224 Zhu Ji and Li Shufen

Propellants, Explosives, Pyrotechnics 24, 224226 (1999)

Aluminum Oxidation in Nitramine Propellant

Zhu Ji and Li Shufen* Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (People's Republic of China)

Oxidation von Aluminium bei Nitramintreibstoffen Trotz der zahlreichen Literaturzitate u ber die Oxidation von Aluminium beim Abbrand von Festtreibstoffen, konzentrieren sich diese chlich auf aluminiumhaltige KomposittreibArbeiten aber hauptsa stoffe. Wenig bekannt ist dagegen u ber die Oxidation von Aluminium bei Nitramintreibstoffen. Der Zweck dieser Kurzmitteilung ist nun, gliche Reaktionen des Aluminiums bei diesen Treibstoffen einige mo zu diskutieren.

base de nitramine Oxydation de l'aluminium dans les propergols a les nombreuses citations que l'on trouve dans la litte rature Malgre sur l'oxydation de l'aluminium lors de la combustion de propergols tudes se concentrent principalement sur des propergols solides, ces e base d'aluminium. En revanche, on canna t peu l'oxycomposites a base de nitramine. dation de l'aluminium dans les propergols a sente publication est donc de pre senter d'e venL'objectif de la pre actions de l'aluminium dans ces propergols. tuelles re

Summary
In spite of the numerous literature on the oxidation of aluminum in sold propellant combustion, these researches mainly focus on aluminum in AP-based composite propellant and little is known about aluminum oxidation in nitramine propellant. The purpose of this note is to discuss some possible reactions of aluminum in such circumstances.

sion: Aluminum in nitramine propellant may also be oxidized by nitrogen oxides. It is assumed that the reactions of interest are: 2 Al 3 NO ! Al2 O3 3y2 N2 2 Al 3 N2 O ! Al2 O3 3 N2 2 Al 3y2 NO2 ! Al2 O3 3y4 N2 2 Al 3 NO2 ! Al2 O3 3 NO 3 4 5 6

1. Aluminum Oxidation in AP Composite Propellant It is well documented now that oxidants of aluminum in AP composite propellant combustion are CO2 and H2O. An examination(1) of the combustion products of a typical nonaluminized propellant shows that the only substances capable of oxidizing Al to Al2O3 which are present in signicant quantities are CO2 and H2O. Consequently, reactions between aluminum and CO2, H2O are: 2 Al 3 CO2 ! Al2 O3 3 CO 2 Al 3 H2 O ! Al2 O3 3 H2 1 2

2. Aluminum Oxidation in Nitramine Propellant The most commonly used nitramines in solid propellant is HMX. Previous studies(2) on gas products of nitramine thermolysis show that nitrogen oxides such as N2O, NO, NO2 etc. have a high concentration in the gas composition. The result together with the fact that nitrogen oxides are excellent oxidizers at high temperature leads to the conclu* Corresponding author. # WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999

Table 1 contains the standard Gibbs free energies of formation Df Go m in the temperature range typical of propellant combustion (1000 K2300 K) for the reactants in reactions (1)(6). The data reported are from JANAF Thermochemical Tables(3). Molar Gibbs free energy changes Dr Go m for reaction (1) to (6) at various temperatures are calculated and shown in Table 2. From Table 2 it is immediately apparent that the Dr Go m for reactions (3)(6) are much more negative than Dr Go m for reactions (1) and (2), which means reactions between aluminum and nitrogen oxides are not only possible at the temperature range, but also more thermodynamically favorable than reactions between aluminum and CO2, H2O. Due to the lack of values for the rate parameters, the feasibility of reactions between aluminum and nitrogen oxides is estimated in this way. Since NO2, NO, N2O can oxidize Cu to CuO at 800 K(4), it stands to reason that a more reactive metal than copper, aluminum, should be easily oxidized to Al2O3 by nitrogen oxides at a much higher temperature about 2000 K, characteristic of aluminized propellant combustion. To further testify this estimation, the activation energies of reactions between Al and CO2, NO2, N2O are calculated. The rate-limiting step of reaction Al and CO2 to form Al2O3(5) is: Al CO2 ! AlO CO 7

0721-3115/99/03060224 $17.50:50=0

Propellants, Explosives, Pyrotechnics 24, 224226 (1999)

Table 1. Thermochemical Constants of Reactant T(K) a-Al2O3 (crystal) Al2O3 (liq)

Aluminum Oxidation in Nitramine Propellant

225

CO

Df Go m (kcal=mol) CO2

H2O

NO

NO2

N2O 37.391 45.996 54.392 59.350 62.630

1000 1500 2000 2300 2500

325.301 286.086 247.619 224.872 209.834

309.805 276.363 243.780 224.673 212.085

47.859 58.241 68.353 74.311 78.247

94.628 94.728 94.752 94.735 94.714

46.040 39.297 32.401 28.229 25.439

18.588 17.069 15.548 14.637 14.033

22.879 30.464 38.002 42.514 45.520

Table 2. Dr Go m of Reaction (1)(6) at Various Temperatures T(K) (1) (2) Dr Go m (kcal=mol) (3) (4) (5) (6)

1000 1500 2000 2300 2500

184.994 176.625 168.422 163.600 162.684

187.181 168.195 150.416 140.185 135.768

381.065 337.293 294.263 268.783 254.184

437.474 424.074 410.795 402.922 399.975

359.62 331.782 304.602 288.643 280.365

338.174 326.271 314.181 308.503 306.546

Similarly, rate-limiting steps of reactions between Al and N2O, NO2 are: Al NO2 ! AlO NO Al N2 O ! AlO N2 8 9

Semiempirical calculations are performed with AMl(6) Hamilton to determine the energy and SADDLE method(7) to locate the highest transition states of reactions (7)(9). The program we use is MOPAC 6.0(8). The aluminum atom is assumed to attack linearly, which means the angle of Al-O-X (X is C or N) is xed at 180 . The calculated heats of formation of reactants, products, transition states of reactions (7)(9) are listed in Table 3. The structures of transition states are seen in Figure 1. Reaction Between Al and CO2 According to the theory of molecular reaction dynamics, the activation energy of reaction (7) is the energy difference between the initial state and transition state. Therefore, the heats of formation of transition state (a), Al, CO2 and the activation energies are calculated at temperatures 1000 K, 1500 K, 2000 K, individually. The results are listed in Table 4.
Table 3. Df Ho m Species of the Three Reactions at Temperature 298.15 K (kcal=mol) Species D f Ho m

ngstro m Figure 1. Structures of transition states (bond lengths are in a and bond angles are in degree).

Because the AMl parameters have been optimized to reproduce properties of a group of compounds at the ground state, using the model on the intermediate sections on potential surface involves inaccuracy. Given the deciency above, the calculated activation energy is in good accordance with the experimental value of 3.0 kcal=mol(5) at temperature range from 1000 K to 2000 K.

Reaction Between Al and NO2, N2O In contrast to the highest transition state on the reaction path of Al and CO2, the energy of the highest transition state of reaction (8) is well below the energy of initial reactant, which implies the existence of a stable intermediate. Thus,
Table 4. Df Ho m of Transition State (a), Al, CO2 and Ea of Reaction (7) at Various Temperatures (kcal=mol) T(K) Df Ho m of Al D f Ho m of CO2 D f Ho m of (a) Ea

Reactant of Reaction (7) Transition State of Reaction (7) Product of Reaction (7) Reactant of Reaction (8) Transition State of Reaction (8) Product of Reaction (8) Reactant of Reaction (9) Transition State of Reaction (9) Product of Reaction (9)

0.34 6.40 2.10 62.9 26.4 8.63 107.9 65.2 18.9

1000 1500 2000

83.0 85.5 87.9

71.8 65.1 58.1

17.2 25.6 34.3

6.0 5.3 4.4

226 Zhu Ji and Li Shufen

Propellants, Explosives, Pyrotechnics 24, 224226 (1999)

the reaction between Al and NO2 process via a stable, energyrich intermediate which then travels over an energy barrier to form the product. The intermediate can pass through the transition state (b) without extra activation energy, which means the activation energy of the reaction between NO2 and Al is zero. The same argument can be applied to the reaction of N2O and Al. Hence, the activation energy at AMl level is zero for both reactions. It seems likely that this would continue to be true at higher level of theory. Because the reactions (8), (9) are highly exothermic, i.e. the heat of reaction is 89 kcal for reaction (8) and 54 kcal for reaction (9) at temperature 298.15 K. So even if a transition state is located by a higher level of theory, the geometry of this transition state should resemble the initial state not the nal state and the activation energy for both reactions would be low. Therefore, semiempirical quantum mechanism calculations further conrm that reactions between Al and nitrogen oxides are feasible in that there exists no high energy barrier on their reaction paths. N. Kubota(9) measured the primacy chemical components in the preparation zone of burning propellant containing 80% HMX at 20 atm. Its results were: 20.9% NO; 6.8% N2O; 9.8% N2; 18.1% CO; 7.3% CO2; 6.7% H2 and some hydrocarbon fragments. This indicates that in the combustion of nitramine propellant, nitrogen oxides have high concentration in combustion products. In such a condition, the reaction between aluminum and nitrogen oxide is capable of oxidizing Al to Al2O3. 3. Conclusion Both thermodynamic and kinetic investigations show nitrogen oxides are feasible to oxidize Al to Al2O3. Due to

high concentration of nitrogen oxides in the gas phase of nitrogen oxides in the gas phase of combustion nitramine propellant, it is very possible that nitrogen oxides play important roles in oxidizing aluminum in the combustion of nitramine propellant.

4. References
(1) R. S. Larson, ``Prediction of Aluminum Combustion Efciency in Solid Propellant Rocket Motors'', AIAA Journal 25 (1), 8291 (1987). (2) S. F. Palopoli and T. B. Brill, ``Thermal Decomposition of Energetic Materials 52. On the Foam Zone and Surface Chemistry of Rapidly Decomposing HMX'', Combustion and Flame 87, 4560 (1991). (3) D. R. Stull, H. Prophet, et al (Eds), ``JANAF Thermochemical Tables, 2nd ed., NSRDR-NBS 37, V. S. Government Printing Ofce, Washington D. C., 1971. (4) Z. L. Cao and Z. Y. Wang, (Eds), ``Handbook of Inorganic Chemical Reactions'' Hunan Science and Technology Publication Cooperation; 1985, pp. 50 (Chinese). (5) M. K. King, ``Modeling of Single Particle Aluminum Combustion'', AD-A050333. (6) M. J. S. Dewar, et al., J. Am. Chem. Soc., 107, 3902 (1985). (7) M. J. S. Dewar, et al., J. Chem. Soc. Faraday Trans. II; 3, 227 (1984). (8) J. J. P. Stewart, ``Mopac: A General Molecular Orbital Package, Version 6.0'' QCPE Program, 1990. (9) N. Kubota, ``Physicochemical Processes of HMX Propellant Combustion'', Nineteenth Symposium (International) on Combustion, The Combustion Institute 1982, [Proc.], pp. 775785.

Acknowledgement

The authors are grateful to the Chinese National Science Foundation for nancial support.

(Received June 19, 1998; Ms 21=98)