8 Scientific Technical Review, 2014,Vol.64,No.4,pp.

8-16

UDK: 621.454/66.621.453/.457
COSATI: 21-09, 21-08

Mechanical Properties of HTPB Composite Propellants in the Initial

Period of Service Life

Nikola Gligorijević1)
Saša Živković1)
Sredoje Subotić1)
Bojan Pavković1)
Momčilo Nikolić1)
Stevan Kozomara1)
Vesna Rodić1)

Uniaxial tensile tests of different composite solid rocket propellant compositions, based on hydroxyl-terminated polybutadiene
(HTPB), have shown that mechanical properties extensively change after curing, up to 100% of their initial values, during the
first few months. After that period, they stabilize and start to return slowly in the opposite direction. Careful measurements of
these features are necessary in order to control the production quality of the propellant and for a comparison of different
propellant compositions or batches. Furthermore, time distributions of the mechanical properties in the initial period after
production and short-time aging should not be neglected, because they strongly affect the propellant grain structural analysis
and a correct estimation of rocket motor reliability

Key words: composite rocket propellant, mechanical properties, aging, tensile strength, deformation, modulus of elasticity.

Nomenclature stabilization of the physical properties.

aT These two conflicting requirements must be adapted to
– Time-temperature shift factor
each other. Therefore, due to the lack of completion of the
D – Cumulative damage curing process, the physical properties of the propellant
E – Modulus, initial, tangent, elasticity continue to change afterwards. These changes depend on a
R – Strain rate, degree of completion of the polymerization process.
t – Time
After production, the mechanical properties of viscoelastic
ε , ε0 – Strain, Initial strain, propellants depend not only on strain rate and temperature
ε m , ε m0 – Ultimate (Allowable) strain, Initial strain [6-10] but also on real time [1-3, 11, 12]. This dependence on
ξ – Reduced time real time in the initial period after propellant production is the
main topic of this paper.
η (t ) – Propellant aging factor
Monitoring and analysing different HTPB composite
η E , ησ , ηε – Aging factor for modulus, stress, strain propellant compositions in the Military Technical Institute
σm – Tensile strength (Ultimate stress) (MTI) have shown that in a short period after production, the
σ m0 , σ m (t ) – Initial strength, Time-dependent strength changes in propellant mechanical properties are extensive.
These changes strongly affect the calculation results of the
propellant grain margin of safety and the structural reliability
Introduction analysis, and they must not be neglected.

C OMPOSITE solid rocket propellants are continuously

exposed to chemical (natural) aging, starting immediately
after casting. This is reflected in the change of their physical
According to the results of uniaxial tension tests carried out
in the Solid Rocket Propellant Department of the MTI, the
changes of the propellant mechanical properties due to
properties. In the initial period after production, especially the chemical aging take place in two phases. During the first
changes in mechanical properties are visible [1-3]. The first phase, which is 2 or 3 months long, sometimes slightly longer,
effects, hardening and softening due to migration of up to 6 months [12], there is an intensive change of the
plasticizer [4, 5], occur even during the curing process. mechanical properties of HTPB based composite propellants.
The changes of propellant physical properties do not finish If it is not expected for a rocket motor to be in use in the very
completely over the curing process and continue afterwards beginning after the propellant grain production, the first phase
with reduced intensity, regardless of the expectation that they may be neglected. For instance, for service life predictions
should be minimized at the end of the process. [11], the initial values of the mechanical properties are
The parameters of the curing are chosen to finish the considered using specimens at the propellant age of two
process as quickly as possible, but to improve efficiently months.

1)
Military Technical Institute (VTI), Ratka Resanovića 1, 11132 Belgrade, SERBIA
 GLIGORIJEVIĆ,N. etc.: MECHANICAL PROPERTIES OF HTPB COMPOSITE PROPELLANTS IN THE INITIAL PERIOD OF SERVICE LIFE 9

This approach may be valid if it is possible to store and keep The NCO/OH ratio between the isocyanate groups of IPDI
propellant after production, until it is stabilized. However, that is to the hydroxy groups was 0.86.
not always the case. Sometimes, especially for small rockets, the The propellant formulations were mixed in a Baker-Perkins
first phase should not be neglected, because it is needed for a planetary 1-gallon mixer at 60oC. The curing agent was added
rocket to be immediately delivered to a customer or to be ready to the mixture at the end of the mixing process. The curing
soon after production, as in the case of an anti-hail rocket [12], was performed for 5 days at 70 ºC.
designed in the MTI for civilian use. In addition, mechanical
tension tests in the initial phase are required due to monitoring of Virgin propellant and the initial mechanical testing
various propellant compositions and their comparison. In the During the implementation of a complete program of
second phase of the propellant aging, mechanical properties mechanical characterization in order to prepare stress, strain
change slowly, in the direction opposite to the first phase [12], and relaxation modulus master curves [6-10] for a fresh
similarly as concluded in [13]. propellant, a need appeared to better define the propellant
from the standpoint of its age. The master curves are required
The data obtained by measuring the changes of mechanical
for a propellant grain structural analysis. The term „virgin
properties in the initial period may be used for a correction of
the results of a complete uniaxial mechanical characterization propellant“ [18, 19] refers to the moment right after
of virgin propellants, in order to make master curves for the production. In practice, it is not possible to conduct such a
ultimate stress, strain and relaxation modulus. program in the short term. A complete propellant mechanical
characterization has to be carried out in a wide range of
various test conditions, with statistically acceptable number of
Parameters of propellant production replicates in each test regime [7, 9, 10]. These tests are more
extensive and include a number of different test temperatures
(in the range between -60oC and +50oC) and different strain
Curing parameters rates, using constant crosshead speeds in the range between
0.5 and 1000 mm/s, with statistically acceptable number of
In the production process of composite propellants, producers replicates in each test regime [7, 9, 10, 19].
themselves define their own optimal production parameters and
terms of casting and curing. For example, the following curing This procedure sometimes could take up to 2 or 3 months
parameters are used in different situations: (50oC and 120 hours) [12]. However, during those 2-3 months, propellant
are used in [13], while 65oC and 7 days are used in [14]. These mechanical properties are extensively changed and it is
conditions are usually defined on the basis of own production necessary to determine the intensity of these changes and an
experience [15] and the analysis of diisocyanate to total hydroxyl acceptable way to take them into account.
ratio (NCO/OH) [14]. During the cure, propellant properties are The propellant tested in the moment right after production
unstable due to the migration of a plasticizer [4, 5, 14, 16] until it should be called “new” or “virgin” because it is important to
distinguish it in relation to the term “unaged”, that some
reaches the equilibrium [4]. Variations from these parameters, as
authors [5, 20, 21] use for a propellant that has not been
well as propellant properties, depend on a number of influencing
subjected to accelerated aging. It is usually expected for a
factors [17], like percentage and composition of polymer binder, propellant to be in use for many years. It means that the term
type, granulation and amount of oxidizer powder, different “aging“ involves a long process, and the term “unaged“ could
additives, etc. wrongly imply a wide period in the beginning of the service
In the MTI, for a class of HTPB-based composite life. In that way, a significant error could be made due to the
propellants with ammonium perchlorate (AP) as oxidizer, it strong change of the propellant mechanical properties in the
was found that the optimal curing parameters (temperature initial period after production.
and time duration) are about 70oC and 120 hours. Sometimes,
small deviations from these parameters are allowed because it Time dependence of the propellant ultimate
is believed that they should not change the optimal curing mechanical properties
conditions significantly and, therefore, these parameters are
usually adopted as standard values for a whole class of similar There is not much information in literature about the
propellant compositions. changing of the propellant mechanical properties in the initial
period after propellant grain production. Most of the
Propellant compositions information deals with the effects of plasticizer’s content and
its migrations in order to analyze the propellant hardening or
Seven similar solid propellant compositions were tested, softening, especially in the area between the propellant and
composed of 23.4 % HTPB-based binder, 75% ammonium- the layer, as well as the impact of this phenomenon on the
perchlorate (AP) as crystalline oxidizer, 1% aluminum (Al) propellant adhesion with the bond. There is a lack of
metal fuel powder, 0.5% lithium-fluoride (LiF) as burning rate information in literature about the effects of natural aging in
depressant and 0.1% carbon black powder (C) as burning the initial period on the propellant itself.
stabilizer. Within the HTPB-based binder, isophorone- Since this issue is not sufficiently considered in literature,
diisocyanate (IPDI) as curing agent (crosslinker) was used, as it could be wrongly concluded that the aging effect on
well as dioctyl-adipate (DOA) as plasticizer, 2,2-methylene-bis- mechanical properties could be neglected in the beginning of
(4-methyl-6-tertiary-butyl phenol) (AO22) as antioxidant and the rocket motor service life.
triethylene-tetramine (ТЕТ), as bonding agent. The differences Some information about the initial tests has been found in
between the compositions are related to oxidizer granulations [13], where it has been concluded that the maximum stress
and mass fractions of plasticizers and curing agents.
( σ m ) and the modulus ( E ) increase first sharply, then
The approximate properties of the binder composition are
slightly, while the strain values ( ε m ) decrease in the same
as follows: molecular weight: 2800 g/mol, hydroxyl
functionality: 2.4-2.6 OH value: 44.2 mg. manner.
10 GLIGORIJEVIĆ,N. etc.: MECHANICAL PROPERTIES OF HTPB COMPOSITE PROPELLANTS IN THE INITIAL PERIOD OF SERVICE LIFE

On the other hand, Sutton [22], for instance, suggests that compositions. They were tested on a universal Instron-1122
changes occur only due to the effects of load, and he does not tester under standard conditions (+20oC and 50 mm/min).
consider the effects of natural aging. It was found that the For the uniaxial tension tests, standard propellant
decrease in mechanical properties is primarily due to specimens of „JANNAF-C“ type [9] were used. In all cases, a
cumulative damage [2, 12, 18, 23, 24, 25]. statistical sample of 7-9 specimen replicates was included.
Sometimes, propellant aging is considered as a unique The initial tests for each propellant composition were
result of a simultaneous action of chemical and physical performed exactly two days after curing and this moment was
effects as well as the effects of mechanical loads [5]. treated as the beginning of the propellant service life ( t = 0 ).
Usually, the effect of environmental loads, primarily This is the moment when the propellant can be treated as
temperature, is often treated in literature separately, as “new” or “virgin”. Starting from the next day, in every
moment, the propellant is considered not as “new”, but as a
cumulative damage [6, 9, 10], and mainly after a long period
material which has been subjected to aging.
of storage, using the methods of accelerated aging [3, 11, 26].
Including the initial tests, all seven propellant compositions
For the structural analysis of the propellant grain, it is
were tested two or three times in the same, standard
necessary, first of all, to determine the ultimate mechanical
conditions, at irregular intervals, over a period of 45 days.
properties of the propellant [6, 8-10]. They are needed for a After that, over the next 10 months, two propellant
failure analysis and a comparison with the values of real stresses compositions from the group of seven were additionally
or strains, which may be significantly variable, depending on the tested, also in standard conditions.
environmental influence or the variable pressure or the thrust of
In parallel, in the second group of tests, one propellant
the rocket motor [27]. The allowable stress and strain are time
composition was tested in different strain rate regimes at
dependent features, σ m (t ), ε m (t ) . These values of tensile standard temperature (20oC). Nine different tester cross-head
strength and allowable strain, in accordance with Heller’s model speeds in the range between 0,2 and 1000 mm/min were used.
[2, 12, 18] are the products of the initial values that represent a The tests were performed in two different periods,
new propellant ( σ m 0 , ε m 0 ), aging factors (ησ ,ηε ) and approximately 15 days and 105 days after curing. The
cumulative damage (1 − D ) , Eqs.1-2: objective of this group of tests was to better explain the aging
influence on the mechanical properties of the propellant.
σ m (t ) = σ m 0 ⋅ησ (t ) ⋅ [1 − D(t ) ] (1)
Test results
The results for the first set of uniaxial tension tests (seven
ε m (t ) = ε m 0 ⋅ηε (t ) ⋅ [1 − D(t ) ] (2) different compositions) in standard conditions (+20oC, 50
mm/min) are presented in Table 1.
The HTPB composite propellant is a viscoelastic material
and the ultimate values of its mechanical properties are highly The propellant tensile strength ( σ m ), the allowable strain
dependent on temperature and strain rate [7, 9, 10]. ( ε m ) and the initial modulus ( E ) were measured. Since the
In Eqs. (1) and (2), these ultimate values of a new absolute values of the measured propellant properties are not
propellant ( σ m 0 , ε m 0 ) are formally represented as constants suitable for comparison, the aging factor distributions are
due to real time, because they are related exactly to the initial made, as the ratios of their current and initial values. The
moment of time after the end of curing. These features are aging factors for the initial modulus and the allowable strain
variables, usually presented in the form of master curves [6- distributions are shown in Figures 1 and 2.
10, 12] that depend on temperature and strain rate. 2,1
Ideally, the master curves should be performed immediately
2,0
after curing, before the natural aging process begins. However,
the procedure of the master curves determination could take a 1,9

long time, sometimes up to several months [12]. At the end of

Modulus aging factor, ηE (-)

1,8
this period, the propellant is no longer “new” or “virgin” because 1,7
its mechanical properties are changed, and it is necessary to
1,6
determine the intensity of these changes in order to find an
acceptable way to take them into account. 1,5

The aging factor is a ratio between a current value of a 1,4

mechanical property and its initial value. This value is 1,3
variable and may be represented by its time dependence.
1,2
For different mechanical properties: tensile strength,
1,1
allowable strain and initial modulus, the aging factors ( ησ ,
1,0
ηε , η E ) are also different.
0,9
In order to define the time-dependence of the aging factors -5 0 5 10 15 20 25 30 35 40 45 50
in the beginning of the service life, in the MTI’s Department Time, t (Days)
for composite propellants, uniaxial tension tests were carried
out for several different HTPB propellant compositions, over Figure 1. Modulus aging factor for seven different HTPB compositions over
the period of 45 days after production. 45 days

Experiment Different symbols correspond to different propellant

Two groups of uniaxial tension tests have been carried out. compositions. The uniaxial aging factor for tensile strength is
The first group of was performed on seven different HTPB shown in Fig.3.
 GLIGORIJEVIĆ,N. etc.: MECHANICAL PROPERTIES OF HTPB COMPOSITE PROPELLANTS IN THE INITIAL PERIOD OF SERVICE LIFE 11

Table 1. Mechanical properties for different short-aged HTPB propellants (+20oC)

Propellant code Time, t Time, t-2 Strain, ε m SD( ε m ) ε ε0 Modulus, E SD( E ) E E0 Strength, σm SD( σ m ) σ σ0
Days Days % - MPa MPa - MPa MPa -
2 0 37.56 0.62 1.00 3.204 0.080 1.00 0.632 0.010 1.00
1. VM 115 5 3 30.88 0.31 0.82 3.558 0.060 1.11 0.626 0.006 0.99
40 38 17.01 1.24 0.45 5.308 0.156 1.66 0.575 0.006 0.91
2 0 44.01 5.61 1.00 2.405 0.060 1.00 0.592 0.008 1.00
2. VM 116 5 3 36.71 2.36 0.83 2.986 0.052 1.24 0.588 0.004 0.99
33 31 20.24 1.54 0.46 4.668 0.163 1.94 0.563 0.010 0.95
2 0 62.52 1.13 1.00 2.022 0.144 1.00 0.490 0.088 1.00
11 9 53.87 1.62 0.86 2.113 0.033 1.04 0.518 0.003 1.06
3. VM 117
18 16 36.88 1.67 0.59 3.086 0.230 1.53 0.548 0.004 1.12
32 30 29.90 0.32 0.48 3.833 0.109 1.90 0.572 0.006 1.17
2 0 66.24 1.97 1.00 1.494 0.127 1.00 0.416 0.008 1.00
11 9 55.00 0.63 0.83 1.859 0.022 1.24 0.452 0.006 1.09
4. VM 118
13 11 54.81 1.74 0.83 2.017 0.064 1.35 0.483 0.051 1.16
25 23 36.46 4.02 0.55 2.790 0.194 1.87 0.537 0.006 1.29
2 0 31.78 0.55 1.00 4.206 0.151 1.00 0.701 0.004 1.00
5. 2183 N 5 3 28.43 0.31 0.89 4.620 0.495 1.10 0.717 0.009 1.02
35 33 17.48 0.34 0.55 6.819 0.173 1.62 0.775 0.003 1.10
2 0 41.74 0.62 1.00 3.351 0.015 1.00 0.720 0.012 1.00
5 3 34.40 0.39 0.82 3.535 0.083 1.06 0.701 0.002 0.97
25 23 26.17 0.31 0.63 4.554 0.265 1.36 0.658 0.013 0.92
6. 2224 N 45 43 22.17 0.25 0.53 6.202 0.044 1.85 0.585 0.009 0.81
82 80 17.66 1.01 0.42 6.846 0.212 2.04 0.562 0.033 0.78
144 142 16.49 0.06 0.40 6.973 0.219 2.08 0.550 0.007 0.76
274 272 20.46 0.84 0.49 6.725 0.111 2.01 0.583 0.012 0.81
2 0 27.43 0.15 1.00 4.495 0.230 1.00 0.784 0.008 1.00
14 12 22.00 0.34 0.80 6.150 0.418 1.37 0.650 0.006 0.83
18 16 19.34 0.59 0.70 6.797 0.502 1.51 0.608 0.012 0.78
7. VM 133 42 40 14.73 0.40 0.54 7.898 0.597 1.76 0.571 0.044 0.73
106 104 12.51 0.22 0.46 8.330 0.197 1.85 0.582 0.010 0.74
185 183 12.89 0.15 0.47 9.036 0.396 2.01 0.629 0.005 0.80
300 298 14.15 0.36 0.52 8.829 0.208 1.96 0.663 0.007 0.85

1,1 1,4

VM - 118
Tensile strength aging factor, ησ (−)

1,3
1,0
VM - 117
m
Allowable strain aging factor, ηε (−)

1,2
m

0,9 2183 N
1,1
VM - 116
0,8
1,0

0,7
0,9 VM - 115

0,6 0,8 2224 N

VM - 133
0,5 0,7

0,6
0,4 -10 0 10 20 30 40 50
-5 0 5 10 15 20 25 30 35 40 45 50
Time, t (Days)
Time, t (Days)

Figure 2. Allowable strain aging factor for seven different HTPB propellants Figure 3. Tensile strength aging factor for seven different HTPB propellant
over 45 days compositions over 45 days

The test results in Figures 1-3 show significant relative The aging factor distributions for the tensile strength, the
changes in the mechanical properties, for each composition in allowable strain and the initial modulus, over the period of ten
the tested group of composite propellants based on HTPB, months for two selected compositions (No6, No7), are shown
over the 45-day period after production. in Figures 4-6.
12 GLIGORIJEVIĆ,N. etc.: MECHANICAL PROPERTIES OF HTPB COMPOSITE PROPELLANTS IN THE INITIAL PERIOD OF SERVICE LIFE

2,2

Tensile strength aging factor, ησ (−)

2,0 1,0

m
Modulus aging factor, ηE (-)

1,8

0,9
1,6

1,4

0,8
1,2

1,0

0,7
0,8
-50 0 50 100 150 200 250 300 350

-50 0 50 100 150 200 250 300 350

Time, t (Days)
Time, t (Days)
Figure 4. Modulus aging factor for two different HTPB propellant compo-
sitions over 10 months Figure 6. Tensile strength aging factor for two different HTPB propellant
1,1 compositions over 10 months

1,0 In the second group of tests, uniaxial tension tests in two

different periods for the HTPB composition labeled in Tab. 1
Allowable strain aging factor, ηε (−)

0,9
as No 7 were done at constant temperature (+20oC).
m

0,8
The tests were carried out at nine different cross-head
speeds: 0.5, 1, 2, 5, 10, 20, 50, 100 and 200 mm/min.
0,7 At first, the tests were carried out approximately 15 days
after curing. The second set was done 105 days after curing.
0,6
The measured values for three characteristic mechanical
0,5
properties ( σ m , ε m , E ) are shown in Table 2.
In the uniaxial tension tests at constant temperature for an
0,4 arbitrary composite propellant as a linear viscoelastic
material, a linear dependence of tensile strength vs. strain rate
0,3
-50 0 50 100 150 200 250 300 350 at constant temperature is expected[7, 8, 10, 28].
Time, t (Days)

Figure 5. Allowable strain aging factor for two different HTPB propellant
compositions over 10 months

Table 2. Mechanical properties of the HTPB propellant in two different periods

Cr.-head Time,
Propellant age Strain rate Strength SD( σ m ) Modul SD( E ) Strain SD( ε m )
speed log t
-1
Days mm/min R (s ) log (1/R) MPa MPa MPa MPa %
17 0.5 0.000121 3.9155 0.286 0.002 4.265 0.099 12.74 0.07
16 1 0.000243 3.6145 0.363 0.003 4.538 0.089 15.33 0.34
15 2 0.000486 3.3134 0.421 0.003 4.925 0.134 16.76 0.28
12 5 0.001215 2.9155 0.468 0.018 4.860 0.112 18.61 0.77
15 10 0.002430 2.6145 0.499 0.010 6.078 0.322 17.61 0.22
12 20 0.004859 2.3134 0.546 0.015 5.859 0.289 19.84 0.64
16 50 0.012148 1.9155 0.608 0.012 6.797 0.502 19.34 0.59
18 100 0.024295 1.6145 0.714 0.009 6.826 0.312 21.50 1.12
18 200 0.048591 1.3134 0.736 0.021 8.044 0.281 21.65 1.41
106 0.5 0.000121 3.9155 0.266 0.004 5.889 0.112 8.39 0.12
105 1 0.000243 3.6145 0.235 0.005 5.689 0.147 7.88 0.29
106 2 0.000486 3.3134 0.267 0.001 6.232 0.212 10.62 0.50
106 5 0.001215 2.9155 0.403 0.017 7.100 0.218 10.14 0.53
105 10 0.002430 2.6145 0.476 0.012 7.239 0.412 11.39 0.45
106 20 0.004859 2.3134 0.499 0.022 8.042 0.179 11.10 0.17
104 50 0.012148 1.9155 0.582 0.010 8.330 0.197 12.51 0.22
105 100 0.024295 1.6145 0.667 0.005 9.150 0.200 14.04 0.89
105 200 0.048591 1.3134 0.719 0.022 9.518 0.338 14.07 1.08
 GLIGORIJEVIĆ,N. etc.: MECHANICAL PROPERTIES OF HTPB COMPOSITE PROPELLANTS IN THE INITIAL PERIOD OF SERVICE LIFE 13

The dependences of all the three characteristic mechanical

11 18
properties for propellant No7 are also linear. These
dependences on strain rate in two different periods are shown 10
18
for the initial modulus, the allowable strain and the tensile 16

Tensile strength, σm (daN/cm )

9 106

2
strength, in Figures 8-10, respectively.
8 105 12
15
100 106 7 106 12
105 15
6 106
90 105 16
Initial modulus, E (daN/cm )

106
2

5
106 106 17
18 4
80
105
105 106 105
3
70
16 105
18 105 2
105
60 12 15 105 1 2 3 4
Reduced time, log t (s)
12 15
50 Figure 9. Tensile strength vs. strain rate and aging time
16
17
40
Discussion
1 2 3 4
Reduced time, log t (s) During the first 45 days after production, in the initial
Figure 7. Modulus vs. strain rate and aging time period after curing, for the whole considered group of seven
different HTPB-based propellant compositions (Table 1),
intensive changes in their mechanical properties appear. The
24
basic tensile tests for analysing the influence of short-term
18 18
22 aging on the propellant mechanical properties, were carried
out only at standard temperature (+20oC). The initial modulus
Strain at maximum stress, εm (%)

20 16 12 12 ( E ) increases in 45 days (Fig.1) and approximately doubles

18 15 its value. In contrast, the allowable strain ( ε m ) decreases, in
15 all cases, and falls bellow 50% of its initial value (Fig.2). The
16
16
105 initial values of the tensile strength ( σ m ) (Fig.3) may change
14 17 in both directions. They may increase or decrease, depending
106
12
105 on the propellant composition, but the maximum change in 45
106 105 days does not exceed 30%.
10 106
105 The propellant compositions labeled in Table 1 as No6 and
106
8 No7 were selected for testing during the next several months.
105 The results (Figs 4-6) have shown that after a certain period,
6
1 2 3 4
all the mechanical properties become stabilized. Then, they
Reduced time, log t (s) even begin to change in opposite directions, returning slowly
to the initial state, as it was concluded in [12, 13].
Figure 8. Allowable strain vs. strain rate and aging time
Sometimes, structural analysts ignore the initial changes of
the mechanical properties. This neglecting is probably
The tester cross-head speed ( V ) is constant in each tension compensated for, because the tension tests are performed
test and allows the direct determination of the specimen strain using the specimens that have been stored for some time after
( ε ) and the strain rate ( ε ): production and whose mechanical properties became
stabilized. However, that is not always possible, because
ε = V ⋅ t = ε ⋅ t (3) storage of propellant itself or propellant grain series in
l0
manufacturers stock is too expensive. Moreover, it is not easy
to recognize exactly the moment of the mechanical properties
d ε = ε( s −1 ) = R = V (mm/min) (4) stabilization. This period is very likely to exceed 2 months,
dt 60 ⋅ l0 (mm) which was adopted as a time limit in the case [11]. There are
also other reasons not to ignore the changes in the mechanical
l0 - Effective gage length; 68,6 mm. properties of the propellant in the initial period.
ε - Strain One of the most important reasons for testing and
All three plots have the same abscissa (19) which monitoring the composite propellant mechanical properties in
represents the reciprocal of the propellant specimen strain rate the initial period is a need to compare different propellant
compositions. To make this comparison have its full meaning,
( ε −1 = R −1 ). The abscissa of each of these diagrams has the it is necessary to define the exact terms of comparing the
dimension of time. The logarithmic scale of the abscissa is mechanical properties of different propellants.
suitable for further analyses. Since all the measurements were
done at standard temperature (+20oC), the time-temperature The moment of initial testing after curing is especially
important because mechanical properties rapidly change in
shift factor ( aT ) [7, 9, 10, 28] does not affect the results.
this period.
14 GLIGORIJEVIĆ,N. etc.: MECHANICAL PROPERTIES OF HTPB COMPOSITE PROPELLANTS IN THE INITIAL PERIOD OF SERVICE LIFE

The procedure of a complete propellant mechanical complex star-shaped channels [6, 22, 29]. According to [2, 9,
characterization is very long and the period of its duration is 10], for the inner-bore surface as the most critical zone of a
sufficient to significantly alter all characteristic mechanical propellant grain, a failure analysis should be performed by
properties. It is not possible to complete the whole procedure comparing bore strains with strain failure data, rather than by
quickly, immediately after curing. For example, for a using the stress criterion. In this case, it is possible to perform
statistical sample of 7÷9 JANNAF-C specimen replicates, at the analysis, even if there is no data on the tensile strength.
single regime with a constant temperature and cross-head
The second set of tests was carried out for two reasons:
speed of 0,2 mm/min, an average elongation at the break point
of a specimen is approximately 10 mm. 1. To explain the effects of the initial aging on the
The full test procedure can last even longer than three mechanical properties and the connectivity between real
months. During these three months, the mechanical properties time, strain rate and temperature, as a basis for the time-
of the propellant change significantly. The tests in this study temperature dependence which is characteristic for
have shown that these changes are of the order of 100%. In viscoelastic materials;
order to get true values of the initial properties, it is necessary 2. To show that the master curves of the propellant
to make corrections due to the aging in the initial period after mechanical properties may be translated along the time
propellant production. axis, only on the basis of periodical tests in standard
For an illustration, there are significant differences between conditions (+20oC, 50 mm/min). It means that, when the
the absolute modulus values for different HTPB-based master curves are determined for a “new” propellant, the
propellant compositions (Table 1). The ratio between the uniaxial tension tests are sufficiently representative for
maximum value and the minimum value is in the range monitoring the propellant mechanical properties over
between one and three. However, the values of the modulus time in all operating regimes.
aging factors are similar for all tested compositions (Fig.1), as In the second set, only one propellant composition has been
well as their time-distributions during the initial period. tested, in different time- and strain rate conditions. The visual
For example, it is possible to define an approximate effect of these tests can be seen in Figures 8-10. There are
average function of a mechanical property distribution in the proper distinctions between the values measured after 15 days
beginning of the service life, for a whole group of different and the values measured 105 days after production.
propellants of the same type, as in the case of seven tested Three pairs of regression lines that correspond to different
HTPB compositions. This function can be used for a time points, for all the three characteristic propellant
preliminary structural analysis, with a very small error. mechanical properties ( E , ε m , σ m ), in each diagram, are linear
In Fig.10 the field contains initial values of the modulus and it seems that they are approximately mutually equidistant.
aging factor for all the seven tested compositions (Table 1). It means that the aging effect on the propellant mechanical
For the period after 45 days, up to 10 months, only the tests properties is approximately the same for all different strain
for the two propellant compositions (No 6 and No 7) were rates.
made, but it seems that it is enough to see the possibility of The values of the propellant initial modulus are shown in
defining an approximate mathematical distribution function Fig.8. On the abscissa, the reciprocal values of the strain rate
that could be used in the absence of more complete results. (time) are shown in the logarithmic time scale. For the time
In addition, according to the results in Table 1 and Fig.2, ( log t = 1.9155 ≈ 2 ) which corresponds to the standard cross-
such a relationship may also be determined for the allowable head speed, ( 50 mm min ), there are two different values of
strain aging factoras well as for all tested compositions. This
regression curve is decreasing exponentially. the modulus: for the propellant tested after 15 days,
E15 ≈ 6, 6 MPa , and for the propellant tested after 105
For the tested group of HTPB compositions (Table 1), it is
not possible to define an equation that describes a general days, E105 ≈ 8, 4 MPa . Over the period 15-105th day, the
aging factor dependence for tensile strength, because there is modulus is changed more than 25%.
scattering in both directions (Fig.3). This difference is less than the modulus change from its
initial value, because there is also a change that occurred
during the first 15 days after production. This result shows
2,0
that the changes in mechanical properties during this period
are important.
Besides the basic results that show a large impact of the
Modulus aging factor, ηE (-)

Equation: y = A1*exp(-x/t1) + y0 initial aging on the propellant mechanical properties, one can
1,5 get some additional conclusions. All the tests in this study
were carried out only at standard temperature (+20oC). It is
y0 2.00398 ±0.04941
A1 -1.01457 ±0.05845
t1 24.30279 ±3.5098
always questionable how the ambient temperature affects the
process of properties change due to aging. When it is
assumed, for small strains, that a composite rocket propellant
1,0 is a linear-viscoelastic material, there exists a strong time-
temperature dependence [6-10].
-50 0 50 100 150 200 250 300 350 The second set of tests has shown that the different strain
Time, t (Days) rates do not affect a relative change of propellant mechanical
Figure 10. General modulus aging factor properties due to aging, because the regression lines for two
different time points are approximately equidistant, with the
However, the values of the first two aging factors, for the
same slope. The aging in this period affects only the spacing
modulus and the allowable strain ( η E ,ηε ), could be sufficient along the abscissa between the regression lines. This is
for a preliminary structural analysis of propellant grains with expected, because the abscissa corresponds to the time line.
 GLIGORIJEVIĆ,N. etc.: MECHANICAL PROPERTIES OF HTPB COMPOSITE PROPELLANTS IN THE INITIAL PERIOD OF SERVICE LIFE 15

The abscissas in these diagrams represent the reciprocal References

values of the strain rate, with the time dimension. If a
regression line that represents the strain rate dependence of a [1] LAYTON,L.H.: Chemical Structural Aging Studies on an HTPB
Propellant, A-Division of Thiokol Corporation, Final Technical
mechanical property is moved horizontally along the abscissa Report, AD A010731, 1975.
to meet and overlap another one, the movement along the [2] HELLER,R.А., SINGH,М.P.: Thermal Storage Life of Solid-
timeline is equal to the aging impact in the observed period. Propellant Motors. Journal of Spacecraft and Rockets, 1983, Vol.20,
According to the time-temperature analogy, it can be No.2, pp.144-149.
concluded that ambient temperature also does not have influence [3] BRINSON,L.C., GATES,T.S.: Effects of Physical Aging on Long-term
on the effects of the aging process. This statement should not be Creep of Polymers and Polymer Matrix Composites, NASA, Technical
Memorandum 109081, 1994.
confused with the real temperature influence on mechanical
[4] GOTTLIEB,L., BAR,S.: Migration of plasticizer between Bonded
properties. It is known [6-10] that the absolute values of Propellant Interfaces, Propellant, Explosives, Pyrotechnics, 2003,
mechanical properties depend on temperature, but their relative Vol.28, No.1, pp.12-17.
change, compared to the initial values are the same, regardless of [5] CERRI,S., BOHN,A.M., MENKE,K., GALFETTI,L.: Ageing Behavior
the environmental constant temperature value. It seems that of HTPB Based Rocket Propellant Formulations, Central European
relative changes due to natural aging are independent of different Journal of Energetic Materials, 2009, Vol.6, No.2, pp.149-165.
constant ambient temperatures. Thus, if the aging process does [6] WILLIAMS,M.L, BLATZ,P.J., SCHAPERY,R.A.: Fundamental
Studies Relating to Systems Analysis of Solid Propellants, Final report
not affect the character of the strain rate dependence, it also will GALCIT 101, Guggenheim Aeronautical Lab., Pasadena, California,
not affect the relative dependence on temperature. 1961.
Finally, it means that it is sufficient to test the aging effect [7] LANDEL,R.F., SMITH,T.L.: Viscoelastic Properties of Rubberlike
on mechanical properties only at standard temperature. Composite Propellants and Filled Elastomers, ARS Journal, 1960,
Vol.31, No.5, pp.599-608.
When it is necessary to make an estimate of rocket motor
[8] WILLIAMS,M.L.: Structural Analysis of Viscoelastic Materials,
reliability at an arbitrary time, the propellant mechanical AIAA Journal, Calif. Institute of Technology, Pasadena California,
properties have to be determined right for this time point. May 1964, pp. 785-798.
This means that all points of each master curve for a virgin [9] FITZGERALD,J.E., HUFFERD,W.L.: Handbook for the Engineering
propellant, represented in Eqs 1 and 2 as formal constants Structural Analysis of solid Propellants. CPIA publication 214, 1971.
( σ m 0 ,ε m 0 ), have to be moved along the real-time axis, due to [10] NASA: Solid propellant grain structural integrity analysis. NASA
Space Vehicle Design Criteria SP-8073, 1973.
aging, in the same manner as the point that corresponds to the
[11] THRASHER,D.I., HILDRETH,J.H.: Structural Service Life Estimate
standard test regime. for a Reduced Smoke Rocket Motor. Journal of Spacecraft, 1982,
Vol.19, No.6, pp. 564-570.
[12] GLIGORIJEVIĆ,N., RODIĆ,V., JEREMIĆ.R., ŽIVKOVIĆ,S.,
Conclusion SUBOTIĆ,S.: Structural Analysis Procedure for a Case Bonded Solid
In the production process of composite rocket propellant Rocket Propellant Grain, Scientific Technical Review, ISSN 1820-
0206, 2011, Vol.61, No.1, pp. 1-9.
grains, in most cases it is necessary to carry out the quality
[13] SHEKHAR,H., SAHASRABUDHE,D.A.: Assessment of Poisson’s
control of ballistic and mechanical propellant properties Ratio for Hydroxy-terminated Polybutadine-based Solid Rocket
immediately after curing. The quality control of the virgin Propellants. Defence Science Journal, 2010, Vol.60, No.5, pp.497-501,
propellant is important for production acceptance, monitoring [14] HOCAOGLU,O., OZBELGE,T., PEKEL,F., OZKAR,S.: Fine-tuning
and relative comparison of different compositions, and for a the mechanical properties of hydroxyl-terminated polybutadiene
proper evaluation of the rocket motor reliability in the initial /ammonium perchlorate-based composite solid propellants by varying
period of its service life. the NCO/OH and triol/diol ratios. Journal of Applied Polymer Science,
2002, Vol.84, No.11, pp.2072-2079.
During the short age period, the mechanical properties of
[15] RODIĆ,V., PETRIĆ,M.: The effect of curing agents on solid composite
the HTPB propellant extensively change. The stabilization of rocket propellant characteristics. Scientific Technical Review, ISSN
the propellant mechanical properties takes place up to 2-3 1820-0206, 2005, Vol.55, No.1, pp.46-50.
months after production, and sometimes even 6 months. [16] LIBARDI,J., RAVAGNANI,S., MORAIS,A., CARDOSO,A.:
Afterwards, the mechanical properties continue to change Diffusion of Plasticizer in a Solid Propellant Based on Hydroxyl-
slowly, in a different way. Terminated Polybutadiene. Polimeros, 2010, Vol.20, No.4, pp.241-
As it was said in the Introduction, this phenomenon is due 245.
to the lack of completion of the curing process. The physical [17] FERRY,D.J.: Viscoelastic Properties of Polymers, 3-rd edition, Willey,
1980.
properties of the propellant continue to change afterwards.
[18] HELLER,R.А., SINGH,М.P., ZIBDEH,H.: Environmental Effects on
These changes depend on a degree of completion of the Cumulative Damage in Rocket Motors. Journal of Spacecraft and
polymerization process. Rockets, 1985, Vol.22, No.2, pp.149-155.
The time distribution of the aging factors can be used to [19] GLIGORIJEVIĆ,N., ŽIVKOVIĆ,S, RODIĆ,V., SUBOTIĆ,S.,
correct the results of the uniaxial mechanical characterization GLIGORIJEVIĆ,I.: Effect of Cumulative Damage on Rocket Motor
which is planned to be done immediately after production, in Service Life, Journal of Energetic Materials, accepted 23.09.2014.
different test regimes. Unfortunately, it is not possible to doi.org/10.1080 07370652. 2014.970245.
make this complete procedure in a very short time after [20] BAUMGARTNER,W.E.: 1974. Aluminum Hydride Propellant
Shelflife. Lockheed Propulsion Company, Final Report, AFRPL-TR-
production. It can last quite a long time and the measured 74-78, ADB001669, November 1974.
values do not correspond to the real virgin values, due to the [21] RODUIT,B., FOLLY,P., SARBACH,A., BERGER, B.: Prediction of
influence of initial aging. These results should be corrected. the Thermal Behaviour of Energetic Materials by Advanced Kinetic
Many authors neglect the changes of the propellant Modeling of HFC and DSC Signals. International Annual Conference -
mechanical properties at the beginning of the rocket motor Fraunhofer Institut Chemishe Technologie, 2009, 40, V3.
service life. However, the uniaxial tension tests during the [22] George,P. Sutton, Oscar Biblarz. Rocket Propulsion Elements. Seventh
short age period have shown that these changes are too large edition. John Wiley&Sons inc, 2001.
and they should not be neglected, because they significantly [23] GLIGORIJEVIĆ,N., BOULAHLIB,M.A, ŽIVKOVIĆ,S.,
KOZOMARA,S., NIKOLIĆ,M., SUBOTIĆ,S.: Solving an Irregular
affect the quality of evaluation of rocket motor reliability and Burning Problem in a Small Rocket Motor, Scientific Technical
service life. Review, ISSN 1820-0206, 2014, Vol.64, No.2, pp.3-13.
16 GLIGORIJEVIĆ,N. etc.: MECHANICAL PROPERTIES OF HTPB COMPOSITE PROPELLANTS IN THE INITIAL PERIOD OF SERVICE LIFE

[24] Structural Assessment of Solid Propellant Grains, Agard Advisory Rocket Motor Thrust Vector Control System, Scientific Technical
Report 350. 1997. Review, ISSN 1820-0206, 2013, Vol.63, No.2, pp.27-38.
[25] LIU,C.T.: Cumulative Damage and Crack Growth in Solid Propellant. [28] BILLS,K.W., Jr.: Time-Temperature Superposition Does Not Hold for
Media Pentagon Report No.A486323, 1997. Solid Propellant Stress Relaxation. Aerojet Solid Propulsion Company,
[26] KADIRESH,P.N., SRIDHAR,B.T.N.: Mechanical and Ballistic Sacramento, California, AIAA Journal, CPIA Publication 283, 1983.
Property Variations of a Solid Propellant During Accelerated Ageing. [29] NASA: Solid propellant grain design and internal ballistics. NASA
Journal on Design and Manufacturing Technologies, 2007, Vol.1, Space Vehicle Design Criteria SP-8076, 1972.
No.1, pp.71-73.
[27] GLIGORIJEVIĆ,N., ŽIVKOVIĆ,S., SUBOTIĆ,S., KOZOMARA,S., Received: 22.12.2014.
NIKOLIĆ,M., ČITAKOVIĆ,S.: Side Force Determination in the

Mehaničke osobine HTPB kompozitnog raketnog goriva u početnom

periodu upotrebe
Jednoosni testovi istezanjem epruveta različitih sastava kompozitnih goriva na bazi hidroksi-terminiranog polibutadiena
(HTPB) pokazali su da se mehaničke osobine goriva intenzivno menjaju posle umrežavanja, čak do 100% početnih vrednosti,
tokom prvih nekoliko meseci. Mehaničke osobine se posle toga stabilizuju i počinju da se polako menjaju u suprotnom smeru.
Pažljiva merenja ovih veličina su potrebna zbog kontrole kvaliteta pri izradi i poređenju različitih sastava i šarži goriva.
Pored toga, vremenska promena mehaničkih osobina u početnom periodu posle izrade ne sme da se zanemari, jer značajno
utiče na rezultate strukturne analize pogonskih punjenja i procenu pouzdanosti raketnog motora.

Ključne reči: kompozitno raketno gorivo, mehaničke osobine, prirodno starenje, zatezna čvrstoća, deformacija, modul
elstičnosti.

Механические свойства ГTПБ композитного твёрдого ракетного

топлива в начальном периоде использования
Одноосные испытания на растяжение пробирок различного состава композиционных топлив на основе гидрокси-
планированого полибутадиена (ГTПБ) показали, что механические свойства топлива изменяются после интенсивной
сети, даже и до 100% от начальных значений в течение первых нескольких месяцев. Механические свойства затем
стабилизируют и начинают постепенно меняется в противоположном направлении. Тщательные измерения этих
величин, необходимы для контроля качества в процессе разработки и ради сравнения различных составов и
топливных партий. Кроме того, временные изменения механических свойств в начальном периоде после
изготовления не следует пренебрегать, так как они существенно влияют на результаты структурного анализа
ракетного топлива и на оценки надёжности ракетного двигателя.

Ключевые слова: композитное ракетное топливо, механические свойства, естественное старение, прочность на
растяжение, деформация, модуль упругости.

Les propriétés mécaniques du HTPB propergol composite dans le

période initial de l’utilisation
Les tests uniaxes par l’extension des éprouvettes de différents compositions des propergols composites à la base du
polybutadiène hydroxyle terminé (HTPB) ont démontré que les propriétés mécaniques des propergols changeaient beaucoup
après le durcissement jusqu’à 100 % des valeurs initiales au cours des premiers mois. Après cela les propriétés mécaniques se
stabilisent et commencent de changer lentement en sens inverse. Les mesurages faits attentivement de ces valeurs sont
nécessaires à cause du contrôle de qualité lors de la production et de la comparaison de différentes compositions et des charges
de propergols. A part cela le changement temporel de propriétés mécaniques dans la phase initiale après la production ne doit
pas être négligé car cela influence considérablement sur les résultats de l’analyse structurale des charges de propulsion et sur
l’estimation de la fiabilité du moteur à fusée.

Mots clés: propergol composite, propriété mécanique, vieillissement naturel, résistance à la tension, déformation, module
d’élasticité.