Propellants, Explosives, Pyrotechnics 27, 229 ± 240 (2002)
Characterization of Aluminum Nanopowder Compositions
Queenie S. M. Kwok, Robert C. Fouchard, Anne-Marie Turcotte, Phillip D. Lightfoot, Richard Bowes
and David E. G. Jones*
Canadian Explosives Research Laboratory, 555 Booth St., Ottawa, Ontario K1A 0G1 (Canada)
Summary
The thermal behaviour of two different Al nanopowders and a
micron-sized Al powder was studied using DSC, simultaneous
TG-DTA, and accelerating rate calorimetry (ARC). The results
show that the reactivity of Al powder increases as the particle size
decreases. The thermal stability of the smaller Al nanopowder
(Als) in water and in a humid atmosphere was determined using
ARC and TG-DTA, respectively. Atomic Absorption Spectro-
metry (AAS), X-Ray Photoelectron Spectrometry (XPS) and
Auger Electron Spectrometry (AES) were used to characterize
the surface chemistry of Alex. The outgassing behaviour for
mixtures of RDX and the various Al powders was investigated
using TG-DTA-FTIR-MS. Evolution of NO2 and N2O from a
chemical interaction between Al nanopowders and RDX was
observed. The effect of Als and Alex on the thermal stability of
TNT, RDX, Comp B, and AP was determined using ARC.
Addition of Als significantly lowered the onset temperature for
TNT and RDX decomposition. Electrostatic discharge (ESD)
sensitivities of Al nanopowders and their mixtures with TNT,
Comp B, RDX and AP were determined. The results show that
the AP/Als mixture is very sensitive to ESD. Standard dust
explosibility tests demonstrated that Alex is highly explosible.
1 Introduction
Aluminum (Al) powder is commonly added to explosives,
propellants and pyrotechnic compositions to improve their
performance. Al is known to add energy to the burning
reaction in propellants and to enhance the blast effect of
explosives, as well as their underwater performance.
Conventional weapons-grade Al powder is typically mi-
cron-sized. However, advances in metal processing tech-
nology have allowed sub-micron particles to become
commercially available. One such type of particle is the Al
powder Alex, produced by electro-exploded wire technol-
ogy(1). There are also other Al nanopowders produced by
plasma technology(2,3).
Because of its large surface area, Al nanopowder can
produce dramatic improvements in the performance of
some energetic materials. Incorporation of Al nanopowder
in propellants results in an increase in the burn rate(4±8).
Some researchers have reported enhancements in detona-
tion properties using Al nanopowders(4,9±14). The replace-
ment of conventional Al with nanometric Al has been
* Corresponding author; e-mail: djones@nrcan.gc.ca
¹ 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
229
shown to increase the detonation velocity and the detona-
tion pressure of some explosives(11,14).
Alex displays unusual behaviour in thermal tests(4, 15±25). It
was originally claimed that low-temperature exothermic
behaviour was related to some ™structural energy∫ due to
defects in the crystal lattice(4). However, a number of
subsequent studies have not found evidence for this internal
energy(5, 15, 17,26). Alex exhibits a strong exothermic peak in air
at temperatures that are 100 ± 200 8C below the melting
point of Al, due to the oxidation of the particles, a
phenomenon only observed with nanoscale powders. It
has been demonstrated that the particle size has an effect on
the reactivity of the Al powders(18,27). Mixtures of nano-
metric Al and nitramines showed a gas evolution in the
Vacuum Stability Test that was dependent on the particle
size(27).
The Canadian Explosives Research Laboratory (CERL)
has published results for Al nanopowders and their mixtures
with various explosives(21±25). This paper summarizes our
continuing work on the characterization of Alex and a
smaller Al nanopowder (Als) produced by plasma explo-
sion. The present paper includes the thermal properties of
various Al powders, the stability of Als in water and in a
humid atmosphere, the surface composition of Alex, the
outgassing phenomena for Alex, Als and their mixtures with
RDX, and the effects of Alex and Als on the thermal
stability of TNT, RDX, Comp B and AP. The explosibility of
dispersed Alex dust, and the electrostatic discharge (ESD)
sensitivity of Alex, Als and their mixtures with TNT, RDX,
Comp B and AP are also reported. Some comparisons were
made with micron-sized Al powder and paint-fine Al in
order to assess the effect of particle size of the Al powders.
2 Experimental
2.1 Materials
Als, Alex, H-15, TNT, RDX, Comp B, AP, mixtures of
Comp B/Alex and Comp B/Als (90 : 10) were obtained from
the Defence Research Establishment Valcartier (DREV).
Als was produced by Tekna Plasma System Inc.(3) and a
mean particle size of 90 nm was given by DREV. Alex was
manufactured by Argonide Corporation(1), and has a
reported mean particle size of 180 nm(28). For H-15, a
0721-3113/02/2703/0229 $ 17.50+.50/0
230 Kwok, Fouchard, Turcotte, Lightfoot, Bowes, Jones
particle size of about 12 mm was provided by DREV. An
additional sample of Alex was received directly from the
manufacturer (Argonide Corporation). Paint-fine Al man-
ufactured by Carlfors Bruk was provided by Orica Canada Inc.
The chunk samples of Comp B, Comp B/Alex and Comp
B/Als mixtures were ground to powders using an IKA model
A10 analytical mill. RDX was dried at 65 8C for a day before
use. Other mixtures of Al powders with TNT, RDX, Comp B
or AP were prepared at CERL for the outgassing, the
thermal stability and the electrostatic sensitivity studies.
2.2 DSC
A TA 5200 Thermal Analysis System with a 2910 DSC
module was used for the thermal studies of Al nanopowders
in air. Al pans containing 5.0 mg of samples were heated
from 300 or 400 to 600 8C at 0.5 8C min 1. Experiments were
carried out in a dry air purge at 50 mL min 1. The DSC was
calibrated for heat flow(29) and temperature with SRM
standards indium, lead and zinc(30).
2.3 TG-DTA-FTIR-MS
A TA 5200 Thermal Analysis System with a simultaneous
TG-DTA 2960 module was used for assessing the thermal
behaviour of Al powders in air and nitrogen. Sample and
reference material (Pt foil) of 10 mg were placed in alumina
pans and heated at 10 8C min 1 from 30 to 1200 8C. TG mass,
DTA baseline and temperature calibrations(30) were per-
formed prior to the experiments.
For the outgassing experiments, the TG-DTA was
interfaced to a Bomem MB100 FTIR and a Balzers
Thermostar GSD300 Quadrupole MS. The TG-DTA-
FTIR-MS data were acquired simultaneously to study the
thermal behaviour and to identify the gases evolved by the
samples. Samples and reference (Pt foil) of 14 ± 25 mg were
placed in alumina pans, heated at 5 8C min 1 to 120 8C, and
then held isothermally for 40 min in helium.
2.4 ARC
The ARC is a commercial automated adiabatic calori-
meter distributed by Arthur D. Little Inc. Samples of about
0.5 or 1.0 g were placed in lightweight spherical titanium
vessels. Unless specified otherwise, the ARC experiments
were started at ambient pressure of air and at an initial
temperature of 100 8C. The standard ARC procedure of
™heat-wait-search∫ was used(31±32).
2.5 ESD Sensitivity
ESD sensitivities of Alex and Als, and their mixtures with
TNT, Comp B, RDX and AP were determined using an ESD
apparatus manufactured by Franklin Applied Physics. The
Propellants, Explosives, Pyrotechnics 27, 229 ± 240 (2002)
apparatus is described elsewhere(33). The ESD tests were
performed with both open and closed sample containers.
The limiting energy for the ESD initiation was determined
by subjecting the sample to sparks of varying energies. A
positive reaction was defined when the sample burned
completely.
2.6 Dust Explosibility Tests
The measurements of maximum explosion pressure
(Pmax), maximum rate of pressure rise ((dP/dt)max) and
limiting oxygen concentration (LOC) of Alex were con-
ducted in a stainless steel, spherical vessel (Siwek appara-
tus), according to standard procedures(34). The minimum
ignition energy (MIE) tests were conducted using a device
known as the MIKE 3, manufactured by Adolf Kuhner AG
(Switzerland).
2.7 Surface Characterization
A UNICAM 929 Atomic Absorption Spectrometer
(AAS) was used to analyze the amount of Al in Alex. A
PHI-5600 X-Ray Photoelectron Spectrometer (XPS) and a
PHI-600 Auger Electron Spectrometer (AES) were also
used to characterize the surface chemistry of Alex.
3 Results and Discussion
3.1 Thermal Behaviour of Al Nanopowders
The TG-DTA results for Als in air are shown in Figure 1.
An exotherm was observed at an onset temperature of
430  5 8C. The onset temperature is the temperature at
which a deflection from the established baseline is observed.
This exotherm corresponds to a 23  1% mass gain observed
on the TG curve between 430 and 550 8C. An enthalpy
change of 5.5  0.2 kJ g 1 was obtained from DSC measure-
ments (Figure 2).
As shown in Figure 3, no exotherm and mass gain were
observed for Als in nitrogen before 550 8C. Therefore, the
exotherm and the mass gain observed between 430 and
550 8C in air were due to the oxidation of Als:
4 Al(s) ‡ 3 O2(g) ˆ 2 Al2O3(s) (1)
The expected mass gain for Reaction (1) is 89%. There-
fore, the 23  1% mass gain obtained from Als in air implies
that approximately 26% of Als was oxidized to Al2O3
between 400 and 550 8C. The remaining 74% of the sample
corresponds to the unreacted Als, as well as the Al oxide in
the original sample. The melting of Al near 660 8C observed
from Als in air (DTA curve in Figure 1) indicates that an
unreacted Al core remained in Als after the early oxidation.
A second mass gain was observed from Als in air above
550 8C (Figure 1). This mass gain may be due to a second
Propellants, Explosives, Pyrotechnics 27, 229 ± 240 (2002) Characterization of Aluminum Nanopowder Compositions 231

Figure 1. TG-DTA results for various Al powders heated in air at 10 8C min 1

Figure 2. DSC results for various Al powders heated in air at 0.5 8C min 1

stage of oxidation (Reaction (1)) and/or a nitridation of the
unreacted Al core, which is described as follows:
2 Al(s) ‡ N2(g) ˆ 2 AlN(s) (2)
The second reaction had a mass gain of 27  1% up to
1200 8C. However, the baseline had not recovered at
1200 8C, which implies the reaction was not complete at
1200 8C.
The TG-DTA results for Als in nitrogen show about 33%
mass gain, which corresponds with a broad exotherm split by
the melting of Al near 660 8C (Figure 3). The mass gain
between 550 and 1200 8C is slightly higher in nitrogen than in
air. A possible explanation for the lower mass gain in air is that
an alumina barrier is formed on the outside layer of the Al
particle, hindering further reaction of the remaining Al core.
The TG-DTA and DSC results for Alex received from
DREV are shown along with those for Als in Table 1 and
Figures 1 ± 3. The oxidation of Alex (DREV) has a higher
onset temperature, a lower mass gain and a lower enthalpy
change compared to Als. No oxidation was observed from
H-15 before 790 8C.
The TG-DTA and DSC results suggest that Als is more
reactive than Alex in air. The two nanopowders differ in
their particle sizes and the smaller nanopowder (Als)
possesses larger surface area. Additionally, the differences
in the reactivity of Al nanopowders may be due to the
different thickness of the oxide layer. As compared in
Table 1 and Figure 2, a different sample of Alex received
directly from Argonide exhibits an enthalpy change that is
70% higher than that obtained for the DREV sample. The
observed differences between the two samples of Alex may
232 Kwok, Fouchard, Turcotte, Lightfoot, Bowes, Jones Propellants, Explosives, Pyrotechnics 27, 229 ± 240 (2002)

Figure 3. TG-DTA results for Als and Alex heated in nitrogen at 10 8C min 1

Table 1. Comparison of DSC and TG-DTA results for various Al powders in air
Sample DSC TG-DTA
To/8C DH/kJ g 1
Dm% To/8C A/8C min mg 1
Dm1% Dm2%
Als 399 5.5 32 430 4.3 23 27
Alex ( DREV ) 460 3.9 25 475 4.0 20 38
Alex ( Argonide) 478 6.6 35 ± ± ± ±
H-15 ± ± ± 790 0.2 11 ±
Paint-fine Al 462 7.8 37 ± ± ± ±

Figure 4. ARC results for Als starting at 0.11 MPa of air

be due to variations in thickness of the oxide layer that result
from differences in the aging of the two samples, i.e.
variations in exposure to air and moisture.
The thermal behaviour of Als in ambient and super-
ambient pressures of air was studied using ARC. An
exotherm, which is defined as a self-heating rate greater
than 0.02 8C min 1, was detected between 110 ± 112 8C
(Figure 4). No other exotherm was detected up to 400 8C.
However, the decrease in pressure (Figure 4), which
corresponds with the depletion of oxygen (and possibly
nitrogen), indicates an oxidation (and possibly nitridation)
of Als. The residual pressure, which is the pressure recorded
after the system was allowed to cool to room temperature,
was 0.27 MPa (Table 2). The higher value for the residual
Propellants, Explosives, Pyrotechnics 27, 229 ± 240 (2002) Characterization of Aluminum Nanopowder Compositions 233

Table 2. Comparison of ARC results for Als, Alex and mixture of Als/H2O
Sample Initial P/MPa Residual P/MPa(a) Mass/g Mass gain% To/8C Rmax/8C min 1

Als 0.11 0.27 1.0 0.2 110 0.02

0.72 0.60 1.0 1.0 105 0.04
Alex(22) 0.11 0.11 1.0 0.15 290 0.02
0.72 0.68 0.5 0.45 150 0.02
Als/H2O (10 : 1) 0.72 2.0 1.1 1.4 32 5.0(b)
(a)
 25 8C
(b)
Automatic termination of experiment

pressure and the mass loss suggest the production of gases as
a result of an outgassing. The outgassing behaviour of Als
will be discussed later in this paper.
In the ARC experiment starting at 0.72 MPa of air, an
exotherm was detected at 105 8C and this exotherm
continued until the run was stopped manually at 210 8C.
This exotherm has a −true× onset temperature (To) of
95  10 8C, determined by extrapolating the self-heating
rate to 0 8C min 1. Therefore the oxidation of Als may occur
before 100 8C at higher pressures of air. Previous ARC
results for Alex show that no exotherm was detected below
150 8C from experiments starting at ambient pressure and
0.72 MPa of air (22). Therefore, Alex has a higher To of
oxidation than Als.
3.2 Surface Characterization of Alex
A concentration of 87.14  0.03 mass% of Al was
obtained from an AAS analysis of Alex. The AAS results
indicate that Alex contains approximately 13 mass% of
oxide layer. The surface characterizations of Alex using XPS
and AES indicate the presence of pure metallic Al on the
surface; however, most of the Al on the surface is mixed with
oxygen, carbon and nitrogen. The XPS results indicate that
Alex has a hydrated oxide layer which also contains sorbed
hydrocarbon vapor, oxy-carbon and oxy-nitrogen species. A
thickness of about 10 nm was obtained for the oxide layer.
The mean particle size of Alex is approximately 180 nm.
Additionally, appreciable AlN was detected at/near the
surface of Alex.
3.3 Stability of Als in Water and in a Humid Atmosphere
The ARC results for a mixture of Als/H2O (10 : 1) are also
shown in Table 2. An exotherm was detected at 32 8C. The
experiment was stopped automatically at 48 8C, when the
self-heating rate exceeded the automatic termination
threshold (5 8C min 1). This exotherm may result from a
reaction between Al and water to form Al2O3 or Al(OH)3.
The reactivity of Al nanopowder with water may cause
aging of Al nanopowder. As discussed earlier, DSC studies
have demonstrated that the reactivity of Alex in air depends
on the aging of the material (Section 3.1). To further study
the aging of Al nanopowder, wetted samples of Als were
prepared by placing Als in a bell jar at a relative humidity
> 90% at room temperature. TG-DTA experiments were
conducted on the wetted samples of Als in air to determine
the Al2O3 or Al(OH)3 formation from a reaction with water.
As shown in Figure 5, a decrease of the mass gain and the
peak area between 430 and 550 8C was observed after Als

Figure 5. TG-DTA results for aged Als heated in air at 5 8C min 1

234 Kwok, Fouchard, Turcotte, Lightfoot, Bowes, Jones
had been exposed to this humid atmosphere for about 47
days. This decrease in the mass gain and the peak area, as
well as the presence of white and light grey powders in the
wetted Als prior to the TG-DTA experiments, suggest that
Al2O3 or Al(OH)3 was formed from exposure to moisture.
Als was completely reacted in 74 days, i.e. no further mass
gain in the TG study (Figure 5). No significant change in
mass gain was obtained from Als exposed to dry air for up to
62 days. A preliminary aging study conducted at 40 8C
showed that Als reacted completely in humid atmosphere in
less than three days.
3.4 Outgassing Studies
Mixtures of nanometric Al powder and nitramines
showed a gas evolution in the Vacuum Stability Test that
was dependent on the particle size(27). Chemical interaction
between Alex and RDX above 100 8C has been reported(23).
In this study, the outgassing behaviour of mixtures of RDX
with Als and micron-sized Al powders was investigated
using TG-DTA-FTIR-MS. The outgassing experiments
Figure 6. (a) TG; (b) FTIR; (c) MS results for RDX/Als heated in helium at 5 8C min
Propellants, Explosives, Pyrotechnics 27, 229 ± 240 (2002)
were also performed on the individual components, to
distinguish between the outgassing behaviour due to each
component and the interaction between the Al powders and
RDX.
Example plots for the outgassing experiments, using the
RDX/Als mixture, are shown in Figure 6. The TG curve and
the sample temperature were plotted against time in
Figure 6 (a). The absorbance (A) versus time for the
evolved gases detected by FTIR are shown in Figure 6 (b).
The MS data are presented as ion current versus time for the
selected mass fragments (Figure 6 (c)). The results obtained
for Als, Alex, H-15 and RDX are summarized in Table 3.
No significant mass loss and no evolved gases were
observed for H-15 and RDX. In contrast, mass losses of
0.98  0.07 and 0.46  0.05% were obtained for Als and
Alex, respectively. The FTIR results show that the desorbed
species were CO2 and H2O. Evolution of H2O (m/z 18) was
also detected by the MS. By comparing the mass losses of the
two Al nanopowders, Als seems to desorb more than Alex.
Therefore, the adsorption of H2O and CO2 is particle size
dependent, with more being adsorbed as the particle size
decreases.
1
to 120 8C and isothermal 40 min
Propellants, Explosives, Pyrotechnics 27, 229 ± 240 (2002) Characterization of Aluminum Nanopowder Compositions 235

Table 3. Summary of outgassing studies

Sample Mass/mg TG mass loss%(a) FTIR results 104 N2O/A mg 1
MS results(b)
RDX 20 0.08  0.05 nd ± nd
H-15 20 0.05  0.05 nd ± nd
Alex 20 0.46  0.05 H2O, CO2 ± m/z 18
Als 14 0.98  0.07 H2O, CO2 ± m/z 18
RDX/H-15 25 0.09  0.04 nd ± nd
RDX/Alex 25 0.55  0.04 N2O, NO2, HCHO, H2O, CO2 0.88 m/z 18, 29, 30, 44
RDX/Als 20 1.25  0.05 N2O, NO2, HCHO, H2O, CO2 2.1 m/z 18, 29, 30, 44
Pre-dried RDX/Als 20 0.84  0.05 N2O, NO2, HCHO, H2O, CO2 1.2 m/z 18, 29, 30, 44
Pre-wet RDX/Als 20 1.68  0.05 N2O, NO2, HCHO, H2O, CO2 2.8 m/z 18, 29, 30, 44
Pre-wet/pre-dried RDX/Als 20 1.03  0.05 N2O, NO2, HCHO, H2O, CO2 1.7 m/z 18, 29, 30, 44
(a)
mass loss at 50 min; the uncertainty of the value represents the TG baseline drift
(b)
m/z 18 ˆ H2O; m/z 29 ˆ H2CO; m/z 30 ˆ N2O, NO2, HCHO; m/z 44 ˆ CO2, N2O
nd ˆ not detected

The outgassing results for the mixtures of RDX and
various Al powders (50 : 50) are compared in Table 3. Mass
losses of 1.55 and 0.55% were obtained for RDX/Als and
RDX/Alex mixtures, respectively. The estimated mass
losses, which are calculated using the TG results for the
neat components, are 0.74 and 0.34% for the RDX/Als and
RDX/Alex mixtures, respectively. Since the observed mass
losses exceeded the expected values from the individual
components, the Al nanopowders appear to interact chemi-
cally with RDX. Evolution of N2O, NO2, and H2CO was
detected by FTIR and the MS starting at about 70 8C. Since
these gases were not observed from neat RDX or from Al
nanopowders, they were generated from the chemical
interaction between Al nanopowders and RDX. As shown
in Table 3, the concentration of N2O evolved from the RDX/
Als mixture is higher than that from the RDX/Alex mixture.
Apparently, the interaction of Al nanopowder with RDX is
particle size dependent. No such interaction was observed
from the mixture of RDX and H-15.
The effect of water on the chemical interaction of Als and
RDX was investigated by conducting outgassing experi-
ments on: (i) pre-dried, (ii) pre-wet and (iii) pre-wet/pre-
dried RDX/Als mixtures. The samples were dried at 85 8C
for 2 hours in the TG-DTA using a helium purge. The wetted
samples were prepared by placing the mixtures in a bell jar at
a relative humidity > 90% for 24 hours. The results for the
treated RDX/Als mixtures are included in Table 3. The
same gases were detected, but they occurred at different
levels from the treated samples. The concentration of N2O
was highest in the pre-wet mixture, and lowest in the pre-
dried mixtures. The presence of water on the surface of the
samples may enhance the interaction between Als and
RDX. Although pre-drying reduced the outgassing, it did
not prevent the occurrence of such interaction. Hence, the
presence of water is not necessary for outgassing to occur.
3.5 Effect of Al Nanopowders on Explosives
The results for a typical ARC experiment, using 0.5 g of
TNT/Als (70 : 30) mixture, are illustrated in Figure 7. An
exotherm was detected with a To ˆ 183  9 8C. The run was
stopped automatically at about 210 8C, when the self-
heating rate exceeded 0.2 8C min 1. Figure 8 shows a plot

Figure 7. ARC results for TNT/Als mixture (T and P vs. time)

236 Kwok, Fouchard, Turcotte, Lightfoot, Bowes, Jones Propellants, Explosives, Pyrotechnics 27, 229 ± 240 (2002)

Figure 8. ARC results for TNT/Als mixture (ln(Rate) vs. 1/T)

of ln(Rate/8C min 1) against 103 K/T. From the slope and the
intercept of the curve, values of E ˆ 157  4 kJ mol 1 and
ln(Z/min 1) ˆ 37  1 were obtained, where E and Z are
respectively the activation energy and the pre-exponential
factor for the decomposition of the TNT/Als mixture.
As shown in Table 4, the addition of Als and paint-fine Al
lowered the onset temperature of the TNT decomposition
by 40 and 20 8C, respectively. E, Z and the rate constant (k)
for the decomposition of the TNT/Als and TNT/paint-fine
Al mixtures are significantly different from the other
compositions (Table 4 and Figure 9). The k values were
calculated using the kinetic parameters in Table 4. The
addition of Als or paint-fine Al significantly lowered the
onset temperature and increased the rate of the thermal
decomposition of TNT. In contrast, H-15 had no effect on
the decomposition of TNTand the effect of Alex was only to
increase the rate of reaction slightly.
The results for RDX and its mixtures with Als and Alex
are compared in Table 4 and Figure 10. The addition of Als
decreases the onset temperature of the RDX decomposition
by  70 8C (Table 4). The kinetic parameters and the rate
constant for the decomposition of the RDX/Als mixture are
significantly different from those for neat RDX (Table 4 and
Figure 10). The lower onset temperature and the higher rate
constant for the decomposition of the RDX/Als mixture
suggest a different decomposition mechanism from that of
RDX alone or for the RDX/Alex mixture. With the neat RDX
and the RDX/Alex mixture, the decomposition occurred
with RDX in the liquid phase, while Als reacted with RDX
below the melting point. Comparing the onset temperatures
of the same types of samples with different mass, no mass
effect was observed for either RDX or RDX/Als mixtures.
As shown in Table 4, the addition of Als, Alex, H-15 and
paint-fine Al had little effect on the thermal decomposition

Table 4. Comparison of ARC results for various formulations

Sample Mass/g To/8C Residual P/MPa(a) E/kJ mol 1
ln( Z/min 1)
TNT 0.25 220  3 0.2 459  18 107  5
TNT/Als (70 : 30) 0.51 183  9 0.2 157  4 37  1
TNT/Alex (70 : 30) 0.30 223  4 0.2 415  21 97  5
TNT/H-15 (70 : 30) 0.30 224  6 0.3 480  23 112  5
TNT/paint-fine Al (70 : 30) 0.30 198  3 0.2 258  27 62  6
RDX 0.2 183  5 0.2 548  111 139  28
0.4 193  4 0.1 918  10 232  8
RDX/Als (80 : 20) 0.5 120  10 0.4 102  4 25  1
1.0 119  8 0.4 123  4 32  1
RDX/Alex (80 : 20) 0.2 172  5 0.2 380  138 97  25
Comp B 0.20 155  7 0.3 178  1 46  1
Comp B/Als (90 : 10) 0.52 152  4 0.2 184  5 48  1
Comp B/Alex (90 : 10) 0.20 155  7 0.4 146  3 37  1
Comp B/H-15 (90 : 10) 0.31 160  6 0.3 216  18 56  5
Comp B/paint-fine Al (90 : 10) 0.30 163  5 0.3 216  3 56  1
AP 0.50 173  2 0.4 138  2 32  1
AP/Als (80 : 20) 1.0 167  13 0.1 163  13 39  1
AP/Alex (80 : 20) 0.50 184  1 0.2 248  4 61  1
(a)
 25 8C
Propellants, Explosives, Pyrotechnics 27, 229 ± 240 (2002)
Figure 9. Comparison of rate constants for TNT formulations
Figure 10. Comparison of rate constants for RDX formulations
of Comp B, in terms of both onset temperature and kinetic
parameters.
The ARC results in Table 4 and Figure 11 summarize the
effect of Al nanopowders on the thermal decomposition of
AP. There are insignificant differences between To of
decomposition for neat AP, and its mixtures with Als and
Alex, when the uncertainty of the values are considered
(Table 4). However, the addition of Als and Alex seems to
slightly increase the rate of AP decomposition (Figure 11).
Overall, Als has a greater effect on the thermal decom-
position of TNT and RDX than Alex. Als lowers the onset
temperature by 40 to 70 8C. It also significantly increases the
rate of decomposition. The addition of Als has a huge effect
on the thermal stability of RDX, therefore a large quantity
of RDX/Als mixture may react at a very low temperature
during production.
Characterization of Aluminum Nanopowder Compositions 237
3.6 ESD Sensitivity
The ESD sensitivities of Als, Alex, TNT, RDX, Comp B,
AP, and their mixtures were determined, and are summa-
rized in Table 5. No ignition was obtained when Als was
placed in a closed sample container and subjected to single
sparks of 25 kV. Hence, the limiting energy is greater than
156 mJ (Table 5). However, when Als was placed in open
containers, it ignited at a charge energy of 6 mJ. Compared
to Alex, which has an ESD limiting energy > 156 mJ, Als is
more electrostatically sensitive than Alex. The ESD
sensitivity of the Al nanopowder increases as the particle
size decreases, because the smaller Al nanopowder (Als) is
more easily dispersed and has a greater surface area.
For the TNT/Als and Comp B/Als mixtures, no ignition
was observed at a charge energy of 156 mJ. By contrast, the
238 Kwok, Fouchard, Turcotte, Lightfoot, Bowes, Jones Propellants, Explosives, Pyrotechnics 27, 229 ± 240 (2002)

Figure 11. Comparison of rate constants for AP formulations

Table 5. Summary of ESD results pressure rise ((dP/dt)max), size-normalized rate of pressure
Sample ESD ignition energy/mJ rise (KSt), limiting oxygen concentration (LOC) and
minimum ignition energy (MIE) for Alex. Values for each
Closed container Open container of these parameters are given in Table 6. Alex can be
Als > 156 6 classified as being among the most violently reactive (St 3)
Alex > 156 > 156 dusts. It also has a very low MIE. Alex clearly presents a dust
TNT > 156 > 156 explosion hazard and appropriate caution must be exercised
TNT/Als (70 : 30) > 156 > 156
TNT/Alex (70 : 30) 156 > 156 in handling this material.
RDX > 156 > 156
RDX/Als (80 : 20) 100 25
RDX/Alex (80 : 20) > 156 > 156 4 Conclusions
Comp B > 156 > 156
Comp B/Als (90 : 10) > 156 > 156
Comp B/Alex (90 : 10) > 156 > 156 TG-DTA and DSC results show an early oxidation of Al
AP > 156 > 156 nanopowders between 430 and 600 8C. The reactivity of Al
AP/Als (80 : 20) 1 6 powders in air depends on the particle size and the history of
AP/Alex (80 : 20) 100 ± the sample. Als is very reactive with water, showing
exothermic activity at 32 8C from an ARC experiment
ESD results show that Als sensitizes RDX and AP to conducted on a mixture of Als/H2O. Aging of Als was
electrostatic discharge. The RDX/Als mixture would not be observed for samples exposed to humid atmosphere at room
described as particularly ESD sensitive. The ESD energy of temperature for more than 47 days, and Als was completely
the AP/Als mixture is similar to that of KDNBF (potas- reacted in 74 days.
siumdinitrobenzofuroxane), which is a primary explosive A value of approximately 13 mass% of aluminum oxide
sensitive to impact, friction and ESD(33). Alex also appears was obtained from the AAS analysis for Alex. The XPS and
to sensitize AP to ESD; however, the material would still not AES results indicate the presence of pure metallic alumi-
be described as very ESD sensitive. nium on the surface; however, most of the aluminum on the
surface is the Al3‡ species, mixed with oxygen, carbon and
nitrogen. A thickness of about 10 nm was obtained for the
3.7 Dust Explosibility oxide layer. Appreciable AlN was also detected at/near the
surface of Alex.
Explosibility tests were conducted to measure the The outgassing studies using TG-DTA-FTIR-MS, show
maximum explosion pressure (Pmax), maximum rate of desorption of H2O and CO2 from Al nanopowders.

Table 6. Alex dust explosibility parameters

1 1
Pmax/Mpa (dP/dT )max/MPa s KSt/MPa m s Dust Class LOC/% MIE/mJ
0.94 118.5 32.2 St 3 5 1±3
Propellants, Explosives, Pyrotechnics 27, 229 ± 240 (2002)
Chemical interactions between these Al nanopowders and
RDX, generating NO2 and N2O, were observed starting at
70 8C. Both the adsorption of H2O and CO2, and the
chemical interaction with RDX increase as the particle size
of Al nanopowder decreases.
The effects of the addition of Al nanopowder on the
thermal stability of TNT, RDX, Comp B, and AP were
determined using ARC. Als has a greater effect on the
thermal decomposition of TNT and RDX than Alex. Als
lowers the onset temperature by 40 to 70 8C. It also
significantly increases the rate of decomposition.
Als and Alex appear to sensitize some energetic materials
to ESD. The AP/Als mixture is very sensitive to ESD.
Standard dust explosibility tests demonstrated that Alex is a
highly explosible dust.
5 References
(1) Internet WEB Site: ARGONIDE NANOMETAL TECH-
NOLOGIES hwww.argonide.comi
(2) Internet WEB Site: TETRONICS LTD. hwww.tetronics.comi.
(3) Internet WEB Site: TEKNA PLASMA SYSTEMS INC.
hwww.tekna.qc.cai.
(4) G. V. Ivanov and F. Tepper, ™Activated Aluminum as a Stored
Energy Source for Propellants∫, in: K. K. Kuo (Eds),
™Challenges in Propellants and Combustion 100 Years After
Nobel∫, Begell House, New York, 1997, pp. 636 ± 645.
(5) M. M. Mench, C. L. Yeh and K. K. Kuo, ™Propellant Burning
Rate Enhancement and Thermal Behavior of Ultra-Fine
Aluminum Powders (Alex)∫, 29th Int. Annual Conference of
ICT, Karlsruhe, Germany, June 30 ± July 3, 1998, pp. 30/1 ± 15.
(6) V. N. Simonenko and V. E. Zarko, ™Comparative Studying
the Combustion Behavior of Composite Propellants Con-
taining Ultra Fine Aluminum∫, 30th Int. Annual Conference
of ICT, Karlsruhe, Germany, June 29 ± July 2, 1999, pp. 21/1 ±
14.
(7) B. Bashung, D. Grune, H. H. Licht, and M. Samirant,
™Combustion Phenomena of a Solid Propellant Based on
Aluminum Powder∫, 5th Int. Symposium on Special Topics in
Chemical Propulsion, Stresa, Italy, June 19 ± 22, 2000.
(8) P. Lessard, F. Beaupre¬, and P. Brousseau, ™Burn Rate Studies
of Composite Propellants Containing Ultra-Fine Metals∫,
32nd Int. Annual Conference of ICT, Karlsruhe, Germany,
July 3 ± 6, 2001, pp. 88/1 ± 11.
(9) A. A. Reshetov, V. B. Shneider, and N. A. Yavorovsky, ™Ultra
Dispersed Aluminum×s Influence on the Speed of Detonation
of Hexagen∫, 1st All-Union Symposium on Macroscopic
Kinetic and Chemical Gas-Dynamics, Chernogolovka, Russia,
October, 1984.
(10) A. J. Tulis, W. K. Sumida, J. Dillon, W. Comeyne and D. C.
Heberlein, ™Submicron Aluminum Particle Size Influence on
Detonation of Dispersed Fuel-Oxidizer Powders∫, Arch.
Comb. 18(1 ± 4), 157 ± 164 (1998).
(11) P. J. Miller, C. D. Bedford, and J. J. Davis, ™Effect of Metal
Particle Size on the Detonation Properties of Various
Metallized Explosives∫, 11th Symposium (International) on
Detonation, Snowmass Village, Colorado, August 31 ±
September 4, 1998, pp. 214 ± 220.
(12) A. LefranÁois and C. Le Gallic, ™Expertise of Nanometric
Aluminum Powder on the Detonation Efficiency of Explo-
sives∫, 32nd Int. Annual Conference of ICT, Karlsruhe,
Germany, July 3 ± 6, 2001, pp. 36/1 ± 14.
(13) P. Brousseau and M. D. Cliff, ™The Effect of Ultrafine
Aluminum Powder on the Detonation Properties of Various
Characterization of Aluminum Nanopowder Compositions 239
Explosives∫, 32nd Int. Annual Conference of ICT, Karlsruhe,
Germany, July 3 ± 6, 2001, pp. 37/1 ± 14.
(14) H. E. Dorsett, P. Brousseau, and M. D. Cliff, ™The Influence
of Ultrafine Aluminium upon Explosives Detonation∫, 28th
Int. Pyrotechnics Seminar, Adelaide, Australia, November 4 ±
9, 2001.
(15) M. M. Mench, K. K. Kuo, C. L. Yeh, and Y. C. Lu,
™Comparison of Thermal Behavior of Regular and Ultra-
Fine Aluminum Powders (Alex) Made from Plasma Explo-
sion Process∫, Comb. Sci. and Tech. 135, 269 ± 292 (1998).
(16) R. Sande¬n, ™Characterization of Electro-Exploded Alumi-
num∫, 29th Int. Annual Conference of ICT, Karlsruhe,
Germany, June 30-July 3, 1998, pp. 77/1 ± 10.
(17) M. D. Cliff, L. de Yong, D. P. Edwards, and D. S. Watt,
™Characterization of Electroexploded Aluminum (Alex)∫,
Report DSTO-TR-0818 (1999), DSTO Aeronautical and
Maritime Research Laboratory, Melbourne, Australia.
(18) P. Brousseau, S. Co√te¬, P. Lessard, and F. Beaupre¬, ™Thermal
Analysis of Aluminum Nanopowders∫, TTCP WTP-4 Work-
shop, Indian Head, MD, USA, April 1999.
(19) I. E. Hooton and J. Pagotto, ™Characterization of Metal
Powders∫, Report DRES-TR-1999 ± 192 (1999), Defence
Research Establishment Suffield, Canada.
(20) P. Pranda, K. Prandova, and V. Hlavacek, ™Particle Size and
Reactivity of Aluminum Powders∫, Comb. Sci. and Tech. 156,
81 ± 96 (2000).
(21) D. E. G. Jones, P. Brousseau, R. C. Fouchard, A.-M. Turcotte,
and Q. S. M. Kwok, ™Thermal Characterization of Passivated
Nanometer Size Aluminum Powders∫, 27th Int. Pyrotechnics
Seminar, Grand Junction CO, July 16 ± 21, 2000.
(22) D. E. G. Jones, P. Brousseau, R. C. Fouchard, A.-M. Turcotte,
and Q. S. M. Kwok, ™Thermal Characterization of Passivated
Nanometer Size Aluminum Powders∫, Journal of Thermal
Analysis and Calorimetry 61, 805 ± 818 (2000).
(23) P. D. Lightfoot, Q. S. M. Kwok, A.-M. Turcotte, R. C.
Fouchard, W. Ridley, and D. E. G. Jones, ™Characterization
of Aluminum Nanopowders∫, Combustion Institute Canadian
Section Spring Technical Meeting, Montreal, Canada, May
13 ± 16, 2001.
(24) Q. S. M. Kwok, P. D. Lightfoot, R. C. Fouchard, A.-M.
Turcotte, W. Ridley, D. E. G. Jones, and P. Brousseau,
™Characterization of Passivated Aluminum Nanopowders∫,
28th Int. Pyrotechnics Seminar, Adelaide, Australia, Novem-
ber 4 ± 9, 2001.
(25) P. D. Lightfoot, R. C. Fouchard, A.-M. Turcotte, Q. S. M.
Kwok, W. Ridley, D. E. G. Jones, and P. Brousseau,
™Characterization of Aluminum Nanopowders∫, 2001 Insen-
sitive Munitions and Energetic Materials Technology Sympo-
sium, Bordeaux, France, October 8 ± 11, 2001.
(26) J. T. DeSena and K. K. Kuo, ™Evaluation of Stored Energy in
Ultrafine Aluminum Powder Produced by Plasma Explo-
sion∫, Journal of Propulsion and Power 15(6), 794 ± 800
(1999).
(27) P. Brousseau, S. Co√te¬, N. Ouellet, and P. Lessard, ™Prelimi-
nary Testing of Energetic Materials Containing Aluminum
Nano-Powders∫, TTCP WTP-4 Workshop, Salisbury, Aus-
tralia, April 2000.
(28) I. M. K. Ismail and T. W. Hawkins, ™Evaluation of Electro
Exploded Aluminum (ALEX) for Rocket Propulsion∫, CPIA
Publication 650(2), 25 (1996).
(29) ASTM E 968, Standard Practice for Heat Flow Calibration of
Differential Scanning Calorimeters, American Society for
Testing and Materials, Philadelphia, PA. USA.
(30) ASTM E967, Standard Practice for Temperature Calibration
of Differential Scanning Calorimeters and Differential
Thermal Analyzers, American Society for Testing and
Materials, Philadelphia, PA. USA.
(31) D. I. Townsend and J. C. Tou, ™Thermal Hazard Evaluation
by an Accelerating Rate Calorimeter∫, Thermochimica Acta
37, 1 ± 30 (1980).
240 Kwok, Fouchard, Turcotte, Lightfoot, Bowes, Jones
(32) ASTM E 1981 ± 98, Standard Guide for Assessing the
Thermal Stability of Materials by Methods of Accelerating
Rate Calorimetry, American Society for Testing and Materi-
als, West Conshohocken. PA, USA.
(33) P. D. Lightfoot, D. E. G. Jones, R. C. Fouchard, Q. S. M.
Kwok, W. Ridley, and A.-M. Turcotte, ™Hazard Character-
ization of KDNBF Using a Number of Different Tech-
niques∫, 29th DoD Explosives Safety Seminar, New Orleans
LA, July 18 ± 20, 2000.
(34) ASTM E1226 ± 94, Standard Test Method for Pressure and
Rate of Pressure Rise for Combustible Dusts, American
Society for Testing and Materials, Philadelphia, PA. USA.
Propellants, Explosives, Pyrotechnics 27, 229 ± 240 (2002)
Acknowledgements
We would like to thank Patrick Brousseau of DREV for
supporting and encouraging our research efforts in this work.
Additionally, we would like to express our gratitude to Fred Tepper
of Argonide Corporation and Joey Viljoen of Orica Canada Inc. for
providing the samples of Alex and paint-fine Al, respectively.
Finally, our appreciation is extended to Dr. Jim Brown of Natural
Resources Canada and Dr. P. Amyotte of Dalhousie University for
the surface characterization work and for the explosibility tests,
respectively.
(Received February 26, 2002; Ms 2002/022)