Full Paper
DOI: 10.1002/prep.201500264
Investigation of the Failure Mechanism of HTPB/AP/Al
Propellant by In-situ Uniaxial Tensile Experimentation in
SEM
Marthinus C. J. van Ramshorst,[a, b] Giuseppe L. Di Benedetto,[a, c] Willem Duvalois,[a] Peter A. Hooijmeijer,[a]
and Antoine E. D. M. van der Heijden*[a, d]
Abstract: The failure mechanism of a propellant consisting
of hydroxyl terminated poly-butadiene filled with ammoni-
um perchlorate and aluminum (HTPB/AP/Al) was deter-
mined by performing in-situ uniaxial tensile tests in a scan-
ning electron microscope (SEM). The experimental test plan
contained uniaxial tensile test experiments performed at
room temperature (25 8C) at three different strain rates (30,
150 and 750 mm min 1). The in-situ images and in-situ
videos collected by the SEM were correlated with the
stress-strain diagrams created with the tensile experiments,
in order to relate the failure mechanism to the features
found in the stress-strain diagram. No significant strain rate
dependency of the failure mechanism was observed when
working with strain rates up to 750 mm min 1 and working
at room temperature. The stress-strain diagram showed in-
Keywords: Propellant · Micromechanical deformation · In-situ tensile testing · In-situ SEM · Mechanical properties
1 Introduction
The aging of propellants has an influence on the mechani-
cal performance and, therefore, has great influence on the
safety of the missile in which the propellant is used. On ig-
nition of a rocket, there is a pressure build up in the com-
bustion chamber and in the bore of the propellant grain.
This pressure is necessary in order to initiate the chemical
reaction that will ignite the propellant grain. This pressure
can get so high that cracks can form in the propellant
grain. These cracks result in a larger burning area and,
therefore, the rate at which gaseous products are released
will be increased. This will raise the pressure finally result-
ing in an increase in the burning rate of the grain. In order
to prevent the propellant from cracking, it is important to
study and understand the failure mechanism of the propel-
lant.
Traditionally, macro-level tensile testing has been used to
study the mechanical properties of propellants [1–8]. How-
ever, any investigation into the failure mechanism of the
propellant must be performed through post-mortem analy-
sis of the ruptured specimen [5, 7]. In-situ tensile testing
techniques coupled with Scanning Electron Microscopy
(SEM) observation have allowed researchers to study the
DOI: 10.1002/prep.201500264  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
dications of existing cracks and voids opening up prior to
the creation of new cracks and/or voids in the sample, de-
bonding of binder with AP particles as well as nucleation
and coalescence of voids. On the fracture surfaces of the
samples, it was apparent that the binder cleanly separated
from the large AP particles but had a better bond with the
aluminum particles. However, a difference in the appear-
ance of a short drawing phase in the stress-strain diagram
of the propellant is observed at different strain rates. The
presented results clearly demonstrate the major advantage
of the combination of microscopic tensile tests with micro-
scopic observations, linking the stress-strain behavior to
the mechanical deformation processes taking place in
these propellant samples at the microscopic level.
failure mechanism of various materials [9–13]. Zheng et al.
[12] investigated the crack initiation, propagation, and ter-
[a] M. C. J. van Ramshorst, G. L. Di Benedetto, W. Duvalois,
P. A. Hooijmeijer, A. E. D. M. van der Heijden
Department of Energetic Materials
TNO Defence, Security and Safety
P.O. Box 45
2280 AA Rijswijk, The Netherlands
*e-mail: antoine.vanderheijden@tno.nl
[b] M. C. J. van Ramshorst
Department of Materials Science and Engineering
Delft University of Technology
Mekelweg 2
2628 CD Delft, The Netherlands
[c] G. L. Di Benedetto
Advanced Materials Technology Branch
U.S. Army RDECOM-ARDEC
Picatinny Arsenal, NJ 07806-5000, USA
[d] A. E. D. M. van der Heijden
Section Intensified Reaction and Separation Systems
Delft University of Technology
Leeghwaterstraat 39
2526 CB Delft, The Netherlands
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Full Paper M. C. J. van Ramshorst, G. L. Di Benedetto, W. Duvalois, P. A. Hooijmeijer, A. E. D. M. van der Heijden
mination on plerosphere particles in a polypropylene
matrix using in-situ tensile testing in SEM. Such an in-situ
analysis on propellants would be invaluable. Tao et al. [14]
applied the research techniques of Kim and Michler [9–10]
and Zheng et al. [12] to study the microstructure deforma-
tion and fracture behavior of propellant simulation materi-
als. These simulation materials consisted of three kinds of
solid filler particles (varying percent mixtures of aluminum,
ammonium perchlorate, and HMX) in an unspecified poly-
meric binder matrix. The total content of the filler particles
was consistently 74 % for each experimental sample. Tao
et al. [14] investigated these propellant simulation materials
under uniaxial tension by using an in-situ tensile test
system under SEM. Tao et al. [14] found that the unspeci-
fied polymeric binder would debond cleanly from the AP
particles and large voids were formed around the particles
in the stress direction. On the other hand, Tao et al. [14]
found that along the Al particles in his material almost no
debonding occurred. The current study advances the work
of Tao et al. [14] by providing a more thorough investiga-
tion into the failure mechanism of a different propellant
composition using in-situ uniaxial tensile testing in SEM.
The failure mechanism of a propellant consisting of hy-
droxyl-terminated polybutadiene (HTPB) filled with ammo-
nium perchlorate (AP) and aluminum (Al) was investigated
by preforming in-situ uniaxial tensile experimentation in
a SEM. The experimental test program contained experi-
ments at the strain rates 30, 150, and 750 mm min 1, which
are very low when compared to macro-level tensile testing
(0.75–1.0 [4, 5], 11.5 [2], 50 [6, 7], 51 [3], 115 [2], 500 [2],
(720–960)  103 [4, 5], (1,080–1,440)  103 mm min 1 [4, 5]).
This was due to limitations of the motor on the tensile/
compression module used and the ability of the SEM to
capture images and videos during the experiments. If
macro-level strain rates were used, the SEM would only
capture blurred images and videos that would not offer the
useful information needed for this study. During experi-
mentation, high magnification on the SEM was not utilized,
and magnifications comparable to optical microscopy were
used. These magnifications offered visual analysis of the
entire width of the samples during the experiments, and
the additional SEM detectors used in this study offered
better contrast between components of the propellant
sample composition than optical microscopy can offer. The
data analysis of the experimental stress-strain diagrams
coupled with the in-situ SEM images and videos of the
specimens helped to understand the mechanical per-
formance and failure behavior of the solid propellant under
uniaxial tensile forces. The understanding of the mechanical
performance and failure behavior of a propellant will allow
focusing on the improvement of the most critical degrada-
tion steps occurring in the propellant as a function of
ageing.
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2 Experimental
2.1 Materials
A propellant composition of 85 wt-% of solid particles and
15 wt-% of a binder component mixture was used in this
study. The solid particles consisted of ammonium perchlo-
rate (AP) (mixture ratio of 7 : 3 by weight for 200 : 15 mm in
size) and aluminum (18 wt-% of the total composition). The
binder component consisted of a mixture of HTPB (R-
45HT), inosine diphosphate (IDP) as plasticizer, isophorone
diisocyanate (IPDI) as curing agent, Tepanol as bonding
agent, and 1-N-cyclohexyl-4-N-phenylbenzene-1,4-diamine
(Flexzone 6 H) as anti-oxidant.
Tensile test specimens were prepared of the propellant
composition. The test specimen design followed the stan-
dard JANNAF C specimen. However, the test specimens
had to be scaled down due to the size limitations of the
tensile/compression module and scanning electron micro-
scope (SEM) used in this study. It was determined that the
test specimens for this study be one-quarter the size of the
JANNAF specimens (as seen in Figure 1).
Figure 1. Schematic with dimensions in millimeters of the one-
quarter sized JANNAF test specimens used in this study.
However, this scaled reduction in sample size allows for
a larger effect of the inhomogeneity of the propellant com-
position on the experimental stress-strain data. In macro-
level tensile testing with full-size JANNAF C specimens, one
single large AP particle (200 mm) amounts to only 2.1 % of
the sample width (9.5 mm) and 1.6 % of the sample thick-
ness (12.7 mm). For the micro-level tensile testing in this
study, one single large AP particle amounts to 8.4 % of the
sample width (2.35 mm) and 6.4 % of the sample thickness
(3.14 mm). Thus, the inhomogeneity of the propellant com-
position can have sixteen times (16 ) the effect on the ex-
perimental data.
2.2 Equipment
2.2.1 Tensile/Compression Module
A tensile/compression module from Kammrath and Weiss
was used to investigate the failure mechanism of the solid
propellant in this study. The tensile/compression module is
designed with two yokes moving symmetrically away from
DOI: 10.1002/prep.201500264
Failure Mechanism of HTPB/AP/Al Propellant
Figure 2. Tensile/Compression module mounted within SEM with
GAD installed under the pole piece. ETD is also present on the top
right.
each other. The movement speed of the yokes can range
from 15 mm min 1 to 1,560 mm min 1. The load cell has
a maximum load of 10000 N. The tensile/compression
module was placed and secured inside the SEM for each
experimental tensile test run (see Figure 2). During this
study, the strain rate (or movement speed of the yokes)
was varied and controlled by software on a computer out-
side of the SEM. Three different strain rates were used in
this study: 30, 150, 750 mm min 1. The load exerted
[Newton], elongation of the specimen [mm], and time [sec-
onds] were recorded on this external computer during
each tensile experiment.
2.2.2 Scanning Electron Microscopy (SEM)
A FEI NovaNanoSEM 650 was utilized in this study. The SEM
has a combination of a SE/BSE (secondary electrons/back-
scattered electrons), in-lens detection and beam decelera-
tion, and high sensitivity retractable SE/BSE and scanning
transmitting electron microscopy (STEM) detectors. The mi-
croscope can operate in high (10 4 Pa) and low vacuum
(10–200 Pa) mode. Both vacuum modes, each mode with
a different detector, were utilized in this study. These two
different detectors allowed a more thorough study of the
test specimens undergoing tensile stress.
The Everhart-Thornley detector (ETD) is a conventional
SE detector for the SEM. It can operate under high vacuum
mode, but not low vacuum mode due to the design of the
detector. The ETD does not have a pressure limiting aper-
ture covering and protecting the SEM pole piece from ex-
posure to water molecules in low vacuum mode. However,
the advantage to not having a pressure limiting aperture
over the pole piece is that there is no limitation to the min-
imum operational magnification with the ETD. This allowed
for the SEM ETD images to show an excellent representa-
tion of the full width of the specimens. The ETD provided
topographical contrast of the propellant specimens in the
DOI: 10.1002/prep.201500264 www.pep.wiley-vch.de
in-situ images and in-situ videos captured prior, through-
out, and after uniaxial tensile stress experimentation. The
in-situ videos were recorded using the High Resolution TV
mode of the SEM with the ETD. Since the ETD is a SE detec-
tor, it collected a lot of secondary electron information in
order to record smooth, clear, high resolution videos.
The gaseous analytical detector (GAD) is a BSE detector
that is mounted under the SEM final lens (pole piece). The
GAD can operate in high or low vacuum mode. It has
a pressure limiting aperture to protect the pole piece from
water molecules in low vacuum mode. In low vacuum
mode, the GAD can provide ultra-high resolution images of
non-conductive or fast contaminating samples. Unfortu-
nately, since the GAD is a BSE detector, it was unable to
collect enough information for clear, high resolution videos.
The GAD provides compositional contrast of the propellant
specimens due to the collection of back-scattered elec-
trons. This allowed the user to track specific particles or fea-
tures of the specimen throughout the uniaxial tensile ex-
perimentation. However, the pressure limiting aperture of
the GAD prevents use of any magnification lower than 350
times (350 ). Thus, SEM GAD images were unable to dis-
play the full width of the propellant specimens. In this
study, the SEM GAD was utilized in low vacuum mode to
collect in-situ images of the propellant specimens undergo-
ing uniaxial tensile stress with a focus on particles and cer-
tain features. The combination of the ETD in-situ images,
ETD in-situ videos, and GAD in-situ images provided
a more thorough study of the details of the failure mecha-
nism of the propellant specimens.
2.3 Experimental Procedure
For each experimental test run, the tensile/compression
module was placed within the SEM chamber, and a HTPB/
AP/Al propellant test specimen was placed into the sample
holder of the module. Vacuum was drawn on the chamber,
and the tensile/compression module was controlled by the
software on a computer. All experiments were conducted
at room temperature (25 8C), but the strain rate was varied
through the software. Three different strain rates were used
in this study: 30, 150, 750 mm min 1. The strain rate was
kept constant from the start of the experiment up to the
point of rupture of the specimen. The load exerted [N],
elongation of the specimen [mm], and time [seconds] were
recorded during each tensile experiment. During the re-
cording of this data, the stress e [mm/mm] and strain
s [MPa] were calculated using the cross-sectional area and
length of the specimen. The cross-sectional area used for
the stress calculations was 7.2 mm2. The length used for
the strain calculations was 12.5 mm. While the sample was
undergoing tensile stress, SEM images and videos were
captured at set locations of the samples. These images
were captured incrementally throughout the experiment
and allow an in-situ view of the effects of tensile stress on
the specimens and their components.
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Full Paper M. C. J. van Ramshorst, G. L. Di Benedetto, W. Duvalois, P. A. Hooijmeijer, A. E. D. M. van der Heijden

3 Results and Discussion

3.1 Strain Rate Measurements

Prior to conducting the experiments in this study, a series
of calibration runs were conducted with the tensile/com-
pression module outside of the SEM in ambient tempera-
ture and atmospheric pressure. These calibration runs were
conducted with samples of different materials as well as an
HTPB/AP/Al propellant sample. These runs successfully cali-
brated the tensile/compression module and offered suc-
cessful evidence that the stress-strain results did not differ
under vacuum and electron beam exposure.
HTPB/AP/Al propellant specimens were tested under ten-
sile stress at strain rates of 30, 150, and 750 mm min 1within
the SEM at 25 8C. Each experimental test run was conduct-
ed according to the procedure explained in Section 2.3.
Stress as a function of strain of the HTPB/AP/Al propellant
specimens at these three strain rates are shown in Fig-
ure 3a–c. The stress and the strain data of phenomena oc-
curring in the specimen are summarized in Table 1. These
results are discussed in more detail in Section 3.2.
While conducting the tensile experiments, in-situ SEM
observance was used to understand the effect of tensile
stress on the HTPB/AP/Al propellant specimens. The ETD
and the GAD of the SEM were utilized to collect in-situ
images and in-situ videos of the propellant specimens un-
dergoing uniaxial tensile stress. Some of these images are
shown in Figure 4. These images correlate to the points in-
dicated in the stress-strain diagram in Figure 3a. The SEM
ETD images were able to show an excellent representation
of the full width of the specimens.
Since the three strain rates tested in this study showed
comparable results, only the stress-strain diagram shown in
Figure 3a and the corresponding SEM ETD images in
Figure 4 recorded at a strain rate of 30 mm min 1 are de-
scribed in more detail herein. In addition some features ob-
served for the other two strain rates, which deviated from

Table 1. Stress and strain for points indicated in Figure 3a–c of

HTPB/AP/Al propellant at different strain rates.
1 1 1
Stress/strain 30 mm min 150 mm min 750 mm min
s1 [MPa] 0.25 0.46 0.43
e1 [mm/mm] 0.038 0.053 0.058
s2 [MPa] 0.19 0.37 0.27
e2 [mm/mm] 0.048 0.095 0.104
s3 [MPa] 0.70 0.67 0.46 Figure 3. Stress-strain diagrams of HTPB/AP/Al propellant at
e3 [mm/mm] 0.174 0.181 0.181 a strain rate of (a) 30 mm min 1, (b) 150 mm min 1, and (c)
s4 [MPa] 0.68 0.59 0.36 750 mm min 1.
e4 [mm/mm] 0.219 0.192 0.201
s5 [MPa] 0.79 0.96 0.74
e5 [mm/mm] 0.251 0.253 0.257 the overall mechanical behavior will also be highlighted.
s6 [MPa] 0.66 0.80 0.59 The effect of the propellant composition inhomogeneity (as
e6 [mm/mm] 0.280 0.301 0.290 explained in Section 2.1) was evident in all of the experi-
s7 [MPa] 0.80 0.90 0.61
e7 [mm/mm] 0.305 0.346 0.319
mental runs and can be seen through the data scatter in
Figure 3.

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Failure Mechanism of HTPB/AP/Al Propellant

Table 2. Mechanical properties of HTPB/AP/Al propellant at differ-

ent strain rates.
1 1 1
Mechanical properties 30 mm min 150 mm min 750 mm min
syield [MPa] 0.25 0.46 0.43
eyield [mm/mm] 0.038 0.053 0.058
E [MPa] 6.58 8.68 7.41
smax [MPa] 0.80 0.96 0.74
emax [mm/mm] 0.305 0.253 0.257

the average stress-strain diagrams from the experimental

test runs and will be discussed in more detail in Section
3.2.
Poisson’s effect was observed in the SEM ETD images on
all of the specimens. As the specimens elongated, their
width decreased. This is seen clearly in e.g. Figure 4 when
comparing the width in Figure 4(0) to Figure 4(7). The re-
duction in width of the sample was on average 7.5 %, 7.9 %
and 8.2 % of the initial width for the strain rates 30, 150
Figure 4. SEM images captured during in-situ uniaxial tensile tests and 750 mm min 1, respectively.
conducted at a strain rate of 30 mm min 1. The number in the During the 30 mm min 1 experiments, a long strain hard-
upper left corner of each picture corresponds with the number of ening phase was present, but no drawing phase was ob-
positions in Figure 3(a). The images were recorded with ETD in served in the stress-strain diagram. The tests were also in
high vacuum. agreement with the micro-mechanistic model of debond-
ing and coalescence of the voids created [9, 15].
At the start of the experiment at the lowest strain rate Figure 5 shows images of the specimen taken at low
tested, the specimen was at a fully relaxed state. This state vacuum with the GAD detector. It is clear when looking at
is shown in Figure 3a point (0). Up to point (1), the yield these images that the large AP particles (ca. 200 mm in di-
point, all the stress that was introduced into the material ameter) separated from the binder and the binder structure
was absorbed by the binder and existing voids. Now
a stress drop occurred to position (2) as shown in Figure 3a.
At this moment some of the interfaces between the large
AP particles and binder debonded, which resulted in a redis-
tribution of the stresses around the particle.
This phenomenon was not clearly observed in Test 2.
This could be due to the inhomogeneous nature of the ma-
terial or that the stress relaxation of the debonding is too
low to measure. From (2) to (3), the voids that were created
by debonding and already existing voids increased, but no
rupture of the binder occurred. All the energy was ab-
sorbed by the binder. At point (3), coalescence of small
voids in the binder occurred, this continued until (4). Now
the stress was distributed sufficiently homogeneously over
the specimen that it was able to hold the load without
having to create new voids or coalescence of voids.
Between (5) and (6), further coalescence occurred, there-
fore showing a stress relaxation in the stress-strain diagram.
Between (6) and (7), an increase in the stress was regis-
tered, which indicated that the stresses around the parti-
cles were low enough to be carried by the binder. After (7),
coalescence of voids occurred until the specimen ruptured. Figure 5. SEM images captured with GAD in low vacuum during
Figure 4(B) shows the sample at its rupture point. in-situ uniaxial tensile tests conducted at a strain rate of
30 mm min 1. Propellant components differ visibly by contrast: Al
The mechanical properties (yield point, elastic modulus,
particles (brightest, white), AP particles (light gray), HTPB binder
maximum stress etc.) of the HTPB/AP/Al propellant at the matrix (dark gray). (a) initial condition; (b) after approximately 5 %
three different strain rates are summarized in Table 2. These elongation; (c) after approximately 10% elongation; (d) at break-
observations and calculations come from Figure 3a–c and ing.

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Full Paper M. C. J. van Ramshorst, G. L. Di Benedetto, W. Duvalois, P. A. Hooijmeijer, A. E. D. M. van der Heijden
opened up. When looking more closely at the fracture sur-
face, it becomes apparent that the binder separated cleanly
from the large AP particles and had greater bonding with
the Al particles.
Figure 6. SEM images captured during in-situ uniaxial tensile tests
conducted at a strain rate of 150 mm min 1. The number in the
upper left corner of each picture corresponds with the number of
positions in Figure 3(b). The images were recorded with ETD in
high vacuum.
Figure 7. SEM images captured during in-situ uniaxial tensile tests
conducted at a strain rate of 750 mm min 1. The number in the
upper left corner of each picture corresponds with the number of
positions in Figure 3(c). The images were recorded with ETD in
high vacuum.
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Figure 8. Progression from point (7) to point (B) in Figure 3(b) of
the rupture of the HTPB/AP/Al propellant at a strain rate of
150 mm min 1. The images show the formation of thin polymer
wires as the voids open up under the tensile load.
Stress as a function of strain of the HTPB/AP/Al propel-
lant specimens at strain rates of 150 and 750 mm min 1 at
25 8C are shown in Figure 3b and c. The effect of the pro-
pellant composition inhomogeneity (as explained in Sec-
tion 2.1) was evident in these experimental runs, and can
be seen through the data scatter in these two plots. The
corresponding SEM ETD images from the video are shown
in Figure 6 and Figure 7. These measurements showed simi-
lar features as the tests at a strain rate of 30 mm min 1,
except that the progression from (5) to rupture could be
considered to be a short drawing phase. Figure 8 shows
the progression from point (7) to point (B) in Figure 6 of
the rupture of the propellant at 150 mm min 1. These
images show the formation of thin polymer wires when
voids open up and coalesce.
Figure 9 shows a feature during the experiment captured
with the GAD. At the beginning, locally, there was no signif-
icant change and the binder was able to hold the stresses
distributing them over the whole specimen. Later, existing
voids opened up in order to release some of the stresses.
Then there was micro-void coalescence in the binder and
this process of growth and coalescence repeated itself until
the last image which was taken right before rupture.
3.2 Mechanical Comparison
During the tests the stress-strain diagrams for each test
were recorded and the average of the recorded stress-
strain diagrams are shown in Figure 10, which represents
the average of three experimental test runs at each strain
rate. As explained in Section 2.1, the effect of the propel-
lant composition inhomogeneity was evident in some of
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Failure Mechanism of HTPB/AP/Al Propellant
Figure 9. SEM GAD images captured approximately every 40 s
[starting at the top left (a), going downwards from left to right,
and ending at the bottom right (p)] during in-situ uniaxial tensile
tests conducted at a strain rate of 750 mm min 1. The images were
recorded with GAD in low vacuum.
Figure 10. Stress-strain diagram of HTPB/AP/Al propellant at a dif-
ferent strain rates. Each stress-strain curve is the average of three
individual measurements.
these experimental runs, and can be seen through the data
scatter in Figure 3a–c.
From the stress-strain diagrams acquired from the experi-
ments, seven points of interest are indicated and shown in
Table 1. No significant strain rate dependency was observed
of the failure mechanism when working with strain rates
up to 750 mm min 1 at 25 8C. Approximately seven indica-
tions were present in the stress-strain diagrams. They con-
sisted of: existing cracks and voids opening up prior to the
creation of new cracks and/or voids in the sample, debond-
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ing of the binder from the larger AP particles and nuclea-
tion and coalescence of voids. On the fracture surfaces of
the samples, it becomes apparent that the binder cleanly
separated from the large AP particles, but had a good
bond with the aluminum particles.
A difference between the strain rates that was observed
was the presence of a short drawing phase in the samples.
The lowest strain rate of 30 mm min 1 experiments had no
indication that a drawing phase occurred. The
150 mm min 1 and 750 mm min 1 experiments did show
a short drawing phase from (5) until rupture. This phenom-
enon is due to the time it takes for the polymers to align
themselves. During the 30 mm min 1 experiments, the poly-
mers have ample time to align themselves during the ex-
periment so only a stress hardening phase is observed after
the yield point. During the 150 and 750 mm min 1 experi-
ments, the strain rate is higher than the polymer alignment
rate. Therefore, a short drawing phase is present in the
stress-strain diagrams of the 150 and 750 mm min 1.
The mechanical properties of the samples determined
from the stress-strain diagrams of the experiments are sum-
marized in Table 2. During the 150 and 750 mm min 1 ex-
periments, the mechanical properties were found to be
very similar. While, during the 30 mm min 1 experiments,
the values found for the yield stress, yield strain and the
elastic modulus were lower. This could once again be due
to the very low strain rate allowing the polymers to align
themselves during the experiment. However, the average
maximum strain during 30 mm min 1 experiments was
slightly higher than the average maximum strain of the
750 mm min 1 experiments.
Prasad et al. [16] presented a systematic study of the
effect of the formulation ingredients and the process pa-
rameters on the fracture toughness of HTPB-based compo-
site solid propellants, containing AP. Macroscopic stress-
strain diagrams at a constant crosshead speed of
50 mm min 1 were recorded on dogbone-shaped propel-
lant samples that varied in e.g. hydroxyl-content of the
HTPB, type of curing agent, curing time, curing catalyst,
and coarse/fine ratio of AP particles etc. The macroscopic
stress-strain diagrams all showed the same, global behav-
ior: a linear stress-strain region at strains up to approx. 10–
20 %, an intermediate region, in which the stress-strain de-
pendence flattens (from ca. 10–20 % to approx. 35–90 %), fi-
nally followed by failure of the specimen. Obviously, the
strain rate of 50 mm min 1 used by Prasad et al. [16] is
much higher than the maximum strain rate used in this
study (750 mm min 1 and lower). Because of the much
lower strain rate in combination with the smaller sample
size scaled down with a factor of four compared to the
conventional dimensions of a dogbone, it is expected that
sample inhomogeneities and relaxation effects show up
much more dominantly in the microscopic tensile tests
than in the macroscopic tensile tests. This implies that the
microscopic stress-strain diagrams cannot be interpreted in
the same way as the stress-strain relations that have been
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Full Paper M. C. J. van Ramshorst, G. L. Di Benedetto, W. Duvalois, P. A. Hooijmeijer, A. E. D. M. van der Heijden
measured on a macroscopic level. The main advantage of
the microscopic tensile tests therefore lies in the unique
possibility to combine a tensile test with microscopic ob-
servations of the mechanical deformation processes taking
place in the sample at a microscopic level, since this pro-
vides much more insight in the (local) failure mechanisms
of propellant samples, or more generally, highly filled elas-
tomers, when subjected to a tensile force.
4 Conclusions
In-situ uniaxial tensile experiments of HTPB/AP/Al propel-
lant specimens were successfully conducted within a SEM
at 25 8C. Each experiment included real-time observation at
the micron-level of the specimen and digital recording of
the stress and strain values. The stress-strain diagrams were
consistent for each specimen, regardless of the strain rate
used.
Stress relaxation of the specimens was present in the
stress-strain diagrams due to nucleation of cracks and voids
in the specimen during experimentation. The in-situ SEM
observance, images and videos confirmed the nucleation
and growth of cracks and voids in all of the specimens.
The SEM images captured using the ETD show an excel-
lent representation of the full width of the specimens,
while the SEM images captured using the GAD show highly
detailed evidence of the specimen microfeatures as the ex-
periment occurred. Poisson’s effect on the specimens was
observed in the SEM ETD images. As the specimens elon-
gated, their width decreased (between 7.5 % and 8.2 % on
average compared to the initial width of the specimen over
all three strain rates). SEM GAD images show details of the
AP and Al particles interface with the HTPB binder matrix.
The HTPB binder matrix detached from the large AP parti-
cles cleanly, while the HPTB binder matrix appeared to
adhere well to the Al particles. The nucleation, growth and
coalescence of cracks and voids and the detaching of the
HTPB binder matrix from the AP particles in the specimens
continued throughout the experiment until the point of
rupture.
The strain hardening and drawing phases in the samples
changed at different strain rates. This phenomenon is due
to the time it takes for the polymers to align themselves.
During the 30 mm min 1 experiments, the polymers have
ample time to align themselves during the experiment so
no drawing phase is observed. During the 150 and
750 mm min 1 experiments, the strain rate is higher than
the polymer alignment rate. Therefore, a short drawing
phase is present in the stress-strain diagrams of the experi-
ments performed with 150 and 750 mm min 1.
Through in-situ SEM observance, images and videos, the
interface of the HTPB binder matrix and the AP particle was
found to be the main source of failure in the HTPB/AP/Al
propellant specimens while under tensile stress.
&8& www.pep.wiley-vch.de  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!
The results presented herein have clearly demonstrated
the major advantage of the combination of microscopic
tensile tests with microscopic observations of the localized
mechanical deformation processes taking place in these
samples. This unique possibility will contribute to an in-
creased understanding of the (local) failure mechanisms of
propellant samples, or more generally, highly filled elasto-
mers, subjected to a tensile force. The tensile module
opens up the potential for many future studies, e.g. study-
ing the mechanical behavior at non-ambient temperatures,
aging effects, binder/particle ratio and particle size effects,
and the optimization of a propellant composition regarding
the selection and development of improved bonding
agents.
Acknowledgments
The authors acknowledge Peter Kuivenhoven at TNO Rijs-
wijk for providing the experimental samples used in this
study. The authors also acknowledge Frans-Peter Weterings
and Jean-Luc Moerel of TNO Rijswijk for providing the pro-
pellant, indicating propellant properties, and sharing their
experience with macrotensile testing.
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Received: October 5, 2015
Revised: February 29, 2016
Published online: && &&, 0000
 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim &9&
These are not the final page numbers! ÞÞ
Full Paper M. C. J. van Ramshorst, G. L. Di Benedetto, W. Duvalois, P. A. Hooijmeijer, A. E. D. M. van der Heijden

FULL PAPERS
M. C. J. van Ramshorst,
G. L. Di Benedetto, W. Duvalois,
P. A. Hooijmeijer,
A. E. D. M. van der Heijden*
&& – &&
Investigation of the Failure
Mechanism of HTPB/AP/Al
Propellant by In-situ Uniaxial Tensile
Experimentation in SEM

&10& www.pep.wiley-vch.de  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/prep.201500264
ÝÝ These are not the final page numbers!