Full Paper
DOI: 10.1002/prep.201200186
Aging of HTPB/Al/AP Rocket Propellant Formulations
Investigated by DMA Measurements
Sara Cerri,[a] Manfred A. Bohn,*[b] Klaus Menke,[b] and Luciano Galfetti[c]
Abstract: Three HTPB-based rocket propellant formulations
containing ammonium perchlorate and aluminum particles,
with different aluminum content and particle size, have
been manufactured. The study has focused on the change
of mechanical properties with aging time by using dynamic
mechanical analysis (DMA). Therefore, propellant formula-
tions underwent an accelerated aging program, in air (RH <
10 %), between 60 8C and 90 8C with aging time adjusted to
a thermal equivalent load of 15 to 20 years at 25 8C. DMA
investigations revealed distinct changes in the shape of the
Keywords: Aging DMA measurements HTPB/Al/AP-based rocket propellant formulations Exponentially modified Gauss distribution
Loss factor modeling
1 Introduction
Solid rocket propellant (SRP) formulations based on ammo-
nium perchlorate (AP), aluminum (Al) and a weakly cross-
linked binder such as hydroxyl terminated polybutadiene
(HTPB) or similar pre-polymers are the main type used in
the current western propellant boosters, because they are
able to achieve high performance with high specific gravi-
metric and volumetric impulses.
In general, such SRPs are relatively resistant to aging
compared to nitrocellulose-based propellants. However,
they change their properties with time, which means they
age during storage and handling. Aging mechanisms with
such materials are: after curing, chain scission by mechani-
cal overload during temperature cycling, oxidative harden-
ing, if the antioxidant is not protective enough, together
with loss in strain capability, oxidative chain scission and
dewetting between fillers and binder matrix, especially
with the coarse AP.
During the in-service time period a solid rocket motor
has to withstand a series of different loads. All the boun-
dary conditions strongly influence the material perfor-
mance and failure types. Currently solid rocket motor users
rely on destructive testing for determining the residual in-
service time of the considered systems. Materials used for
the surveillance program are often taken from operational
assets. The procedure is quite expensive and changes to
the aging surveillance activities are taking place [1].
In this study, the aging of three HTPB/Al/AP formulations
having different aluminum size and content was investigat-
ed with dynamical mechanical analysis (DMA) in torsion
190  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
loss factor curve. These curves were modeled with three ex-
ponentially modified Gaussian (EMG) functions in order to
get the molecular interpretation of the involved aging phe-
nomena by separating the binder fractions with different
mobility. Aging of propellant formulations can be followed
by considering only two parameters: the areas of the
second and third loss factor transition peaks (A2, A3), and
the corresponding maximum temperature values of the as-
signed Gauss peaks (Tc2, Tc3).
mode. The accelerated aging range was between 60 8C and
90 8C with aging times adjusted to a thermal equivalent
load of 15 to 20 years at 25 8C.
2 Experimental Section
2.1 Formulations
Three HTPB/Al/AP-based propellant formulations, manufac-
tured at Fraunhofer ICT, were investigated: AV03 and AV05
contain 6 mass-% of Al, whereas the formulation named
AV04 has 12 mass-% of Al. Propellants AV03 and AV04 have
micrometric aluminum (Alcan, Grade X-81, 8 mm, Eckart,
Austria). Propellant AV05 contains only nanometric alumi-
num (ALEX, 100200 nm, USA). All AV-propellants contain
84 mass-% of solid load: AP (78 mass-% odd-numbered, 72
mass-% even-numbered) as oxidizer, aluminum as fuel,
DOA as plasticizer (4 mass-%), HX-878 (Mach I, USA) as
bonding agent for AP (0.19 mass-%), Irganox 565 as antioxi-
[a] S. Cerri
Independent consultant, 28060, Cureggio, Italy
[b] M. A. Bohn, K. Menke
Fraunhofer Institut fuer Chemische Technologie (ICT), 76318,
Pfinztal-Berghausen, Germany
*e-mail: Manfred.Bohn@ict.fraunhofer.de
[c] L. Galfetti
Dipartimento Ing. Aerospaziale, Politecnico di Milano, 20156,
Milano, Italy
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Aging of HTPB/Al/AP Rocket Propellant Formulations Investigated by DMA Measurements
Table 1. Applied accelerated aging conditions (time and tempera-
ture) simulating an in-service time of up to 20 years at 25 8C.
Natural or in-service aging
In-service temperature TE [8C] In-service time tE [a]
25 5 10 15
Accelerated aging conditions based on TEL with F = 2.5 in GvH
Aging temperature TT [8C] Aging timea) tT [d]
90 5 10 15
85 7.5 15 22.5
80 12 25 40
70 30 60 90
60 75 150 225
a) Given aging times are rounded up.
dant and isophorone diisocyanate (IPDI) as curing agent
(0.89 mass-%). A curing catalyst (D22 or DBTDL) was added.
The equivalent ratio (Req = NCO/OH) was maintained con-
stant at 0.87.
All formulations were prepared in a vertical kneader
(Drais T FHG, Germany) having a 5 L volume and cured in
an electrical oven cabinet (company Memmert, Germany)
for 2 days at 60 8C.
2.2 Sample Preparation and Aging Conditions
Samples were aged from 60 8C to 90 8C in air, with RH <
10 % and in load-free conditions (no effects of stress and/or
strain caused by the motor case are occurring) to simulate
15 to 20 years of natural aging. The thermal accelerated
aging program was carried out in PID temperature con-
trolled ( 0.3 8C) aging ovens (design based on former com-
pany Julius Peter, Germany). To establish the aging plan the
principle of Thermal Equivalent Load (TEL) was used to-
gether with the generalized vant Hoff rule (GvH) [2, 3].
Table 1 shows the aging conditions determined using a scal-
ing factor F = 2.5 per 10 8C temperature change.
The study has focused on the accelerated aging of the
surface-layer of SRPs, which means no in core analysis
was intended. Therefore the sampling did not follow the
STANAG 4581 [4]. The specimen geometry was already the
one suitable for the DMA measurements, here small rectan-
gular bars: 10 mm wide, 4 to 5 mm thick, 50 mm long.
DMA samples were stored in glass tubes having ground
glass stoppers. Stoppers were not fixed with a clamp and
not sealed by grease. Twice a week, stoppers were re-
moved to let fresh air to flow inside.
2.3 DMA Measurements
All DMA measurements were carried out in torsion mode
using a DMA instrument of type ARESTM (Advanced Rheo-
metric Expansion System) manufactured by Rheometric Sci-
Propellants Explos. Pyrotech. 2013, 38, 190 198  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
entific (now belonging to Waters Inc., BU TA Instruments).
A liquid nitrogen cooling accessory was used for the low
and high temperature operations. The investigated temper-
ature range was 100 8C to + 70 8C, with heating up in
steps of 1 8C min1 and a soak time of 28 s. Specimens were
20 tested at four deformation frequencies (0.1, 1, 10, 56 Hz)
using a strain control with maximum strain of 0.0012, in
order to be in the linear range domain, which means the
modulus is independent of strain. Measurement reproduci-
bility is very high, so only one sample per each test condi-
20 tion was used. In case of anomalous behavior a second
30 measurement was performed.
50
120
300
3 Results
HTPB-based propellants show no simple thermo-rheological
behavior [57] due to the presence of secondary relaxation
phenomena appearing at higher temperature. Each investi-
gated AV0x formulation shows two apparent maxima. The
pure binder shows a similar tand curve structure [8].
The intensity of the second peak is influenced by the
plasticizer content and by Req. By fixing both of these pa-
rameters the viscoelastic properties of the polymeric mate-
rial are strongly influenced by the presence of fillers by
their following properties: morphology, particle size, sur-
face characteristic (presence of OH-groups), and binder
filler interactions.
Figure 1 shows the trend of the loss factor (tand = G/G,
where G is the storage modulus and G is the loss modu-
lus) of AV04 with aging. The same considerations can be
applied for the other investigated formulations. For every
aging time the presence of two maxima can be seen. Both
peaks are shifted to higher temperatures by increasing the
deformation frequency, which means by increasing the de-
formation rate. The first maximum is located between
80 8C and 60 8C, depending on the applied deformation
frequency. The second maximum is broader than the first
one and appears at higher temperature values [3]. The loss
factor is a composed distribution function (non-normalized
density function) describing the distributions of the glass
transitions of the structural elements of the propellant
polymer networks. The first maximum, also called main
peak, is associated with the glass transition of the HTPB
main chain elements, the so-named soft-segment units
[5, 6], where the main chain molecular motion ceases or
starts. The temperature corresponding to the maximum of
the peak is called Tgunrest. The second peak is related to the
motions within the range of the short hard-segment units
(urethane groups) and/or strongly mobility restricted soft-
segment regions, caused by the presence of fillers and by
binder-filler interactions [5, 6, 912]. In order to highlight
the restriction, the temperature corresponding to the maxi-
mum of the second peak was named Tgrest. The different
nature of these two relaxation phenomena can also be
seen considering the apparent activation energy (E a* ) ob-
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Figure 1. Loss factor tand and storage modulus G vs. measurement temperature for AV04 formulation as function of aging at 70 8C.
Table 2. Apparent activation energy (Ea*) of the first and second peak of the unaged AV03, AV04, and AV05 propellant formulations using
the data from all four applied deformation frequencies [13].
First peak
Ea*(Tgunr) [kJ mol1] log(f0(Tgunr) [Hz])
AV03 136  9 35.08  2.22
AV04 149  9 38.55  2.31
AV05 155  11 40.01  2.82
tained from the shift of the temperature values of the
maxima with deformation frequency [13] (Table 2).
The thermal history of the material does not influence
the position and shape of the first tand peak. Values of
Tgunrest are only slightly influenced by aging. This result
agrees with the DSC measurements [3]. Instead, remarkable
changes were found for the second peak [6, 12, 14] and for
the value of the storage shear modulus. G increases with
aging, whereas the values of tand decrease. In particular,
the area under the tand curves decreases. Other studies
have been carried out in order to follow the aging of pro-
pellant formulations with DMA measurements. Husband
[15] has found a linear relationship between log(G) and the
aging time. The aging rate was temperature dependent. An
activation energy of about 200 kJ mol1 between 60 8C and
80 8C was obtained. De la Fuente et al. [6] also found a tem-
perature dependence of the aging rates obtained from the
E and tand measurements. The activation energy was not
evaluated, but the authors noticed that the area under the
second peak decreased with aging. Ashcroft et al. [14] have
not only observed that the height and position of the
second peak tend to change with aging, but also evaluated
the area under the second peak (however, no baseline cor-
rection was applied) and found that a strong correlation
between this value and the aging time and temperature
exists. Unfortunately the activation energy was not evaluat-
192 www.pep.wiley-vch.de  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
S. Cerri, M. A. Bohn, K. Menke, L. Galfetti
Second peak
R2(Tgunr) Ea*(Tgr) [kJ mol1] log(f0(Tgr) [Hz]) R2(Tgr)
0.996 74  5 14.87  0.96 0.996
0.996 79  5 15.46  0.95 0.996
0.995 77  4 15.04  0.76 0.997
ed. In the present study, aging was followed by evaluating
the area of the second peak after a baseline correction.
3.1 Modeling of the Loss Factor Curve Baseline Correction
The energy used during the DMA measurements is partly
transmitted loss free from the donor to the acceptor of the
specimen holder, and partly used by the propellant speci-
men. This second part has two contributions: a purely dissi-
pative one in which the energy is transformed to heat by
frictional effects inside the sample, and a contribution used
for the molecular rearrangements of the binder network.
The rearrangement energy is taken up to separate molecu-
lar chains in the energy elastic state to allow multiple con-
figurations in the entropy determined state and, on the
other side, to overcome diffusion barriers in the entropy
elastic state to reach the optimal arrangements for the
energy determined state. Outside the glass transition re-
gions only dissipative consumptions occur, which are usual-
ly small, particularly in the energy-elastic state. For filled
elastomers the dissipative effects can become significant in
the entropy-elastic state [8]. Thermoplastic and weakly
cross-linked polymers change from a glass-like to rubber-
like behavior as the temperature is increased. In the glassy
state, at low temperature, the behavior is related to
changes in the stored elastic energy by small displace-
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Aging of HTPB/Al/AP Rocket Propellant Formulations Investigated by DMA Measurements
Figure 2. Baseline correction of the loss factor of the AV04 unaged
propellant formulation.
ments of atoms and atom groups from their equilibrium
positions. In the rubbery state, at high temperature, molec-
ular chains have much more flexibility because of increased
free volume and can adopt a large number of chain confor-
mations, which lead to a maximum of entropy. Scanning
the temperature from one state region to the other one,
the material goes across an intermediate region, where the
changes occur in molecular arrangements. Generally this
phenomenon is named glass transition region.
A visual sign for the dissipative part is the baseline offset
between the start and the end point of the loss factor
curve (Figure 2). The separation of the dissipative part can
be done by applying a suitable iterative baseline correction
function (BLC) shown in Equation (1), using a transient
function a(T), Equation (3), which is a cumulative partition
variable, to adjust the baseline weights along the loss
factor curve. The BLC function considers that on both sides
the loss factor curve ends in plateau values. This is not the
case in using a straight line as BLC. The formula can take
into account also small non-plateau situations by including
the slopes.
BLa(T) Baseline correction function based on a(T) be-
tween Ta and Tb ;
a(T) Cumulative distribution of tand(T), [];
Propellants Explos. Pyrotech. 2013, 38, 190 198  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Figure 3. Baseline corrected loss factor vs. temperature at different
aging times for the aged AV04 formulation (aging temperature
was 70 8C).
tand(Ta) Value of uncorrected tand(T) at temperature Ta,
[];
tand(Tb) Value of uncorrected tand(T) at temperature Tb,
[].
Ta Lower baseline setting temperature with slope Sa,
[8C] in tand(Ta);
Tb Upper baseline setting temperature with slope Sb,
[8C] in tand(Tb);
Tst Scaled temperature T, [8C];
T Measurement temperature between Ta and Tb,
[8C];
Sa Slope at Ta in tand(Ta), [8C1];
Sb Slope at Tb in tand(Tb), [8C1];
Baseline corrected loss factor curves are presented in
Figure 3. The iteration procedure is fast and stable. Usually,
already after 5 to 6 cycles the final BLC curve is obtained.
3.2 Modeling of the Loss Factor Curve Evaluation with
Distribution Function
After the baseline correction a suitable function must be
chosen in order to separate and evaluate the area under
the peaks. Some distribution functions have been analyzed
in another paper [16]. The function must describe the ex-
perimental data and extract from them the indications for
the different regions of molecular rearrangement processes
corresponding to the elastomer fractions with different mo-
bility. If the values of the molecular interaction energies
and of molecular docking regions are randomly distributed
in the isotropic material, a Gauss distribution should de-
scribe the processes, Equation (4). Loss factor curves of the
investigated materials are not symmetrical as a Gauss distri-
bution, which means that the data still contain some dissi-
pative parts. These dissipative effects can be considered
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with relaxation curves, which are mostly represented by ex-
ponentially decreasing functions, Equation (5).
The combined processes have been described by an ex-
ponentially modified Gauss distribution function (EMG)
[12], which is a convolution between Equation (4) and (5).
Due to the fact that the whole loss factor curve is com-
posed of several molecular rearrangement types originating
from different mobility of several binder fractions, a sum of
the fitting functions is shown in Equation (6).
T Measurement temperature, [8C];
tandBLC Loss factor curve after the BLC as function of T,
[];
Ai Peak areas of the EMG peaks i, also equal to the
area of the Gauss peak i alone, [8C];
wi Half peak width at half height of only Gaussian
part i, [8C];
Figure 4. Description of the loss factor of the unaged AV04 propellant formulation with three EMG functions.
194 www.pep.wiley-vch.de  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
S. Cerri, M. A. Bohn, K. Menke, L. Galfetti
Tci Temperature at peak maxima in the Gaussian part
i of EMG (not the peak maxima of EMG), [8C];
ti Relaxation parameter in exponential part i of EMG,
[8C]; in Figure 4 ti is named Toi
td0 Residual offset in tand data (for these evaluations
the value was set to 0), [];
N Number of EMG fit functions;
erf Error function.
Equation (6) is adjusted to the baseline corrected data by
non-linear fit algorithm with N equal to the numbers of ex-
tractable mobility regions. A LevenbergMarquardt algo-
rithm was used provided by the OriginTM program package
[17].
The use of only two EMGs could not describe the valley
region very well between the two apparent peaks [16],
therefore a value of N equal to 3 was used. The loss factor
description of the unaged AV04 propellant formulation
with three EMGs is shown in Figure 4. Now the previously
not apparent third peak is clearly defined. The same data
treatment was done also for the other two unaged and
aged formulations (AV03, AV05), in order to follow the mo-
lecular changes with aging.
By plotting the values of the peak areas vs. the aging
time, different tendencies can be highlighted (Figure 5).
The area of the first transition (A1) stays quite constant with
aging, whereas the other two show a tendency to increase
(A3) and to decrease (A2). The change of these areas (Ai) can
be described by a formal rate equation of zero order, Equa-
tion (7).
Propellants Explos. Pyrotech. 2013, 38, 190 198
Aging of HTPB/Al/AP Rocket Propellant Formulations Investigated by DMA Measurements

For the investigated formulations the following equa-

tions were considered:

A2 t,T A2 0 S  kA2T  t; S 1 9

A3 t,T A3 0 S  kA3T  t; S 1 10

A linear dependence of A2(t) and A3(t) with aging time

was observed.
By plotting the natural logarithm of the slopes named
ln(kAi) of these lines vs. 1/T (temperature is in [K]) as shown
in Figure 6, Equation (11), values of the activation energies
Ea are obtained (Table 3). The same aged formulations were
Figure 5. Trends of peak areas with aging time for AV04 propel- also investigated with other experimental techniques,
lant. namely sol-gel analysis (SGA) and gel permeation chroma-
tography (GPC), and the activation energies were evaluat-
ed. The values of all the activation energies are the same
kAi(T) Change rate constant for area Ai, [8C d1];
considering the accuracy of determinations [18].
S Sign factor, S is 1 for decreasing area with time, S
is + 1 for increasing area with time. Because the areas Ai have the unit [8C], the decrease rates
have the unit 8C/time here [8C d1].
The integration of Equation (7) gives:

Ai t,T Ai 0 S  kAiT  t 8

Figure 6. Time and temperature dependence of the peak areas of the second transition peak (A2).

Table 3. Arrhenius parameters for rate constants of change of the peak areas A2 and A3 with aging for AV03, AV04, and AV05 propellant
formulations.
Transition 2 with area A2 Transition 3 with area A3
1 1
Ea(A2) [kJ mol ] log(Z(A2)[8C d ] 2
R (A2) Ea(A3) [kJ mol1] log(Z(A3)[8C d1)] R2(A3])
AV03 70.1  7 9.223  0.96 0.996 69.3  6 9.128  0.82 0.994
AV04 77.8  3 10.458  0.44 0.999 95.0  10 12.769  1.48 0.990
AV05 76.1  5 10.356  0.72 0.996 72.3  20 9.167  3.00 0.931

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Figure 7. Trends of maximum temperature values Tci with aging time for propellant AV04.
Considerations can be applied also for the change of
values with aging of the maximum temperature Tci, which
corresponds to the peak maxima of the Gauss parts
(Figure 7). The temperature of the first transition (Tc1) stays
quite constant with aging, whereas the other two parame-
ters show a tendency to increase (Tc2) and to decrease (Tc3)
with aging time [8].
4 Discussion
4.1 Meaning of Loss Factor
A molecular interpretation of the viscoelastic behavior con-
sidering the loss factor and the glass transition temperature
(Tg) is given in the following. The term glass transition de-
fines a temperature induced transition region of an amor-
phous polymer phase from its energy-elastic state to its en-
tropy-elastic one, and vice versa. The reason is to reach
always an energetic minimum, here in Gibbs free energy
DG, Equation (12).
DGp,T DHp,TT  DSp,T 12 pointed out the possibility of extracting information from
In the energy-elastic state the internal energy is con-
trolled by lattice like energetic interactions between poly-
mer molecules. The enthalpy term, DH, controls the Gibbs
free energy. Because of lower temperature values the free
volume is reduced and distances between polymer chains
are small. Therefore the mobility is restricted and local
dipole-dipole interactions have a strong effect in lowering
the internal free energy: the enthalpy DH becomes appreci-
ably negative. The entropy term plays nearly no role, be-
cause there are little configuration changes of polymer
chains and it is significantly smaller than the enthalpy term.
On the contrary, in the entropy-elastic state the internal
energy is not controlled by lattice like energetic interac-
196 www.pep.wiley-vch.de  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
S. Cerri, M. A. Bohn, K. Menke, L. Galfetti
tions. The increased available free volume at higher tem-
perature values gives molecules more possibilities to realize
many configurations, which means that the entropy in-
creases. The term T DS in Equation (12) gets more positive
and DG gets more negative and the entropy term T DS
controls now the Gibbs free energy. The enthalpy DH in-
creases, which means it is less negative than in the energy-
elastic state. It plays now nearly no role, its value varies
only a little because the distances between chain elements
have increased. Local dipole-dipole interactions are less ef-
fective because of averaging out [19] by the thermal move-
ments of the chain elements. Any effect that reduces the
possibility of realizing polymer chain configurations (pres-
ence of filler and binder-filler interactions) will reduce the
entropy part and increase the enthalpy part by making the
material less entropy elastic and strain capability should
become smaller.
4.2 DMA Modeling
The procedure used to analyze DMA measurements has
the loss factor curve. The considered EMG modeling is not
specific to the investigated formulations but it can be used
for other pre-polymers [20], as well as for other fillers [19],
as it was done in Ref. [12]). The baseline correction of the
data is necessary to get a quantification of the individual
contribution of the different mobility ranges and mobility
types. Without this procedure, the fitting would not be suc-
cessful and the contributions of the ranges would be
wrongly weighed.
Three main relaxation processes are embedded in the
HTPB binder systems, corresponding to binder fractions
with different mobility. The N extractable mobility ranges
are obtained with the use of N EMG functions. The number
of fit parameters is equal to N times 4, where 4 is the
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Aging of HTPB/Al/AP Rocket Propellant Formulations Investigated by DMA Measurements
number of the EMG parameters, namely: Ai, wi, Tci, Toi. They
must be found in a unique way. This is possible due to the
in-built limitations of the EMG function in reproducing the
curve shape, which means that the EMG contains the con-
straints within its mathematical structure and cannot de-
scribe any shape. However, the necessary curve structure
must be in the data in order to correctly determine the pa-
rameters [19].
Other authors have modeled the loss factor curve with
some phenomenological models. The model presented by
Nevire et al. [21] is based on the assumption that there
are two coexisting species in the propellant polymer net-
work, which are statistically distributed, and each one is re-
sponsible of a particular peak. With this model the loss
factor (without BLC) was modeled with the sum of two
Gaussian functions. Tsagaropoulos et al. [12] have observed
the presence of a tail on the right side of the loss factor of
several polymers filled with very fine silica particles. Due to
this asymmetry the loss factor was modeled with two EMG
functions.
4.3 Interpretation of the Transition Regions
The increasing transition intensity of peak 3 indicates an in-
crease in free volume or less mobility restriction by interac-
tions between particles and binder chains. Also chain split-
ting could help to lower mobility restrictions. The active Al
particle surface can sustain the oxidative chain splitting
and thus lowering the mobility restrictions. Also surface
modifications of the Al particles should be taken into ac-
count. Residual water can support the dissolving of the
bonding agent from the AP surface.
The explanation for the changes in peak 2 is the follow-
ing. The not bonded chains extracted by SGA and analyzed
by GPC are cross-linked to the binder during ageing, which
reduces the free volume in the urethane bonding regions,
in spite of some chain scission occurring. This leads to
a more rigid phase, which corresponds to a reduction in
loss factor intensity of area A2 and in slight shift of the
maximum of the corresponding loss factor part to higher
temperature values.
The time-temperature evolution of the loss factor can
have many causes. During the oxidative aging two compet-
itive processes take place: chain scission and chain (re)com-
bination with cross-linking [22]. A loss factor decrease
means the presence of recombination reactions leading to
the formation of more cross-linked, and therefore more
rigid three-dimensional network. A loss factor increase char-
acterizes an increase of the macromolecular mobility, which
can be caused by chain scission [23] and/or by dewetting
between binder and filler particles [24]. Additional informa-
tion on changes in tand and their causes can be found in
Refs. [19, 25]. SEM images presented in a previous work
[16] have not evidenced the presence of clear dewetting
phenomena with respect to AP particles in the investigated
aged propellant formulations, therefore chain scission is
Propellants Explos. Pyrotech. 2013, 38, 190 198  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
seen as the main, but not the only one, cause to explain
this trend. The analysis of the EMG modeling with three
molecular transitions allows to recognize the presence of
these two competitive processes and to follow their trend
with aging: the decrease of A2 with aging can be associat-
ed with a decrease of the molecular mobility (cross-linking),
whereas the increase of A3 is assigned to chain scission
causing an increase of free volume in the binder shell
around the filler particles.
5 Conclusion
DMA in torsion mode was employed to investigate the
aging behavior of three HTPB-based SRP formulations
having different aluminum particle size and content. The
accelerated aging range was between 60 8C and 90 8C with
aging times adjusted to a thermal equivalent load of 15 to
20 years at 25 8C. For this correlation the generalized vant
Hoff rule was applied with F = 2.5. DMA measurements evi-
denced the simultaneous presence of two competitive pro-
cesses: chain scission and cross-linking. An Arrhenius pa-
rameterization was done and the activation energies ob-
tained are similar in values with the ones obtained with
SGA and GPC, reported in another paper [18].
Loss factor curves were modeled with 3 EMG functions
in order to get a molecular or microscopic interpretation of
the involved phenomena in the binder. Aging of the pro-
pellant formulations can be followed by considering two
parameters, namely: the areas of the second (A2) and third
(A3) transition peaks, and the corresponding temperature
values of the assigned Gauss peaks called Tc2 and Tc3. The
modeling has also shown that the glass transition tempera-
ture of the apparent second peak (Tgrest) is composed of
two different molecular phenomena represented by the
transition temperature values Tc2 and Tc3. More detailed
analysis can be achieved by the investigation of specifically
tailored model formulations designed to pronounce specif-
ic effects and allow an indirect evaluation of molecularly
based phenomena [8, 13]. A further cause of cross-linking
could be oxidative attack on the amino groups of the
bonding agent for AP.
Symbols and Abbreviations
Al Aluminum, fuel
AP Ammonium perchlorate, oxidizer
BLC Baseline correction
DBTDL Di n-butyltin dilaurate (also named D22)
DOA Dioctyl adipate, plasticizer
DSC Differential scanning calorimetry
Ea Activation energy, [kJ mol1]
EMG Exponentially modified Gaussian
EOMV End of mix viscosity
GPC Gel permeation chromatography
www.pep.wiley-vch.de 197
Full Paper S. Cerri, M. A. Bohn, K. Menke, L. Galfetti

GvH Generalized vant Hoff rule [9] R. F. Boyer, Dependence of Mechanical Properties on Molecu-
HTPB Hydroxyl terminated polybutadiene lar Motion in Polymers, Polym. Eng. Sci. 1968, 8.
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the Factors Affecting the Two Glass Transition Behavior of
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SGA Sol-gel analysis omers, Macromolecules 1995, 28, 6067 6077.
SRP Solid rocket propellant [13] S. Cerri, Characterisation of the Ageing of Advanced Solid
TE In-service temperature, [8C] Rocket Propellants and First Step Design of Green Propellants,
tE In-service time, [a] PhD Thesis, Politecnico di Milano, Dipartimento di Energia,
TEL Thermal equivalent load Dottorato di Ricerca in Energetica, XXII ciclo, 2011.
[14] M. Ashcroft, T. Cunliffe, R. Dale, C. Hobman, K. Rawley, D. Tod,
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P. Wylie, Oxidative Ageing of HTPB-Based Composite Propel-
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tT Aging time, [d]. ruhe, Germany, June 2427, 2008.
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[16] S. Cerri, M. A. Bohn, K. Menke, L. Galfetti, Ageing Behavior of
Composite Rocket Propellant Formulations, 3rd European Con-
This work was carried out as part of the PhD Thesis of Sara Cerri
done at Politecnico di Milano, Energy Dept. (Italy) and Fraunhofer ference for Aerospace Science (EUCASS), Versailles, France, July
ICT (Germany) [13]. Authors would like to thank both institutions. 69, 2009.
[17] Origin Version 7.0 (German), SR 4, v7.0552, Data Analysis and
Graphing Software, OriginLab Corporation, Round House
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198 www.pep.wiley-vch.de  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Propellants Explos. Pyrotech. 2013, 38, 190 198