418–422, 2001
Translated from Fizika Goreniya i Vzryva, Vol. 37, No. 4, pp. 58–62, July–August, 2001.
Original article submitted April 11, 2000; revision submitted September 5, 2000.
The reactivity of aluminum powders is determined using the following parameters: the
temperature of the onset of oxidation, maximum oxidation rate, degree of conversion
(degree of oxidation) of aluminum, reduced (conditional) ratio of the thermal effect
to the weight increment. These parameters for estimating the activity of aluminum
powders were chosen from the results of nonisothermal oxidation of powders of various
particle sizes under conditions of programmed heating (oxidizer–air). In accordance
with the testing method proposed, the most reactive powder studied was STPA-4
ultrafine aluminum powder produced by electrical explosion of conductors.
TABLE 1
α, %
Sample No. Ssp (BET), m2 /g as , µm CAl0 , % ρ0 , g/cm3 Ton , ◦ C
up to 660◦ C up to 1000◦ C
1 0.15 80.0 99.5 1.60 920 0.65 52.2
2 0.38 9.0 98.5 0.87 820 2.5 41.8
3 5.91 Powder 96.0 0.315 580 8.0 40.5
4 11.00 0.20 86.0 0.21 555 39.9 69.3
5 12.10 0.18 94.8 — 548 39.4 45.0
6 7.80 0.28 91.0 0.13 560 23.9 74.3
7 16.00 0.13 89.0 0.11 540 50.1 78.6
ing did not exceed 3% and for sample No. 3 it did not Fig. 1. The oxidation of sample No. 7 proceeds in two
exceed 10%. For ultrafine aluminum powders (sample macroscopic stages: the first stage begins at a temper-
Nos. 4–7), the degree of conversion of aluminum before ature of 550◦ C and the second, less intense stage be-
the melting point was more than 20% (the maximum gins at 750◦ C and continues up to complete oxidation
value of 50.1% was obtained for sample No. 7). The of aluminum (more than 1000◦ C). For sample No. 2,
zone of the most intense oxidation was determined from it is possible to distinguish four stages of oxidation:
the TG curve (segments AB and A0 B0 in Fig. 1). The 1) 560–640◦ C; 2) 810–970◦ C; 3) 970–980◦ C; 4) 980◦ C
highest oxidation rate was observed for sample No. 4. and then until complete oxidation. The degrees of ox-
Sample Nos. 1, 2, 6, and 7 had comparable oxidation idation of sample Nos. 7 and 2 before melting were
rates, whereas intense oxidation of sample Nos. 1 and 2 50.1 and 2.5%, respectively. The first macrostage of
began at 920 and 820◦ C, respectively, and oxidation oxidation of sample No. 7 also includes several stages:
of sample Nos. 6 and 7 began at about 400◦ C below one can see four segments of increase and decrease in
than that for samples 1 and 2. The specific heat re- temperature on the DTA and DTG (differential ther-
lease S/∆m was determined by dividing the area of the mogravimetry) curves. Several powder fractions of close
peak of heat release (DTA curve) by the corresponding sizes are unlikely to burn out separately at T > 2000◦ C:
increase in sample weight (mg) (TG curve). The pa- the particle distribution of ultrafine aluminum powders
rameter S/∆m is maximal for sample No. 7 and more produced by electrical explosion is not tetramodal but
than four times larger than that for sample No. 1. bimodal (maxima are in regions 1–3 and 0.1 µm). We
can explain this unique phenomenon for ultrafine alu-
minum powders if we assume that combustion proceeds
under quasiadiabatic conditions. Apparently, an abrupt
DISCUSSION OF RESULTS
increase in temperature leads to the “actuation” of en-
dothermic processes, primarily, aluminum boiling, ni-
An analysis of the data given in Table 1 shows that
tration with further formation of AlN or AlON, and va-
in accordance with the testing parameters proposed, the
porization and dissociation of aluminum oxide. Thus,
most active powder is sample No. 7 (STPA-4 powder).
the heat expended in vaporization of 1 mole of Al2 O3
Derivatograms of sample Nos. 2 and 7 are shown in
Reactivity of Aluminum Powders 421
a CONCLUSIONS
REFERENCES
at the boiling point is equivalent to the amount of heat
released in the combustion of 1.2 moles of the metal in 1. P. F. Pokhil, A. F. Belyaev, Yu. V. Frolov, V. S. Lo-
oxygen under adiabatic conditions [1]. Consuming the gachev, and A. I. Korotkov, Combustion of Powdered
heat of the reactive system, endothermic processes de- Metals in Reactive Media [in Russian], Nauka, Moscow
crease the temperature, and this can occur several times (1972).
(for example, four times for sample No. 7). The self- 2. S. Sarner, Propellant Chemistry, New York (1966).
organization processes involved in the high-rate com- 3. V. G. Shevchenko, V. I. Kononenko, I. N. Latosh, et al.,
bustion of the powders occur via the feedback described. “Effect of the size factor and alloying on oxidation of
The possibility of endothermic reactions is confirmed by aluminum powders,” Fiz. Goreniya Vzryva, 30, No. 5,
chemical analysis and electron microscopy. In the pho- 68–71 (1994).
tographs shown in Fig. 2, the combustion products of 4. A. L. Breiter, V. M. Mal’tsev, and E. I. Popov “Means
sample No. 7 are submicron needles, and the combus- of modifying metallic fuel in condensed systems,” Fiz.
tion products of sample No. 2 are spheres. Thus, the Goreniya Vzryva, 26, No. 1, 97–104 (1990).
microstructure of the combustion products of STPA-4 5. V. G. Shevchenko, V. L. Volkov, V. I. Kononenko, et
ultrafine powder changed radically in comparison with al., “Influence of sodium and potassium polyvanadates
the initial powder, while the microstructure of the com- on aluminum-powder oxidation,” Fiz. Goreniya Vzryva,
bustion products of the commercial powder remained 32, No. 4, 91–94 (1996).
unchanged. Obviously, the appearance of combustion 6. F. Tepper, G. Ivanov, M. Lerner, and V. Davidovich,
products in the form of needles of submicron diameters “Energetic formulations from nanosize metal powders,”
results from participation of the gaseous phase in the in: Proc. Int. Pyrotechn. Seminars, No. 24, Chicago
formation of the final products [15]. (1998), pp. 519–530.
422 Il’in, Gromov, and Yablunovskii
7. V. F. Petrunin and L. D. Ryabev, “State and prospects 12. A. P. Il’in and L. T. Proskurovskaya, “Oxidation of met-
of the problem of ultradisperse (nano-) systems,” in: als in the ultradisperse state. Part II: High-temperature
Physicochemistry of Ultradisperse Systems: Proc. IV oxidation of aluminum: Size and structural factors,”
All-Union Conf., Moscow Eng.-Phys. Inst., Moscow Cherkassy (1988). Deposited at ONII TÉKhIM XII,
(1998), pp. 15–20. No. 905.
8. N. A. Yavorovskii, “Production of ultradisperse powders 13. M. M. Mench, K. K. Kuo, C. L. Yeh, and Y. C. Lu,
by electric explosion of conductors,” Izv. Vyssh. Uchebn. “Comparison of thermal behaviour of regular and ultra-
Zaved., Fiz., No. 4, 114–135 (1996). fine aluminum powders (Alex) made from plasma ex-
9. W. Wendtland, Thermal Methods of Analysis, Wiley, plosion process,” Combust. Sci. Technol., 135, 269–292
New York (1974). (1998).
10. A. P. Il’in, “On the excess energy of ultradisperse pow- 14. M. I. Lerner, “Control of the formation of ultrafine
ders produced by explosion of wires,” Fiz. Khim. Obrab. particles under conditions of electric explosions of con-
Mater., No. 3, 94–97 (1994) ductors,” Candidate’s Dissertation in Tech. Sci., Tomsk
11. V. G. Ivanov and O. V. Gavrilyuk, “Regularities of ox- (1988).
idation and self-ignition of electric explosive ultrafine 15. A. P. Il’in, G. V. Yablunovskii, A. A. Gromov, et al.,
metal powders in air,” Fiz. Goreniya Vzryva, 35, No. 6, “Combustion of mixtures of ultrafine powders of alu-
53–60 (1999). minum and boron in air,” Fiz. Goreniya Vzryva, 35,
No. 6, 61–64 (1999).