Propellants, Explosives, Pyrotechnics 33, No.
4 (2008)
Full Paper
Effect of Voids inside AP Particles on Burning Rate of AP/HTPB
Composite Propellant
Makoto Kohga*
Department of Applied Chemistry, National Defense Academy, Hashirimizu 1-10-20, Yokosuka, Kanagawa 239-8686
(Japan)
Received: June 21, 2007; revised version: June 23, 2008
DOI: 10.1002/prep.200700234
Abstract
Bubble contamination in an ammonium perchlorate (AP)-
based composite propellant has a positive effect on the burning
rate. However, the quantitative effect of the bubble contamina-
tion on the burning rate has never been revealed. In order to
clarify the relationship between the increase in the burning rate
and the void fraction of the propellant, propellants were prepared
with fine porous AP particles (PoAP) or fine hollow AP particles
(HoAPs), and their burning rate characteristics were investigated.
The voids inside AP particles have the effect of increasing the
burning rate. The increase in the burning rate is enhanced linearly
as the void fraction increases. The effect of the void fraction on
the burning rate for a propellant containing PoAP is not identical
with that for a propellant containing HoAP. It was found that the
effect of the void fraction on the burning rate could be estimated
by the void fraction when the bubble contamination is uniform in
size and shape.
Keywords: Ammonium Perchlorate, Bubble Contamination,
Burning Rate, Composite Propellant, Void Fraction
1 Introduction
In order to accommodate a diversity of rocket motors, it is
necessary to expand the range of the burning rate of the
propellant, especially in the higher burning rate region.
Recently, ammonium perchlorate (AP)/hydroxyl-terminat-
ed polybutadiene (HTPB) composite propellant is widely
used as a solid propellant. It is generally known that the
burning rate of the AP/HTPB composite propellant in-
creases with the decreasing particle diameter of the AP
particles contained in the propellant. Fine AP particles are
required to obtain a high burning rate AP/HTPB composite
propellant. However, it is difficult to safely prepare fine AP
particles by grinding [1, 2] because fine AP is easily ignited
and explodes with any slight impact or friction. It was
reported that some fine porous or hollow AP particles
* Corresponding author; e-mail: kohga@nda.ac.jp
C 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
249
(HoAPs) were safely prepared by a spray-drying method
[3 7].
It is possible that bubble contamination is scattered in the
solid propellant grains during their manufacture. Bubble
contamination in the solid propellant grains loaded in a
rocket motor might induce a serious problem. Some
influences of cracks or voids in solid propellant grains on
combustion have been investigated [8 10]. Yamaya et al.
[10] caused bubble contamination in the binder by adding
some microspheres, e.g., hollow carbon, hollow glass, and
hollow plastic microspheres, to the uncured AP-based
composite propellant, and they investigated the influences
of the bubble contamination on the burning characteristics.
It was reported that the bubbles, of which the average
diameter was in the range of 43 200 mm, in the binder have
a positive effect on the burning rate [10].
The fine hollow and porous AP particles (PoAPs) have
empty spaces in these particles. It can be considered that a
propellant prepared with PoAP and HoAP would have
bubble contamination because voids inside the PoAP and
HoAP cannot be completely charged with HTPB. In the
previous paper [11], twenty AP samples including eight
kinds of PoAPs and HoAPs were used as an oxidizer, and
the burning characteristics of the propellant prepared with
fine PoAPs or HoAPs were investigated. It was found that
there was bubble contamination in the propellant pre-
pared with PoAPs and HoAPs, and the voids in the PoAPs
and HoAPs had a positive effect on the burning rate.
However, the quantitative effect of the bubble contami-
nation on the burning rate was not revealed. In this study,
an attempt was made to clarify the relationship between
the increase in the burning rate and the void fraction of the
propellant.
250 M. Kohga

2 Experimental Table 1. Compositions and properties of propellants.

Symbol HoAP PoAP GrAP HTPB Dw Density Void
2.1 Sample % % % % mm g cm 3 fraction
A1 8 72 20 220 1.60 0
2.1.1 AP Samples A2 24 56 170 1.59 0.004
A3 40 40 130 1.56 0.024
In this study, three kinds of AP particles were used as an A4 48 32 100 1.55 0.033
oxidizer: PoAP, HoAP, and a ground commercial AP B1 8 72 220 1.57 0.018
(GrAP). PoAP and HoAP were prepared by spray-drying B2 24 56 20 170 1.51 0.058
B3 40 40 120 1.44 0.097
methods [5, 7]. GrAP was prepared by grinding a commer- C 80 20 240 1.60 0
cial AP with a vibration ball mill for 5 min. The scanning
electron microscope (SEM) photographs of PoAP and
HoAP are shown in Figure 1. According to the external view
of these AP particles, PoAP has some small holes in the PoAP or HoAP alone because these AP samples are fine
crust, and the voids in the porous particles are connected to particles.
the outside [5]. The shape of HoAP appears spherical in the The upper limit of AP content incorporated in the
SEM photograph. However, HoAP has voids in the propellant prepared with fine particles increases on replac-
particles, indicating a hollow sample [7]. GrAP has a ing fine particles with coarse particles [14]. GrAP was a
spherical shape. The weight mean diameter (Dw) of AP coarse AP sample. An attempt was made to prepare the
was measured using the SEM photographs. The Dw of PoAP, propellant containing 80% AP with bimodal AP mixed with
HoAP, and GrAP are 9, 4, and 240 mm, respectively. PoAP or HoAP and GrAP. PoAP could not be contained at
The thermochemical behavior and crystallographic prop- more than 48% in the propellant with 80% AP, and HoAP
erties of a particle would be altered by quick recrystalliza- could not be contained at more than 40%. Table 1 shows the
tion. Differential thermal analysis (DTA), thermogravim- composition of the propellant used to investigate the effect
etry (TG), and X-ray diffractometry (XRD) were employed of the void fraction in the propellant on the burning rate. The
in preliminary experiments. The DTA TG thermograms Dw of AP included in the propellant was calculated
and the XRD patterns of AP samples were almost the same theoretically from the proportion of AP and each Dw of
and closely coincided with the typical DTA TG thermo- the AP sample. The propellants prepared in this study were
gram and XRD pattern of AP, respectively. These results designated by the symbols shown in Table 1. Three batches
indicate that the AP samples used in this study have almost of propellants were prepared with the same AP sample, and
the same thermochemical behavior and crystallographic the burning rate characteristics of these propellants were
properties. measured.

2.1.2 Propellant Sample 2.2 Measurement of Propellant Density

In this study, the propellants were prepared with 80%AP.
HTPB was used as a binder. HTPB was cured with
isophorone diisocyanate. Eight percent of isophorone
diisocyanate related to HTPB was added.
The upper limit of AP content incorporated in the
propellant exists due to limitations in the formulation of
AP/HTPB composite propellant, and the upper limit of AP
content decreases with decrease in size of the AP [12, 13].
The propellant with 80% AP could not be prepared with
The propellant strands were prepared using the AP
samples shown in Table 1. Approximately 14 propellant
strands were prepared for one batch. As mentioned in
Section 2.1.2, three batches of propellants were prepared
with the same AP sample. The densities of all propellant
strands were calculated from the volume and weight. The
weight of the strand was determined with an electric balance
with a minimum reading of 0.01 g. The size of the strand was
measured with a vernier caliper, the minimum scale of which
was 0.05 mm.

2.3 Measurement of Burning Rate

The size of each strand was 10 mm  10 mm in cross-

Figure 1. SEM photographs of AP samples.
section and 40 mm in length. The burning rate was measured
in a chimney-type strand burner which was pressurized with
nitrogen at 288  1.5 K. The range of pressure was from 0.5
to 7 MPa. The strand sample was ignited by an electrically
heated nichrome wire attached on the top of each strand
sample. Two fuse wires were threaded through the strand
sample at 25 mm distance. The fuse wire was cut as soon as

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Effect of Voids inside AP particles on Burning Rate of AP/HTPB Composite Propellant 251

the burning surface passed through the fuse wire. The

burning rate was calculated using the cutoff period of two
fuses.

3 Results and Discussion

3.1 Void Fraction

A PoAP has some small holes in the crust, and the voids in
the particle are connected to the outside, as described in
Section 2.1.1. HoAP has a void in the particle. The bubble Figure 2. Relationship between content of PoAP or HoAP and
contamination in a propellant prepared with porous or void fraction.
hollow AP would be inside the AP particles because the
voids in porous or hollow AP cannot be completely charged
with HTPB. In this section, the propellant density was
measured and the void fraction of the propellant was
estimated on the basis of the density.
The propellant density is tabulated in Table 1. The
deviation of the density measurements remained within
0.01 g cm 3. The density decreases with the increase in
content of PoAP or HoAP. The propellant was prepared
with 80% AP in this experiment. The densities of AP and
cured HTPB were 1.95 and 0.93 g cm 3, respectively.
The theoretical density of the propellant at 80% AP was
1.60 g cm 3. The densities of propellants A2 A4 and B1
B3 were below the theoretical value. The densities of
propellants A1 and C agreed with the theoretical value. The
proportion of the bubble contamination in the propellant Figure 3. Burning rate characteristics.
was estimated based on the propellant density. Table 1 also
provides the void fractions of the propellants. The void
fraction of propellants A1 and C was zero. This indicates When the proportion of the bubble contamination in the
that these propellants did not have bubble contamination. composite propellant containing 80% AP exceeds the void
Despite the fact that propellant A1 contained 8% PoAP, the fraction of 0.02, the burning rate is influenced by the bubble
voids inside this propellant were undetectable by the contamination and, consequently, a reproducible burning
technique used in this experiment, while the voids inside rate cannot be obtained [10]. However, the combustion of a
the propellant B1 prepared with 8% HoAP were detected. composite propellant, in which the proportion of bubble
This was because of the difference in the particle properties, contamination is 0.10, can be kept at a steady state when the
especially the size and shape of the voids in the AP particles diameter of the bubbles in the propellant ranges from 10 to
and the particle diameter, between PoAP and HoAP. The 350 mm and the bubbles do not contact each other [10]. Even
void fraction was in the range of 0.004 0.097, and that for though the void fraction of propellants A3, A4, B2, and B3
propellant B3 was the greatest in this study. were above 0.02, these propellants had reproducible burn-
Figure 2 shows the influence of the content of PoAP or ing rates as indicated in Figure 3. The bubble contamination
HoAP on the void fraction. The void fractions increase in propellants A2 A4 and B1 B3 would be inside PoAP
linearly with the increase in content of PoAP or HoAP. This and HoAP particles as stated in Section 3.1. This suggests
indicates that the void fractions can be estimated by the that the voids were very small, less than the size of the AP
content of PoAP or HoAP. particles, and numerous small voids would be distributed
independently. Therefore, the combustion of the propel-
lants prepared with PoAP and HoAP can evidently be
3.2 Burning Rate maintained at a steady state even if the propellants have
bubble contamination above a void fraction of 0.02.
Figure 3 presents the burning rate characteristics. A
reproducible burning rate was obtained, and an approx-
imately linear relationship existed between log(pressure) 3.3 Effect of Void Fraction on Burning Rate
and log(burning rate) in this pressure range. The burning
rate increases with the increase in concentration of PoAP or Table 2 shows the burning rates (r) at 1 and 7 MPa
HoAP. determined on the basis of the burning rate characteristics.
At constant AP content and combustion pressure, the

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252 M. Kohga

Table 2. Burning rate characteristics of propellant.

Propellant 1 MPa 7 MPa
r r* r/r* r r* r/r*
1 1 1 1
mm s mm s mm s mm s
A1 3.9 3.9 1.00 8.6 8.6 1.00
A2 4.4 4.1 1.07 9.9 9.7 1.02
A3 6.2 4.8 1.29 13.8 10.9 1.27
A4 7.1 5.2 1.37 16.3 12.2 1.34
B1 4.7 4.1 1.15 9.3 8.9 1.04
B2 5.4 4.3 1.26 11.4 9.7 1.18
B3 7.6 4.9 1.55 14.5 11.1 1.31
C 3.9 3.9 1.00 8.5 8.5 1.00

Figure 4. Influence of Dw on burning rate.

burning rate of the propellant without bubble contamina-

tion is dependent on Dw [11, 15, 16]. Figure 4 depicts the
relationship between the burning rates measured at 1 and 7
MPa and Dw. For each propellant including PoAP or HoAP, r
relates to Dw as well. The r increases with decrease in Dw.
However, the relationship between r and Dw of the
propellant containing HoAP is not identical to that of the
propellant containing PoAP. The r of the propellant
containing HoAP is higher than that of the propellant
containing PoAP at constant Dw.
At 72% AP, the voids in PoAPs and HoAPs have a
positive effect on the burning rate [11]. The relationship
between the burning rate for propellant with 80% AP and
Dw was reported in Ref. [16]. The relationship between r and
Dw of the propellant prepared with spherical AP [16] is also
shown by the broken line in Figure 4. The burning rate of the
propellant containing PoAP or HoAP is greater than that
shown by the broken line. This indicates that the burning
rates of propellants prepared with PoAP and HoAP
exceeded that of the propellant with spherical AP at a
constant Dw. It is confirmed that the voids inside AP
particles also have the effect of increasing the burning rate at
80% AP.
Table 2 shows that the burning rate (r*) of the propellant
prepared with spherical AP, the Dw of which was the same as
that of AP shown in Table 1, was determined on the basis of
the broken line. In order to clarify the difference in the
burning rate, the ratio of r to r* (r/r*) was calculated, and the
results are also shown in Table 2. The relationship between
r/r* and the void fraction is plotted in Figure 5. The r/r*
increases linearly with increase in void fraction at each
combustion pressure.
The burning rate increases with an increase in temper-
ature gradient in the vicinity of the burning surface. The
flame of an AP-based composite propellant is called a
diffusion flame, and the multiple-flame model [17] is
generally accepted as the flame structure model. This model
has the flame structure of AP-based composite propellant
consisting of the AP monopropellant flame, the primary
flame, and the final diffusion flame. The AP monopropel-
lant flame, which is composed of AP decomposition
products, is not considered to occur at the propellant surface
but rather to extend out from the surface. The primary flame
Figure 5. Effect of void fraction on r/r* (R squared values are
over 0.98).
is a premixed flame with the oxidizer and binder decom-
position products mixing completely before reaction occurs.
The final diffusion flame follows the primary flame.
According to this flame model, because the regression rate
of the AP particles is larger than that of HTPB, the location
of each flame is brought closer to the burning surface and,
consequently, the temperature gradient in the vicinity of the
burning surface increases. The regression rate of porous and
hollow AP would be greater than that of spherical AP at a
constant Dw because the flame propagation velocity in voids
inside porous and HoAPs would be higher than that in
nonvoid AP particles [11]. Therefore, the location of each
flame would be moved close to the burning surface, and the
burning rate would be increased because of the use of PoAP
and HoAP contained in the propellant, compared with the
propellant using a spherical AP alone. The flames would
move close to the burning surface as the concentration of
PoAP and HoAP in the propellant increased. According to
Figure 2, the void fraction was enhanced as the content of
PoAP and HoAP increased. Therefore, r/r* would increase
with the increase in void fraction.
The relationship between r/r* and the void fraction of the
propellant containing HoAP did not agree with that of the
propellant containing PoAP. For HoAP, the increase in r/r*
versus the void fraction at 1 MPa is definitely larger than

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Effect of Voids inside AP particles on Burning Rate of AP/HTPB Composite Propellant
that at 7 MPa. For PoAP, the increment at 1 MPa is slightly
larger than that at 7 MPa. The influence of the void fraction
on the r/r* of PoAP is greater than that of HoAP.
When the burning surface of a propellant, extinguished by
rapid depressurization, was observed, at lower pressure, the
AP particles protrude above the exposed surface of the
binder to a greater height, and at higher pressure, they recess
[18, 19]. This fact indicates that the regression rate of AP at a
higher pressure is greater than that at a lower pressure. The
flame propagation velocity in the voids inside PoAPs and
HoAPs would be higher than that of a non-void AP particle
[11]. The overall regression rate of AP at a lower pressure
would show a remarkable increase due to the PoAPs and
HoAPs present, compared to that at a higher pressure,
because the regression rate of AP at a higher pressure is
sufficiently great even with non-void AP particles. There-
fore, r/r* at 1 MPa would be greater than that at 7 MPa.
HoAP has voids in the particles and the voids in the
hollow particles are isolated from the outside. On the other
hand, PoAP has some small holes in the crust, and the voids
in the porous particle are connected to the outside. Some
entries of the voids in PoAP would be clogged with HTPB.
Because the combustion process of the propellant prepared
with HoAP was different from that of the propellant with
PoAP, the relationship between r/r* and the void fraction of
the propellant containing HoAP would not be identical to
that of the propellant containing PoAP. It was found that the
influence of the bubble contamination on the burning rate
was not presumed due to the void fraction alone. The
combustion process of the AP-based composite propellant
is greatly dependent on the particle properties of AP. The
influence of the void fraction on the burning characteristics
would vary due to the difference in the particle properties
between PoAP and HoAP, e.g., the mean diameter of AP
and the size and shape of voids in AP particles.
As mentioned in Section 3.1, the void fraction increases
linearly with the increase in content of PoAP and HoAP.
Also, r/r* is enhanced with the increasing void fraction at
each combustion pressure as shown in Figure 5. It was found
that the effect of the void fraction on the burning rate would
be determined by the content of PoAP and HoAP. These
facts suggest that the effect of the void fraction on the
burning rate would be estimated by the fraction when the
bubble contamination is uniform in size and shape.
4 Conclusion
In order to reveal the effect of void fraction on the burning
rate, the propellants were prepared with fine PoAP and fine
HoAP, and their burning rate characteristics were inves-
tigated. From this study, the following conclusions were
obtained: (i) the propellants prepared with PoAP and
HoAP have bubble contamination. The void fractions of
these propellants are in the range from 0.004 to 0.097. (ii)
The combustion of propellants prepared with PoAP and
HoAP was steady even if these propellants have bubble
contamination. This is because of the fact that the void size
C 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.pep.wiley-vch.de Propellants, Explos., Pyrotech. 33, No. 4, 249 254
253
in the propellant with PoAP and HoAP is very small, less
than the particle diameter of AP, and numerous fine voids
are distributed independently of one another. (iii) The voids
inside the AP particle have the effect of increasing the
burning rate. The effect of the void fraction on the burning
rate for the propellant containing PoAP is not identical with
that for the propellant containing HoAP. The effect would
be estimated by the fraction when the bubble contamination
is uniform in size and shape.
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