Anda di halaman 1dari 9

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 loss factor curve. These curves were modeled with three ex-
containing ammonium perchlorate and aluminum particles, ponentially modified Gaussian (EMG) functions in order to
with different aluminum content and particle size, have get the molecular interpretation of the involved aging phe-
been manufactured. The study has focused on the change nomena by separating the binder fractions with different
of mechanical properties with aging time by using dynamic mobility. Aging of propellant formulations can be followed
mechanical analysis (DMA). Therefore, propellant formula- by considering only two parameters: the areas of the
tions underwent an accelerated aging program, in air (RH < second and third loss factor transition peaks (A2, A3), and
10 %), between 60 8C and 90 8C with aging time adjusted to the corresponding maximum temperature values of the as-
a thermal equivalent load of 15 to 20 years at 25 8C. DMA signed Gauss peaks (Tc2, Tc3).
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- mode. The accelerated aging range was between 60 8C and
nium perchlorate (AP), aluminum (Al) and a weakly cross- 90 8C with aging times adjusted to a thermal equivalent
linked binder such as hydroxyl terminated polybutadiene load of 15 to 20 years at 25 8C.
(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. 2 Experimental Section
In general, such SRPs are relatively resistant to aging 2.1 Formulations
compared to nitrocellulose-based propellants. However,
they change their properties with time, which means they Three HTPB/Al/AP-based propellant formulations, manufac-
age during storage and handling. Aging mechanisms with tured at Fraunhofer ICT, were investigated: AV03 and AV05
such materials are: after curing, chain scission by mechani- contain 6 mass-% of Al, whereas the formulation named
cal overload during temperature cycling, oxidative harden- AV04 has 12 mass-% of Al. Propellants AV03 and AV04 have
ing, if the antioxidant is not protective enough, together micrometric aluminum (Alcan, Grade X-81, 8 mm, Eckart,
with loss in strain capability, oxidative chain scission and Austria). Propellant AV05 contains only nanometric alumi-
dewetting between fillers and binder matrix, especially num (ALEX, 100200 nm, USA). All AV-propellants contain
with the coarse AP. 84 mass-% of solid load: AP (78 mass-% odd-numbered, 72
During the in-service time period a solid rocket motor mass-% even-numbered) as oxidizer, aluminum as fuel,
has to withstand a series of different loads. All the boun- DOA as plasticizer (4 mass-%), HX-878 (Mach I, USA) as
dary conditions strongly influence the material perfor- bonding agent for AP (0.19 mass-%), Irganox 565 as antioxi-
mance and failure types. Currently solid rocket motor users
[a] S. Cerri
rely on destructive testing for determining the residual in- Independent consultant, 28060, Cureggio, Italy
service time of the considered systems. Materials used for
[b] M. A. Bohn, K. Menke
the surveillance program are often taken from operational
Fraunhofer Institut fuer Chemische Technologie (ICT), 76318,
assets. The procedure is quite expensive and changes to Pfinztal-Berghausen, Germany
the aging surveillance activities are taking place [1]. *e-mail: Manfred.Bohn@ict.fraunhofer.de
In this study, the aging of three HTPB/Al/AP formulations [c] L. Galfetti
having different aluminum size and content was investigat- Dipartimento Ing. Aerospaziale, Politecnico di Milano, 20156,
ed with dynamical mechanical analysis (DMA) in torsion Milano, Italy

190  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Propellants Explos. Pyrotech. 2013, 38, 190 198
Aging of HTPB/Al/AP Rocket Propellant Formulations Investigated by DMA Measurements

Table 1. Applied accelerated aging conditions (time and tempera- entific (now belonging to Waters Inc., BU TA Instruments).
ture) simulating an in-service time of up to 20 years at 25 8C. A liquid nitrogen cooling accessory was used for the low
Natural or in-service aging and high temperature operations. The investigated temper-
In-service temperature TE [8C] In-service time tE [a] 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
25 5 10 15 20 tested at four deformation frequencies (0.1, 1, 10, 56 Hz)
using a strain control with maximum strain of 0.0012, in
Accelerated aging conditions based on TEL with F = 2.5 in GvH order to be in the linear range domain, which means the
modulus is independent of strain. Measurement reproduci-
Aging temperature TT [8C] Aging timea) tT [d]
bility is very high, so only one sample per each test condi-
90 5 10 15 20 tion was used. In case of anomalous behavior a second
85 7.5 15 22.5 30 measurement was performed.
80 12 25 40 50
70 30 60 90 120
60 75 150 225 300
3 Results
a) Given aging times are rounded up.
HTPB-based propellants show no simple thermo-rheological
behavior [57] due to the presence of secondary relaxation
dant and isophorone diisocyanate (IPDI) as curing agent phenomena appearing at higher temperature. Each investi-
(0.89 mass-%). A curing catalyst (D22 or DBTDL) was added. gated AV0x formulation shows two apparent maxima. The
The equivalent ratio (Req = NCO/OH) was maintained con- pure binder shows a similar tand curve structure [8].
stant at 0.87. The intensity of the second peak is influenced by the
All formulations were prepared in a vertical kneader plasticizer content and by Req. By fixing both of these pa-
(Drais T FHG, Germany) having a 5 L volume and cured in rameters the viscoelastic properties of the polymeric mate-
an electrical oven cabinet (company Memmert, Germany) rial are strongly influenced by the presence of fillers by
for 2 days at 60 8C. their following properties: morphology, particle size, sur-
face characteristic (presence of OH-groups), and binder
filler interactions.
2.2 Sample Preparation and Aging Conditions
Figure 1 shows the trend of the loss factor (tand = G/G,
Samples were aged from 60 8C to 90 8C in air, with RH < where G is the storage modulus and G is the loss modu-
10 % and in load-free conditions (no effects of stress and/or lus) of AV04 with aging. The same considerations can be
strain caused by the motor case are occurring) to simulate applied for the other investigated formulations. For every
15 to 20 years of natural aging. The thermal accelerated aging time the presence of two maxima can be seen. Both
aging program was carried out in PID temperature con- peaks are shifted to higher temperatures by increasing the
trolled ( 0.3 8C) aging ovens (design based on former com- deformation frequency, which means by increasing the de-
pany Julius Peter, Germany). To establish the aging plan the formation rate. The first maximum is located between
principle of Thermal Equivalent Load (TEL) was used to- 80 8C and 60 8C, depending on the applied deformation
gether with the generalized vant Hoff rule (GvH) [2, 3]. frequency. The second maximum is broader than the first
Table 1 shows the aging conditions determined using a scal- one and appears at higher temperature values [3]. The loss
ing factor F = 2.5 per 10 8C temperature change. factor is a composed distribution function (non-normalized
The study has focused on the accelerated aging of the density function) describing the distributions of the glass
surface-layer of SRPs, which means no in core analysis transitions of the structural elements of the propellant
was intended. Therefore the sampling did not follow the polymer networks. The first maximum, also called main
STANAG 4581 [4]. The specimen geometry was already the peak, is associated with the glass transition of the HTPB
one suitable for the DMA measurements, here small rectan- main chain elements, the so-named soft-segment units
gular bars: 10 mm wide, 4 to 5 mm thick, 50 mm long. [5, 6], where the main chain molecular motion ceases or
DMA samples were stored in glass tubes having ground starts. The temperature corresponding to the maximum of
glass stoppers. Stoppers were not fixed with a clamp and the peak is called Tgunrest. The second peak is related to the
not sealed by grease. Twice a week, stoppers were re- motions within the range of the short hard-segment units
moved to let fresh air to flow inside. (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
2.3 DMA Measurements
the restriction, the temperature corresponding to the maxi-
All DMA measurements were carried out in torsion mode mum of the second peak was named Tgrest. The different
using a DMA instrument of type ARESTM (Advanced Rheo- nature of these two relaxation phenomena can also be
metric Expansion System) manufactured by Rheometric Sci- seen considering the apparent activation energy (E a* ) ob-

Propellants Explos. Pyrotech. 2013, 38, 190 198  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.pep.wiley-vch.de 191
Full Paper S. Cerri, M. A. Bohn, K. Menke, L. Galfetti

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 Second peak
Ea*(Tgunr) [kJ mol1] log(f0(Tgunr) [Hz]) R2(Tgunr) Ea*(Tgr) [kJ mol1] log(f0(Tgr) [Hz]) R2(Tgr)
AV03 136  9 35.08  2.22 0.996 74  5 14.87  0.96 0.996
AV04 149  9 38.55  2.31 0.996 79  5 15.46  0.95 0.996
AV05 155  11 40.01  2.82 0.995 77  4 15.04  0.76 0.997

tained from the shift of the temperature values of the ed. In the present study, aging was followed by evaluating
maxima with deformation frequency [13] (Table 2). the area of the second peak after a baseline correction.
The thermal history of the material does not influence
the position and shape of the first tand peak. Values of
3.1 Modeling of the Loss Factor Curve Baseline Correction
Tgunrest are only slightly influenced by aging. This result
agrees with the DSC measurements [3]. Instead, remarkable The energy used during the DMA measurements is partly
changes were found for the second peak [6, 12, 14] and for transmitted loss free from the donor to the acceptor of the
the value of the storage shear modulus. G increases with specimen holder, and partly used by the propellant speci-
aging, whereas the values of tand decrease. In particular, men. This second part has two contributions: a purely dissi-
the area under the tand curves decreases. Other studies pative one in which the energy is transformed to heat by
have been carried out in order to follow the aging of pro- frictional effects inside the sample, and a contribution used
pellant formulations with DMA measurements. Husband for the molecular rearrangements of the binder network.
[15] has found a linear relationship between log(G) and the The rearrangement energy is taken up to separate molecu-
aging time. The aging rate was temperature dependent. An lar chains in the energy elastic state to allow multiple con-
activation energy of about 200 kJ mol1 between 60 8C and figurations in the entropy determined state and, on the
80 8C was obtained. De la Fuente et al. [6] also found a tem- other side, to overcome diffusion barriers in the entropy
perature dependence of the aging rates obtained from the elastic state to reach the optimal arrangements for the
E and tand measurements. The activation energy was not energy determined state. Outside the glass transition re-
evaluated, but the authors noticed that the area under the gions only dissipative consumptions occur, which are usual-
second peak decreased with aging. Ashcroft et al. [14] have ly small, particularly in the energy-elastic state. For filled
not only observed that the height and position of the elastomers the dissipative effects can become significant in
second peak tend to change with aging, but also evaluated the entropy-elastic state [8]. Thermoplastic and weakly
the area under the second peak (however, no baseline cor- cross-linked polymers change from a glass-like to rubber-
rection was applied) and found that a strong correlation like behavior as the temperature is increased. In the glassy
between this value and the aging time and temperature state, at low temperature, the behavior is related to
exists. Unfortunately the activation energy was not evaluat- changes in the stored elastic energy by small displace-

192 www.pep.wiley-vch.de  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Propellants Explos. Pyrotech. 2013, 38, 190 198
Aging of HTPB/Al/AP Rocket Propellant Formulations Investigated by DMA Measurements

Figure 2. Baseline correction of the loss factor of the AV04 unaged Figure 3. Baseline corrected loss factor vs. temperature at different
propellant formulation. aging times for the aged AV04 formulation (aging temperature
was 70 8C).

ments of atoms and atom groups from their equilibrium tand(Ta) Value of uncorrected tand(T) at temperature Ta,
positions. In the rubbery state, at high temperature, molec- [];
ular chains have much more flexibility because of increased tand(Tb) Value of uncorrected tand(T) at temperature Tb,
free volume and can adopt a large number of chain confor- [].
mations, which lead to a maximum of entropy. Scanning Ta Lower baseline setting temperature with slope Sa,
the temperature from one state region to the other one, [8C] in tand(Ta);
the material goes across an intermediate region, where the Tb Upper baseline setting temperature with slope Sb,
changes occur in molecular arrangements. Generally this [8C] in tand(Tb);
phenomenon is named glass transition region. Tst Scaled temperature T, [8C];
A visual sign for the dissipative part is the baseline offset T Measurement temperature between Ta and Tb,
between the start and the end point of the loss factor [8C];
curve (Figure 2). The separation of the dissipative part can Sa Slope at Ta in tand(Ta), [8C1];
be done by applying a suitable iterative baseline correction Sb Slope at Tb in tand(Tb), [8C1];
function (BLC) shown in Equation (1), using a transient
function a(T), Equation (3), which is a cumulative partition Baseline corrected loss factor curves are presented in
variable, to adjust the baseline weights along the loss Figure 3. The iteration procedure is fast and stable. Usually,
factor curve. The BLC function considers that on both sides already after 5 to 6 cycles the final BLC curve is obtained.
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
3.2 Modeling of the Loss Factor Curve Evaluation with
the slopes.
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
BLa(T) Baseline correction function based on a(T) be- investigated materials are not symmetrical as a Gauss distri-
tween Ta and Tb ; bution, which means that the data still contain some dissi-
a(T) Cumulative distribution of tand(T), []; pative parts. These dissipative effects can be considered

Propellants Explos. Pyrotech. 2013, 38, 190 198  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.pep.wiley-vch.de 193
Full Paper S. Cerri, M. A. Bohn, K. Menke, L. Galfetti

with relaxation curves, which are mostly represented by ex- Tci Temperature at peak maxima in the Gaussian part
ponentially decreasing functions, Equation (5). 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


The combined processes have been described by an ex- non-linear fit algorithm with N equal to the numbers of ex-
ponentially modified Gauss distribution function (EMG) tractable mobility regions. A LevenbergMarquardt algo-
[12], which is a convolution between Equation (4) and (5). rithm was used provided by the OriginTM program package
Due to the fact that the whole loss factor curve is com- [17].
posed of several molecular rearrangement types originating The use of only two EMGs could not describe the valley
from different mobility of several binder fractions, a sum of region very well between the two apparent peaks [16],
the fitting functions is shown in Equation (6). 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
T Measurement temperature, [8C]; aging, whereas the other two show a tendency to increase
tandBLC Loss factor curve after the BLC as function of T, (A3) and to decrease (A2). The change of these areas (Ai) can
[]; be described by a formal rate equation of zero order, Equa-
Ai Peak areas of the EMG peaks i, also equal to the tion (7).
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 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

Propellants Explos. Pyrotech. 2013, 38, 190 198  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.pep.wiley-vch.de 195
Full Paper S. Cerri, M. A. Bohn, K. Menke, L. Galfetti

Figure 7. Trends of maximum temperature values Tci with aging time for propellant AV04.

Considerations can be applied also for the change of tions. The increased available free volume at higher tem-
values with aging of the maximum temperature Tci, which perature values gives molecules more possibilities to realize
corresponds to the peak maxima of the Gauss parts many configurations, which means that the entropy in-
(Figure 7). The temperature of the first transition (Tc1) stays creases. The term T DS in Equation (12) gets more positive
quite constant with aging, whereas the other two parame- and DG gets more negative and the entropy term T DS
ters show a tendency to increase (Tc2) and to decrease (Tc3) controls now the Gibbs free energy. The enthalpy DH in-
with aging time [8]. 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
4 Discussion have increased. Local dipole-dipole interactions are less ef-
fective because of averaging out [19] by the thermal move-
4.1 Meaning of Loss Factor ments of the chain elements. Any effect that reduces the
A molecular interpretation of the viscoelastic behavior con- possibility of realizing polymer chain configurations (pres-
sidering the loss factor and the glass transition temperature ence of filler and binder-filler interactions) will reduce the
(Tg) is given in the following. The term glass transition de- entropy part and increase the enthalpy part by making the
fines a temperature induced transition region of an amor- material less entropy elastic and strain capability should
phous polymer phase from its energy-elastic state to its en- become smaller.
tropy-elastic one, and vice versa. The reason is to reach
always an energetic minimum, here in Gibbs free energy 4.2 DMA Modeling
DG, Equation (12).
The procedure used to analyze DMA measurements has
DGp,T DHp,TT  DSp,T 12 pointed out the possibility of extracting information from
the loss factor curve. The considered EMG modeling is not
In the energy-elastic state the internal energy is con- specific to the investigated formulations but it can be used
trolled by lattice like energetic interactions between poly- for other pre-polymers [20], as well as for other fillers [19],
mer molecules. The enthalpy term, DH, controls the Gibbs as it was done in Ref. [12]). The baseline correction of the
free energy. Because of lower temperature values the free data is necessary to get a quantification of the individual
volume is reduced and distances between polymer chains contribution of the different mobility ranges and mobility
are small. Therefore the mobility is restricted and local types. Without this procedure, the fitting would not be suc-
dipole-dipole interactions have a strong effect in lowering cessful and the contributions of the ranges would be
the internal free energy: the enthalpy DH becomes appreci- wrongly weighed.
ably negative. The entropy term plays nearly no role, be- Three main relaxation processes are embedded in the
cause there are little configuration changes of polymer HTPB binder systems, corresponding to binder fractions
chains and it is significantly smaller than the enthalpy term. with different mobility. The N extractable mobility ranges
On the contrary, in the entropy-elastic state the internal are obtained with the use of N EMG functions. The number
energy is not controlled by lattice like energetic interac- of fit parameters is equal to N times 4, where 4 is the

196 www.pep.wiley-vch.de  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Propellants Explos. Pyrotech. 2013, 38, 190 198
Aging of HTPB/Al/AP Rocket Propellant Formulations Investigated by DMA Measurements

number of the EMG parameters, namely: Ai, wi, Tci, Toi. They seen as the main, but not the only one, cause to explain
must be found in a unique way. This is possible due to the this trend. The analysis of the EMG modeling with three
in-built limitations of the EMG function in reproducing the molecular transitions allows to recognize the presence of
curve shape, which means that the EMG contains the con- these two competitive processes and to follow their trend
straints within its mathematical structure and cannot de- with aging: the decrease of A2 with aging can be associat-
scribe any shape. However, the necessary curve structure ed with a decrease of the molecular mobility (cross-linking),
must be in the data in order to correctly determine the pa- whereas the increase of A3 is assigned to chain scission
rameters [19]. causing an increase of free volume in the binder shell
Other authors have modeled the loss factor curve with around the filler particles.
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-
5 Conclusion
work, which are statistically distributed, and each one is re-
sponsible of a particular peak. With this model the loss DMA in torsion mode was employed to investigate the
factor (without BLC) was modeled with the sum of two aging behavior of three HTPB-based SRP formulations
Gaussian functions. Tsagaropoulos et al. [12] have observed having different aluminum particle size and content. The
the presence of a tail on the right side of the loss factor of accelerated aging range was between 60 8C and 90 8C with
several polymers filled with very fine silica particles. Due to aging times adjusted to a thermal equivalent load of 15 to
this asymmetry the loss factor was modeled with two EMG 20 years at 25 8C. For this correlation the generalized vant
functions. 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-
4.3 Interpretation of the Transition Regions
rameterization was done and the activation energies ob-
The increasing transition intensity of peak 3 indicates an in- tained are similar in values with the ones obtained with
crease in free volume or less mobility restriction by interac- SGA and GPC, reported in another paper [18].
tions between particles and binder chains. Also chain split- Loss factor curves were modeled with 3 EMG functions
ting could help to lower mobility restrictions. The active Al in order to get a molecular or microscopic interpretation of
particle surface can sustain the oxidative chain splitting the involved phenomena in the binder. Aging of the pro-
and thus lowering the mobility restrictions. Also surface pellant formulations can be followed by considering two
modifications of the Al particles should be taken into ac- parameters, namely: the areas of the second (A2) and third
count. Residual water can support the dissolving of the (A3) transition peaks, and the corresponding temperature
bonding agent from the AP surface. values of the assigned Gauss peaks called Tc2 and Tc3. The
The explanation for the changes in peak 2 is the follow- modeling has also shown that the glass transition tempera-
ing. The not bonded chains extracted by SGA and analyzed ture of the apparent second peak (Tgrest) is composed of
by GPC are cross-linked to the binder during ageing, which two different molecular phenomena represented by the
reduces the free volume in the urethane bonding regions, transition temperature values Tc2 and Tc3. More detailed
in spite of some chain scission occurring. This leads to analysis can be achieved by the investigation of specifically
a more rigid phase, which corresponds to a reduction in tailored model formulations designed to pronounce specif-
loss factor intensity of area A2 and in slight shift of the ic effects and allow an indirect evaluation of molecularly
maximum of the corresponding loss factor part to higher based phenomena [8, 13]. A further cause of cross-linking
temperature values. could be oxidative attack on the amino groups of the
The time-temperature evolution of the loss factor can bonding agent for AP.
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 Symbols and Abbreviations
means the presence of recombination reactions leading to
the formation of more cross-linked, and therefore more Al Aluminum, fuel
rigid three-dimensional network. A loss factor increase char- AP Ammonium perchlorate, oxidizer
acterizes an increase of the macromolecular mobility, which BLC Baseline correction
can be caused by chain scission [23] and/or by dewetting DBTDL Di n-butyltin dilaurate (also named D22)
between binder and filler particles [24]. Additional informa- DOA Dioctyl adipate, plasticizer
tion on changes in tand and their causes can be found in DSC Differential scanning calorimetry
Refs. [19, 25]. SEM images presented in a previous work Ea Activation energy, [kJ mol1]
[16] have not evidenced the presence of clear dewetting EMG Exponentially modified Gaussian
phenomena with respect to AP particles in the investigated EOMV End of mix viscosity
aged propellant formulations, therefore chain scission is GPC Gel permeation chromatography

Propellants Explos. Pyrotech. 2013, 38, 190 198  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 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.
IPDI Isophorone diisocyanate, curing agent [10] J. Ramier, C. Gauthier, L. Chazeau, L. Stelandre, L. Guy, Payne
Effect in Silica-Filled Styrene-Butadiene Rubber: Influence of
mass-% Percentage by mass Surface Treatment, J. Polym. Sci. B 2007, 45, 286298.
NCO Isocyanate group [11] G. Tsagaropoulos, A. Eisenberg, Direct Observation of Two
PID Proportional-integral-differential Glass Transitions in Silica-Filled Polymers. Implications for the
OH Hydroxyl functional group Morphology of Random Ionemers, Macromolecules 1995, 28,
Req Equivalent ratio between the functional groups 396 398.
of curing agent and binder (NCO/OH), [] [12] G. Tsagaropoulos, A. Eisenberg, Dynamic Mechanical Study of
the Factors Affecting the Two Glass Transition Behavior of
RH Relative humidity
Filled Polymers. Similarities and Differences with Random Ion-
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,
Tg Glass transition temperature, [8C]
P. Wylie, Oxidative Ageing of HTPB-Based Composite Propel-
TT Aging temperature, [8C] lant Rocket Motors, 39th Int. Annual Conference of ICT, Karls-
tT Aging time, [d]. ruhe, Germany, June 2427, 2008.
[15] D. M. Husband, Use of Dynamic Mechanical Measurements to
Determine the Aging Behavior of Solid Propellant, Propellants
Acknowledgments Explos. Pyrotech. 1992, 17, 196 201.
[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
Plaza, Northhampton, MA 01060, USA.
References [18] S. Cerri, M. A. Bohn, Ageing of Composite Solid Rocket Formu-
lations Containing Micro and Nano Aluminum Particles Investi-
[1] R. S. Hyde, A Solid Rocket Motor Manufacturers View of Sen- gated with Sol-Gel Analysis and Gel Permeation Chromatogra-
sors and Aging Surveillance, RTO AVT Specialist Meeting on Ad- phy, Cent. Eur. J. Energ. Mater. to be published in 2013.
vances in Rocket Performance Life and Disposal, Aalborg, Den- [19] M. A. Bohn, G. Mubach, S. Cerri, Influences on the Loss
mark, September 2326, 2002. (published in RTO-MP-091, Factor of Elastomer Binders and its Modeling, 43rd Int. Annual
NATO unclassified). Conference of ICT, Karlsruhe, Germany, June 2629, 2012.
[2] M. A. Bohn, Prediction of Equivalent Time-Temperature Loads [20] S. Cerri, M. A. Bohn, Ageing Behavior of Rocket Propellant For-
for Accelerated Ageing to Simulate Preset in-Storage Ageing mulations with ADN as Oxidizer Investigated by DMA, DSC
and Time-Temperature Profile Loads, 40th Int. Annual Confer- and SEM, 42nd Int. Annual Conference of ICT, Karlsruhe, Germa-
ence of ICT, Karlsruhe, Germany, June 2326, 2009. ny, June 28July 1, 2011.
[3] S. Cerri, M. A. Bohn, K. Menke, L. Galfetti, Ageing Behaviour of [21] R. Nevire, M. Guyard, DMA: A Powerful Technique to Assess
HTPB Based Rocket Propellant Formulation, Centr. Eur. J. Energ. Ageing of MED, 37th Int. Annual Conference of ICT, Karlsruhe,
Mater. 2009, 6, 149 165. Germany, June 2730, 2006.
[4] STANAG 4581, Explosives, Assessment of Ageing Characteris- [22] M. Coquillat, J. Verdu, X. Colin, L. Audouin, R. Nevire, Thermal
tics of Composite Propellants Containing an Inert Binder, Mili- Oxidation of Polybutadiene. Part 3: Molar Mass Changes of
tary Agency for Standardization, NATO, Final Draft Edition, Additive-Free non-Crosslinked Polybutadiene, Polym. Degrad.
2003. Stab. 2007, 92, 13431349.
[5] J. L. de la Fuente, M. Fernndez-Garca, M. L. Cerrada, Viscoe- [23] A. Kumar, S. Commereuc, V. Verney, Ageing of Elastomers:
lastic Behavior in a Hydroxyl-Terminated Polybutadiene Gum a Molecular Approach Based on Rheological Characterization,
and its Highly Filled Composites: Effect on the Type of Filler Polym. Degrad. Stab. 2006, 85, 751757.
on the Relaxation Processes, J. Appl. Polym. Sci. 2003, 88, [24] A. Lepie, A. Adicoff, Dynamical Mechanical Behavior of Highly
17051712. Filled Polymers: Dewetting Effect, J. Appl. Polym. Sci. 1972, 16,
[6] J. L. de la Fuente, O. Rodrguez, Dynamic Mechanical Study on 11551166.
the Thermal Aging of a Hydroxyl-Terminated Polybutadiene- [25] S. Cerri, M. A. Bohn, Separation of Molecular Mobility Ranges
Based Energetic Composite, J. Appl. Polym. Sci. 2003, 87, in Loss Factor Curves by Modeling with Exponentially Modi-
2397 2405. fied Gauss Distributions, 41st Int. Annual Conference of ICT,
[7] R. G. Stacer, D. M. Husband, Small Deformation Viscoelastic Re- Karlsruhe, Germany, June 29July 2, 2010.
sponse of Gum and Highly Filled Elastomers, Rheol. Acta 1990,
29, 152 162.
[8] S. Cerri, M. A. Bohn, K. Menke, L. Galfetti, Ageing of HTPB/Al/
AP Rocket Propellant Formulations Investigated by DMA
Measurements, Sol-Gel and GPC Analysis, 41st Int. Annual Con- Received: November 5, 2012
ference of ICT, Karlsruhe, Germany, June 29July 2, 2010. Published online: February 11, 2013

198 www.pep.wiley-vch.de  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Propellants Explos. Pyrotech. 2013, 38, 190 198