spots thermally insulated from micron-scale Al particles. Another factor that could contribute to the increased ignition sensitivity associated with nano-Al is the physical change of the alumina layer during heating. The oxide layer of the nano-Al particles is less than 5 nm thick and amorphous (Table 1). Upon heating, Trunov and co-workers [23] showed that the amorphous alumina shell undergoes a phase transition just below 500C to form -Al2O3. This phase change corresponds to an increase in density by about 20 % (from 3050 to 3660 kg/m3) [23]. This density increase will cause the aluminum core to become exposed to air within void pockets and surrounding MoO3 particles. Because this phase transition occurs at

temperatures corresponding to the ignition temperature of the nanocomposite, exposure of the solid-Al core may be a rate-determining step in the solid-solid diffusion mechanism of the nano-Al and MoO3 reaction. This step may not be as critical in the ignition of micron-composites because the aluminum surface particles of the aluminum core of a micron-Al particle make up a much smaller portion of the total aluminum 25

content. When considering the same amount of active aluminum for the nano-Al and micron-Al particles, nano-Al will have much more aluminum core surface area that can be exposed during the phase transition of the Al2O3 shell since there are so many more particles for the same amount of mass. The energy released from the nano-Al during this step would be much larger than the energy release of the micron-Al, which could greatly increase ignition sensitivity of these nanoparticles.

5.2 Combustion Velocity The combustion wave speeds shown in Figs. 10 and 11 increase from roughly 1 to 40 m/s as nanometer Al content increases. The most interesting behavior is observed in Fig. 11 in which a sharp transition from relatively slow to fast flame propagation occurs between 50 and 70 % nanometer Al content. A similar trend was previously observed in porous explosive charges and attributed to a transition from normal to convective burning [43]. When convective burning takes precedence over thermal conduction and radiation, energy and mass transfer in the burning zone are driven by gas jets that penetrate into the pores of the energetic material. Bobolev et al. [43] explain that in some cases penetration of the combustion into the pores is followed by the establishment of a regime of stationary convective burning whose rate substantially exceeds the normal burning rate. In an effort to identify this burning regime, an analysis of porous energetic material combustion under constant pressure conditions has lead to a stability criterion known as the Andreev number, An (Eq. (5.1)) [43]. This non-dimensional parameter is similar to

26

the Peclet number except tailored for reacting flow through porous media. An=

bUd h c p
kg

=const.

(5.1)

In this equation, b is the bulk density of the composite, U is the measured combustion wave speed, dh is the hydraulic pore diameter, cp is the heat capacity of the composite and

kg is the thermal conductivity of the gas. If this value exceeds a certain constant,
combustion penetrates into the porous structure and convective mechanisms dominate flame propagation. In making this calculation it is necessary to estimate the characteristic pore size which is termed the hydraulic pore diameter, dh, given by Eq. (5.2) [44].

dh =

4 Ao (1 )

(5.2)

In this equation is the bulk void volume, Ao is the specific surface area based on the solid volume and is calculated as the solid surface area divided by the solid volume (As/Vs), and (1-) is the solid volume fraction [44]. Table 2 shows the calculated values of the physical and thermal parameter for both the 4 and 20 micron containing bimodal mixtures. These calculations are based on the assumption of kg = 0.137 W/mK corresponding to air at an average temperature of 2000 K. For each estimate, the An number is significantly less than 1.0. Bobolev et al. [43] calculated critical An numbers between 3 and 10 and generalized that if the An > 6.0 combustion will penetrate into the pores and convective mechanisms will play the primary role in accelerating the flame front.

27

Table 2. Calculated thermal and physical parameters for all Al-MoO3 composites
For 80 nm Al mixed with 4 micron Al particles and MoO3
% nano Al content 0 10 20 30 40 50 60 70 80 90 100 (kg/m ) 2272 2270 2268 2266 2264 2262 2260 2258 2256 2253 2251
3

Cp (J/kgK) 885.4 884.4 883.4 882.5 881.5 880.5 879.5 878.5 877.5 876.5 875.5

Total Surface 2 Area (m ) 0.165 0.982 1.798 2.615 3.431 4.248 5.064 5.881 6.698 7.514 8.331

(1/m) 1.2678E-03 7.5389E-03 1.3810E-02 2.0081E-02 2.6352E-02 3.2623E-02 3.8894E-02 4.5165E-02 5.1437E-02 5.7708E-02 6.3979E-02

/(1) 1.98E-08 1.97E-08 1.96E-08 1.95E-08 1.94E-08 1.93E-08 1.92E-08 1.91E-08 1.90E-08 1.89E-08 1.87E-08

Hydraulic Pore Diameter (m) 5.27E-14 8.83E-15 4.80E-15 3.29E-15 2.50E-15 2.01E-15 1.68E-15 1.44E-15 1.26E-15 1.11E-15 9.99E-16

Andreev Number 3.24E-07 1.78E-07 2.83E-07 1.92E-07 1.33E-07 2.85E-07 3.19E-07 3.70E-07 3.93E-07 3.56E-07 5.44E-07

For 80 nm Al mixed with 20 micron Al particles and MoO3

% nano Al content 0 10 20 30 40 50 60 70 80 90 100 (kg/m ) 2278 2276 2274 2272 2269 2267 2264 2261 2258 2254 2251
3

Cp (J/kgK) 889.8 888.4 887.0 885.5 884.1 882.7 881.2 879.8 878.4 876.9 875.5

Total Surface 2 Area (m ) 0.033 0.863 1.692 2.522 3.352 4.182 5.012 5.841 6.671 7.501 8.331

(1/m) 2.5289E-04 6.6255E-03 1.2998E-02 1.9371E-02 2.5743E-02 3.2116E-02 3.8488E-02 4.4861E-02 5.1234E-02 5.7606E-02 6.3979E-02

/(1) 2.01E-08 2.00E-08 1.99E-08 1.98E-08 1.96E-08 1.95E-08 1.94E-08 1.92E-08 1.91E-08 1.89E-08 1.87E-08

Hydraulic Pore Diameter (m) 2.67E-13 1.02E-14 5.16E-15 3.45E-15 2.58E-15 2.06E-15 1.71E-15 1.46E-15 1.27E-15 1.12E-15 9.99E-16

Andreev Number

7.60E-08 6.89E-08 7.68E-08 1.53E-07 3.43E-07 6.26E-07 6.33E-07 5.90E-07 4.37E-07

The above analysis suggests that the transition from low to high combustion wave speeds may not result from a shift in the flame propagation mechanism. A better explanation for this behavior may be related to the ignition insensitivity of the micron-scale Al particles. Because the micron-scale particles require more time and higher temperatures to ignite, the nano-Al reactions may proceed too quickly to allow the micron-Al particles to participate in the reaction. In this way, reactants containing large amounts of micron-Al particles may experience significant incomplete combustion which would result in reduced combustion velocities. For mixtures with mostly nano-Al particles (70-90% nano Al), the micron-Al particles make up a significantly smaller portion of the volume and impede the nano-Al/ 28

MoO3 reaction much less. Channels of nano-Al and MoO3 exist throughout the powder or pellet, allowing the reaction to propagate without micron Al obstructions hindering the velocity. These channels allow the measured velocity to be the same as a mixture of pure nano-Al and MoO3 but may still result in incomplete reactions between micron Al and MoO3. To test the theory that incomplete combustion is responsible for the reduced velocities in Figures 10-12, a series of pressure measurements were performed using the pressure cell described previously. Figure 13 shows the peak pressure of both the 4 and 20 m Al loose powder mixtures as a function of percent nano-Al content. The pressure is displayed on a per unit mass basis because a slight pour density change occurred as the size distribution of the aluminum particles changed. The constant volume sample cup
35 30 Pressure Output, kPa/mg 25 20 15 10 5 0 0 20 40 60 80 100 Percent 80nm Al Content

20m and 80nm Al 4m and 80nm Al Calculated Pressure

Figure 13. Pressure output as a function of percent nano-Al content for loose powder AlMoO3 mixtures with 4m and 20m Al.

29

holds more material if composed of the more-dense micron particles. The sample amount slightly increased as a result, but, more importantly, the volume of the pressure vessel remained constant. No data points exist for the 0-20% nano-Al content due to the difficulty of igniting the mixture with the YAG laser. The maximum peak pressure of the powder samples increases as the amount of nano-Al in each mixture increases (Figure 13). The pressure increase corresponds linearly to the increase in nano-Al content. This trend suggests that the micron-Al particles do not contribute to raising the peak pressure. For example, assuming a complete reaction between all Al particles and MoO3, the maximum peak pressure for the mixture can be calculated assuming the peak pressure results from the rapid expansion of high temperature gasses present in the parr-bomb chamber under roughly adiabatic flame temperature conditions. Equation 4.3 is the ideal gas law, which assumes that the gas behavior at the flame temperature is ideal.

P=

mRT V

(4.3)

In this equation, P is the peak pressure, T is evaluated at the adiabatic flame temperature of the mixture 3200 C [1], which is sufficiently high enough to consider an ideal gas assumption. The gas constant (R) for air at 3200 C is used in conjunction with the volume (V) of the combustion chamber, 9.26cm3. The mass (m) of gas present in the chamber is estimated as 8.75 mg based on [1] which states that 25% of the products of this reaction are gaseous. With these values in Eq. (4.1), the maximum peak pressure for a complete reaction is 25.2 kPa/mg, and is shown in Fig. 13 as the dashed line. The measured peak pressures approach 25.2 kPa/mg only when a significant percent of nano-

30

Al is included in the mixture, indicating that the micron-Al particles may not be contributing to the overall reaction enough to raise the peak pressure to the theoretical value. Increased levels of nano-Al may also enhance the radiant heat transport through the mixture. Yang et al. [32] showed nano-scale Al particles absorb more energy compared to their micron scale counterparts. The increased levels of absorbed energy may generate a more intense radiation field and elevate the temperature of the preheat zone. Higher preheat temperatures will induce increased combustion velocities. If too few nano-particles are present in the composite, the thickness and intensity of this preheat zone will diminish and result in comparably slower combustion velocities. Still frame images and light traces captured during powder ignition experiments also complement the theory that micron scale particles are either not participating in the reaction or react much slower than the reaction between nano-Al and MoO3. The six frames of Figures 14-16 show the combustion of three different powder mixtures. The frames of Figure 14 show the reaction of 100% 80nm Al and MoO3.

Figure 14. Combustion of 100% 80nm Al and MoO3 loose powder mixture

31

The reaction appears to consume all particles, which rise into the air and convectively cool as smoke. More importantly, all of the particles seem to react at the same time, although a few get forced out onto the sample platform as seen in the third frame. This whole reaction is outside the range of the photodiode in as little as 9 ms.. A different looking reaction appears in Figure 15, which is a mixture of 10% 80nm Al and 90% 20 m Al with MoO3. The reaction of the nano Al and MoO3 can be seen in the first two frames with a convective plume similar to Figure 14. Many other particles can be seen radiating in these frames. The micron Al particles may only begin reacting during the nano-Al reaction with MoO3 and forced into the air while still radiating and reacting. These radiating particles appear to burn much slower and are

Figure 15. Combustion of loose powder Al and MoO3 mixture with 10% 80nm Al and 90% 20m Al

32

Figure 16. Combustion of 100% 4m Al and MoO3 loose powder mixture. apparent even after the nano-Al plume has disappeared. The time duration of these six frames is about 13 times the time duration of the frames of Figure 14; therefore, it can be seen that the micron particles react more slowly than the nano Al with MoO3. This finding is consistent with the peak pressure measurements which indicate that the micron particles do not contribute to increasing the measured peak pressure. The frames of Figure 16 show a reaction with 4 m Al and MoO3. This reaction also occurs slowly relative to the reaction in Figure 14, about 2.5 times as slow. The reaction spreads from the left to the right across the sample cup in the first three frames and sends a bright plume of radiating particles into the air. Radiating particles can still be seen floating in the air in the final two frames. It is apparent that the reaction of micron Al particles, even as small as 4 m, with MoO3 occurs much more slowly than the nano Al reaction. Products of a pellet reaction with 50% 80 nm Al and 50% 20 m Al mixed with MoO3 are shown in Figure 17. These micron particles were removed from the test apparatus after combustion. The surfaces of these particles are of both smooth and rough nature. The smooth sections are typically indicative of unreacted Al, as seen in Figure 1.

33

The rough sections, however, indicate aluminum that has reacted with oxygen. These SEMs show that micron Al particles in this mixture are not completely reacting, which supports the still frame images of Figures 15 and 16.

A.

B.

C. Figure 17. SEM images of products of 50% 80 nm Al and 50% 20 m Al pellet mixtures with MoO3

34

The results obtained for bimodal mixtures in a thermite composite are similar to results of bimodal Al mixtures reacting with air made by Popenko [18]. They suggest incomplete combustion for nano-Al concentrations less than 20 % [18]. This finding is consistent with the slower reacting (or incomplete combustion) micron Al particles observed in this study. Also, Dokhan [36] showed a plateau in burning performance for 70 % nano-Al concentration in bimodal Al mixtures added to AP. Our work suggests 70 % nano-Al concentration will optimize the combustion wave speed in thermites. The results presented here may have implications towards the use and handling of thermites. Nano-scale Al particles can be costly, significantly more so than micron scale particles. It may be advantageous to use mixtures of nano and micron scale material for large scale formulations. This work shows that ignition sensitivity is heightened by small additions of nano-Al to the mixture. However, what is gained in ignition sensitivity is sacrificed in performance through reduced velocities that result from incomplete (or significantly slower) micron-Al reactions.

35

CHAPTER VI CONCLUSIONS

The ignition delay time and combustion wave speed of thermite composites composed of Al and MoO3 were examined as a function of Al particle size distribution. Bimodal Al size distributions consisting of 80 nm combined with either 4 or 20 m particles showed increased sensitivity to ignition with only a 10 % concentration of nanoscale particles. The increased ignition sensitivity is explained by the solid-solid phase ignition mechanism associated with nano-Al particles compared with the liquid-gas phase mechanism associated with micron-Al particles. The nano-Al particles are more reactive and stimulate ignition two orders of magnitude faster than with purely micron-Al containing mixtures. Although the energy generated from the localized reaction between nano-scale Al and oxidizer is enough to initiate the reaction, in some cases the reaction is not self-sustaining. For example, with 10 % nano-Al particles combined with 20 micron particles the initiated reaction is quickly quenched as heat is lost to the surrounding media too quickly to permit a sustained reaction. This study indicates that at least 20 % nano-Al particles are required to ensure reduced ignition delay times and are on the same order as with mixtures containing 100 % nano-Al. The combustion velocity increases linearly with nano-Al content from roughly 1 to 40 m/s. This is consistent with prior investigations on bimodal Al size distributions concerning Al with air and Al as a propellant additive. Slow (and incomplete)

combustion of micron Al particles leads to the decrease of the combustion wave speed for mixtures in which the micron Al particles make up a large part of the volume. For 36

mixtures with small amounts of micron Al, the reaction speed is significantly increased since the nano Al can react with MoO3 in channels that exist around the micron particles.

37

CHAPTER VII IMPLICATIONS AND FUTURE RESEARCH

Research in nanotechnology has advanced in the past decade. Within the field of nano-energetic materials, research is still needed to help characterize the materials for many combustion and thermal properties. Safety, longevity, and reliability are all factors that are important in the use and predictability of these materials, and further research in these areas will expediate the use of nano-energetics in many applications.

7.1 Nano-scale Aluminum Properties Nano-aluminum obviously has striking combustion property differences from micron-aluminum, as seen in this work, but a potential for significant differences in its physical properties may also exist. One of these physical properties that has not been extensively studied is radiation absorbance. Nano-aluminum appears a very dark gray color, while micron-aluminum is light gray. This color difference shows optical properties of aluminum change in the visible light spectrum with decreased particle size, possibly due to dependent scattering. Groundwork has been laid on the potential for this property difference [32, 33, 34], but the range of wavelengths researched is not broad. Integrating spheres have been used for gaining reflectance information of aluminum surfaces [45] and could be very useful for the evaluation of powder aluminum samples. Lindseth et al. [45] experimentally determined that the rolling of aluminum surfaces can reduce the reflectivity of the surface by over 10%. Thermites and other

38

nano-aluminum mixtures are often ignited using laser irradiation, and the absorbance, transmittance and reflectance properties of nano-aluminum could explain which wavelengths are most effective in this ignition process. An important safety consideration of many materials, especially energetic materials, is the risk of dust explosions, to which even common grains are susceptible. The risk of micron-sized aluminum in regard to random dust explosions has been heavily documented, but due to its recent development, nano-aluminum risks in this area have not been studied. The enhanced ignition capabilities of nano-aluminum compared to micronaluminum could pose a much higher threat to explosion and must be assessed to sustain proper usage procedures. Nano-sized aluminum is much less dense than micron

aluminum in its powder form and can more easily be dispersed in air due to its increased surface area. The addition of nano-Al to explosives, for increased energy output, poses another significant risk that should be assessed. Kwok et al. [30] have shown that the addition of nano-scale aluminum to ammonium perchlorate decreases the minimum electro-static discharge ignition energy from greater than 156 mJ to 6 mJ. In order to safely handle nano-Al, more research is being done to quantify the risk of nano-Al dust explosions and the proper precautionary measures for prevention.

7.2 Mixing Techniques The enhanced performance of nano-composites over their micron counterparts is largely due to the superior mixing distribution of the fuel and oxidizing particles. In order to harness the full potential of these materials, techniques to produce optimum

39

mixing of these particles are necessary. Also, inconsistent performance of these materials that could hinder their reliability could be reduced through research in this area. Current mixing techniques utilize sonication of alcohols and other non-reactive solvents to break up particle agglomerations and create a homogeneous mixture of fuel and oxidizing particles. Research regarding mixing behaviors has begun [46], and sol-gel chemistry solutions through nano-structuring are also being investigated [47-49]. Mixing

techniques will continue to be an important factor in the development and production of nano-energetic applications in the future.

7.3 Preliminary Molybdenum Trioxide Study After completing the bimodal aluminum distribution study, a preliminary study was performed on the combustion effects related to environmental alterations of molybdenum trioxide. During lab operations, a color change was noticed in molybdenum trioxide nanoparticles that were exposed to light and the effects of the color change on combustion speeds were unknown. This drew the attention to what environmental

conditions caused this change and what other environmental conditions could cause the material to react differently. Metal oxides like molybdenum oxide have been known for over 40 years to exhibit photochromic properties [50-57]. Ultraviolet (UV) light has been shown to cause several chemical, mechanical, and electrical properties of metal oxides to change. Indium oxide thin films have been shown to become much more electrically conductive through exposure to UV radiation [55]. When in an oxygen-present environment,

40

amorphous zinc oxide thin films will crystallize due to UV irradiation [56]. Photodarkening in these same zinc oxide films has been attributed to photoreduction effects. Li has shown similar UV-induced color formation and photoreduction

observations in tungsten oxide nanoparticles, which are claimed to describe a change of the oxide from WO3 to W2O5 [58]. Molybdenum oxide also exhibits photochromic properties. S. K. Deb [57] reports the formation of color centers which result in a significant increase in optical density due to UV irradiation. He describes this color change as being due to an increase in oxygen vacancies in the lattice structure. He also describes a thermal bleaching process, which entails heating the sample to 300 C in the presence of oxygen. The bleached molybdenum oxide particles are rid of these color centers and do not form new color centers in the presence of UV irradiation. In the past ten years, new technologies have allowed the formation of nanoparticle molybdenum oxide (MoO3), which seem to have a stronger photochromic properties. Absorbance measurements by Li have shown

nanoparticle MoO3 to be 15 times more absorbent of UV irradiation than their bulk MoO3 counterparts. Raman spectroscopy has also been used to characterize MoO3 [59-60]. According to S. H. Lee [59], heat treatment of amorphous thin films, in a manner similar to the thermal bleaching described previously, causes alpha MoO3 crystal formation to occur. Raman spectroscopy experiments from Lee shown sharp peak formation previously not seen with the amorphous samples.

41

More information in this area of research is needed to describe variability and inconsistency seen in performance parameters, such as combustion rate and ignition sensitivity. Plantier has shown standard deviations of Al/Fe2O3 formulations to be as high as 15% of the mean combustion velocity [49]. Granier has shown ignition time and combustion speed standard deviations in Al/MoO3 formulations of greater than 20% of the mean values [61]. Although the ability of MoO3 optical properties to change through exposure to UV irradiation is known, little is known about how the combustion properties are affected by similar environmental factors. A change in combustion characteristics could lead to a greater knowledge of causes of variations in the performance of nano-composites. This information would lead to the development of more consistent nano-composites and expediate the use of environmentally responsible primer formulations. Therefore, the scope of this preliminary study was to evaluate how the combustion behavior of nanocomposite Al/MoO3 formulations is affected by MoO3 particles that have been altered through exposure to fluorescent light, UV irradiation and high relative humidity levels, common environmental factors which may change the combustion performance of these materials. The aluminum used in this study was 120 nm, and the same molybdenum oxide product from Climax was used as in the bimodal distribution study. This molybdenum oxide was tested in its original form as received from Climax and after a heat treatment of 400C. SEMs of the untreated and heat treated MoO3 are shown in Figure 18.

42

a.

b.

Figure 18. SEM micrographs of a. Untreated MoO3 and b. Heat treated MoO3 Powders were prepared in a process similar to the preparation process mentioned previously and were tested in an open channel setup with spark ignition. The

molybdenum oxide, both untreated and heat treated, was exposed to three different environmental conditions for up to 4 days before being mixed with the aluminum: UV light exposure, fluorescent light exposure, and a 99% relative humidity environment. Figures 19-21 show the combustion velocities as a function of exposure to fluorescent light, UV light, and high humidity levels.

43

500 450 400

Burn Velocity (m/s)

350 300 250 200 150 100 50 0 Untreated Heat Treated

20

40

60

80

10 0

Exposure to Fluorescent Light (hrs)

Figure 19. Burn rate of Al/MoO3 as a function of fluorescent light exposure

450 400 350

Burn Velocity (m/s)

300 250 200 150 100 50 0 0 20 40 60 80 100 Untreated Heat Treated

Exposure to UV (hrs)

Figure 20. Burn rate of Al/MoO3 as a function of UV light exposure

44

400 350 300 250 200 150 100 50 0 0 20 40 60 80 100 Untreated Heat Treated

Burn Velocity (m/s)

Exposure to 99% Relative Humidity (hrs)

Figure 21. Burn rate of Al/MoO3 as a function of 99% relative humidity The untreated MoO3 powder changed color from yellow to blue after both fluorescent and UV light exposure, which has been attributed to a desporption of oxygen from the molecules [57]. However, these types of exposure had little effect on the burn rate of the mixture. The white heat treated MoO3 did not change color after both light exposures, due to the differing crystal phase structure shown in Figure 18. Like the untreated MoO3, light exposure had little effect on the burn rate. Although light had little effect on the combustion performance for both MoO3 samples, exposure to high humidity levels drew a clear difference between the samples. The untreated MoO3 sample burned at speeds less than a meter per second after just one

45

day of exposure, which was probably due to water molecules that had absorbed onto the MoO3 particles. The heat treated MoO3 sample showed no change after two days

exposure and a moderate decrease thereafter. The heat treated MoO3 has not been thoroughly studied and could provide an alternative for untreated MoO3 in harsh environmental applications. Based on this preliminary study, it seems environmental factors can play a significant role in the performance of thermites. Increased humidity levels can reduce the combustion performance of thermites very quickly, an light exposure has the potential to decrease the performance over a longer period of time. In order to utilize these materials in ordinance applications, environmental factors must be addressed to accurately predict how these materials will perform. Future research could provide a more definite

correlation of the effects of these and other environmental factors on thermite materials.

46

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