Original Article

High Performance Polymers

1–9
Influence of different crosslinking ª The Author(s) 2020
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DOI: 10.1177/0954008320940359
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of composite solid rocket propellants
based on HTPB

Islam K Boshra1, Guo Lin1 and Ahmed Elbeih2

Abstract
The crosslinking agent is a vital key which affects the mechanical properties of composite solid rocket propellants (CSRPs).
Under this scheme, the effect of crosslinking mixtures (CMs) based on trimethylolpropane (TMP) as a triol crosslinker and
butanediol (BD) as a chain extender on CSRPs based on hydroxyl-terminated polybutadiene was investigated. A series
of 27 propellant compositions was formulated to study the mechanical properties of the prepared CSRPs. The effect of
changing the weight ratio of TMP to BD in the CM was studied. In addition, the influence of increasing the percentage of
CM (from 0% to 0.5%) in the prepared samples was investigated. Also, the effect of the CM on CSRPs containing different
curing ratio of NCO/OH ¼ 0.7, 0.75, and 0.8 was studied to generate the largest possible strain-ability with high strength
over different levels of curing conditions. The mechanical characteristics (tensile strength and strain) of the prepared
CSRPs have been measured and plotted versus CM content, NCO/OH and TMP:BD ratio. Generally, the addition of CM
leads to a remarkable enhancement in the propellant mechanical properties. Samples containing TMP:BD (2:1) provide the
highest strength while samples containing TMP:BD (1:2) show the highest strain over all the NCO/OH ratios.
Formulations with TMP:BD (1:1) give high strength with moderate strain. Variation in CM content has a remarkable
influence on the mechanical properties of CSRPs. A wide range of tensile strength and strain were obtained from this
study to offer variety of results suitable for different applications in the CSRPs technology.

Keywords
Hydroxyl-terminated polybutadiene (HTPB), crosslinking mixture, mechanical properties, trimethylolpropane, butanediol

Introduction by producing high amounts of stable compounds, such as

carbon monoxide, carbon dioxide, and water vapors.6,7 To
Among the most popular implementation of polyurethane
accomplish its function efficiently through design consid-
(PU) elastomers is as a polymeric binder matrix in compo-
erations, a solid rocket motor needs to maintain its structural
site solid rocket propellant (CSRP). The main components
stability and should have appropriate tensile strength and
of PU-based CSRP are elastomeric binder (inert or ener-
strain under the wide range of mechanical stresses applied
getic), inorganic oxidizer, and metallic fuel all together as
during production, transport and handling, storage, ship-
a heterogeneous mixture.1 The polymer network with three-
ping, thermal cycling, instant ignition pressure, and accel-
dimensional structure attaches both oxidizer and metal fil-
eration overload during rocket engine flight.8,9
lers to generate a rubbery network; it can be called a densely
loaded PU structure. It provides the propellant grain with the
sufficient microstructure to preserve its structural integ-
rity.1–3 From the physical and chemical point of view, PU 1
Beijing University of Aeronautics and Astronautics, Beijing, China
has several applications in the military and civilian fields.4,5 2
Military Technical College, Kobry Elkobbah, Cairo, Egypt
PU is compatible with the traditional oxidizers and other
Corresponding author:
materials under standard conditions of storage. As it basi- Ahmed Elbeih, Military Technical College, Kobry Elkobbah, Cairo, Egypt.
cally has hydrogen and carbon, it decomposes throughout Email: elbeih.czech@gmail.com
combustion to increase the rocket motor specific impulse
2 High Performance Polymers XX(X)
Such propellants are designed to have a reliable long-
lasting storage ability based on studies of chemical struc-
tural aging. The composite propellant has a PU binder of 10–
15%. Nonetheless, the propellant grain mechanical and
process-ability characteristics are determined primarily by
the polymer matrix consisting of three parts: (1) a large chain
prepolymer (polyol), (2) a di- or triisocyanate curing
agent, and (3) a crosslinking mixture (CM) containing
chain extender (1,4-butanediol (BD)) and crosslinker
(1,1,1-trimethylolpropane (TMP)), together with other
ingredients like plasticizer, burn-rate modifier, cure cata-
lyst, and so on.10,11 The mechanical characteristics of the
propellants play a major role in the decision regarding the
type of application to be performed to the grain (free stand-
ing or case bonded).12,13 The hydroxyl-terminated polybu-
tadiene (HTPB) is the most popular polyol applied in recent
years.14 This liquid prepolymer has outstanding physical
characteristics including the low temperature of glass
transition, high tensile ability, and strong chemical resis-
tance.14,15 HTPB-based propellants have distinct advan-
tages such as very high reliability, good processing, and
unequaled mechanical performance.16,17 Hocaoğlu et al.18
discussed the alteration in the mechanical behavior of the
solid propellants based on HTPB and ammonium perchlo-
rate (AP) during the curing process in relation to variation in
the crosslink density (CLD) which was mainly calculated
via the curing ratio (R value), defined as the equivalent ratio
of diisocyanate to total hydroxyl value, besides the corre-
sponding ratio of triol to diol (triol/diol).
Manjari et al.10,19 investigated HTPB-based propellant
composition adjustment for improved mechanical proper-
ties, in addition to using HTPB with various molecular
weights and hydroxyl numbers in the production of CSRP
samples to discuss the effect of the processing parameters on
the resulting propellant properties. Based on their study, it
has been concluded that HTPB prepolymer with hydroxyl
numbers (OH value) of hydroxyl value 40–50 mg KOH/g is
favorable for the production of large-scale propellants
grains as this eliminates batch-to-batch fluctuation in
mechanical properties. CSRP was prepared with curing ratio
within 0.7–0.9. The composition was approved by perform-
ing experiments using a specified materials batch. However,
certain shortcomings in production such as lack of appropri-
ate HTPB grade allow researchers to use certain additives to
achieve desirable mechanical and thermal properties in
crosslinking processes. Both crosslinkers and chain exten-
ders are two of the most effective additives categories
besides bonding agents which enhance PU performance by
transforming its structure from linear to branched network
morphology.20–22 Chain extenders for PUs have been widely
researched. Adding chain extenders, like diols of low mole-
cular weight (BD), in gum stock compositions improves the
elastomeric characteristics of the finished PU product,
owing to the fact that the small diols link with diisocyanates
and make hard sites to act as a physical crosslink for PU
chains.23,24
Transformation of the PU matrix from linear to branched
network structure was needed to enhance its mechanical
properties.25,26 PU crosslinking could be performed in dif-
ferent ways.27,28 Low molecular weight triols such as TMP
and triethanolamine were used as crosslinkers in different
types of research.29–35 The most significant key parameter
for binder system is the CLD which defined as moles of
elastically effective matrix chains per unit volume. In addi-
tion to CLD, there are other parameters which determine the
mechanical and physical properties of the binder such as
network configuration, micro inhomogeneity, and polymer
chains chemical nature. Furthermore, it is possible to explain
more accurately the gum stock structure of the binder system
if the network molecular structure, side chains content, and
length allocation in the elastically efficient and side chains
are identified uniquely.36,37 The CLD can be tailored by
changing the proportional quantities of the prepolymer diol,
curing agent, and CM consisting of triol crosslinker TMP/
diol extender BD.38,39 These components react with each
other to produce one integral PU network that makes the
matrix softer or tougher at the end of the curing period.
Accordingly, the reacting species equivalent ratios, the
NCO/OH ratio, the CM composition (triol/diol) ratio, and
CM content, are important tools for adjusting and being tai-
lored in a strict range, and for this reason the material will
maintain its process-ability for casting.40 From an applicable
angle, those factors must be fine-tuned for obtaining satis-
factory mechanical properties. This needs a complete under-
standing of the influence of NCO/OH and triol/diol ratios on
the propellant mechanical behavior.41–43
In this contribution, 27 propellant samples based on PU
binder were prepared. The purpose of this study is to
enhance the mechanical properties of the propellant by using
advanced crosslinking additives at various NCO/OH ratio
ranging from 0.7 to 0.8. Three different CMs based on var-
ious combinations of TMP as a triol crosslinker and BD as a
diol chain extender were used and overall study performed
to discuss the impact of its content on the binder structure.
Mechanical characteristics were investigated to know how
the used CM influences it to determine the relationships of
structural properties depending on NCO/OH, CM composi-
tion, and CM content.
Experimental section
Materials
HTPB (R-45M; density: 0.9 g/mL, hydroxyl number: 0.84
meq/g, manganese: 2800 g/moL, viscosity at 25 C: 5800
cps) and tris(1-(2-methyl)aziridinyl)phosphine oxide
(MAPO) were purchased from Zibo Qilong Chemical Indus-
try Co., Ltd (Shandong, China). TMP 97% and BD 99% were
received from Aladdin Reagents (China) (Figures 1 and 2)).
Boshra et al. 3

Table 1. Mechanical properties of propellant samples with differ-

ent CM at NCO/OH ¼ 0.7.

Tensile strength
Sample CM (TMP:BD) CM (wt%) Strain (%) (kgf/cm2)

S1 1:1 0.15 30.1 6.9

S2 0.3 35.1 8.14
S3 0.5 38.0 11.3
S4 2:1 0.15 28.6 8.2
Figure 1. 1,1,1-Trimethylolpropane. S5 0.3 31.8 11.2
S6 0.5 34.0 12.6
S7 1:2 0.15 33.8 6.4
S8 0.3 37.5 7.35
S9 0.5 40.7 10.6

Figure 2. 1,4-Butanediol. CM: crosslinking mixture; TMP: trimethylolpropane; BD: butanediol.

Dibutyltin dilaurate (DBTDL) 95%, hexamethylene diiso- Table 2. Mechanical properties of propellant samples with differ-
cyanate (HMDI), and dioctyl azelate (DOZ) were supplied ent CM at NCO/OH ¼ 0.75.
by Sigma-Aldrich (Germany). AP and aluminum obtained
Tensile strength
from commercial source were used. Sample CM (TMP:BD) CM (wt%) Strain (%) (kgf/cm2)

S10 1:1 0.15 28.2 7.4

Preparation of CSRP by casting technique S11 0.3 32.0 9.2
S12 0.5 35.1 12.5
To study the effect of using CM on the improvement of S13 2:1 0.15 24.3 10.1
propellant mechanical properties, we maintained the sizes, S14 0.3 27.1 12.5
distribution, and solids amounts constant within 86% solid S15 0.5 29.2 14.1
S16 1:2 0.15 31.0 7.2
content (68% AP, 18% Al) in addition to the percentage and
S17 0.3 35.6 8.4
characteristics of the bonding agent (MAPO 0.3%) through- S18 0.5 37.1 11.3
out all the propellant samples in the study. By using three
different CMs consists of different combination of TMP as a CM: crosslinking mixture; TMP: trimethylolpropane; BD: butanediol.
triol crosslinker and BD as a chain extender (TMP:BD ratio
¼ 1:1, 2:1, and 1:2). Twenty-seven CSRP compositions performed for a minimum of three trials of each prepared
were prepared by changing the NCO/OH ratio (0.7, 0.75, sample and the average value of the results obtained was
and 0.8) with CM contents of 0.15, 0.3, and 0.5%. The CM reported. The test was carried out under normal temperature.
was prepared separately by continual mixing of the propor- The cross-head speed was 50 mm/min with 0.5 accuracy.
tional ratios of chain extender (BD) and crosslinker (TMP)
in a vacuumed rotating mixer for 2 h with temperature of 50–
60 C. A comparative study conducted by the preparation of Results and discussion
propellant samples without the addition of CM (CM ¼ 0%) Twenty-seven propellant experiments were produced using
to investigate the influence of both crosslinker and chain various CMs to analyze the dependency of the mechanical
extender on the crosslinking process and propellant mechan- properties on network crosslinking additives. CMs contain
ical behavior. selected combinations of the chain extender BD and triol
Casting technique was used to prepare the propellant sam- crosslinker TMP while varying the total CM content from
ples, starting with the mixing of various ingredients of HTPB 0% to 0.5% over curing ratios (NCO/OH) 0.7, 0.75, and 0.8.
prepolymer, CMs, bonding agent, and DOZ as plasticizer All of the prepared propellant samples were studied for their
with the solids for 1 h using an 8 kg vacuumed stainless steel mechanical properties such as tensile strength and elonga-
mixer followed by the addition of calculated quantity of the tion. The results obtained are presented in Tables 1 to 4.
diisocyanate HMDI and catalyst DBTDL 0.018 % (curing
catalyst: 10% solution of (DBTDL) in toluene) at 40 C, after
Effect of changing NCO/OH ratio on the mechanical
that starting the vacuum casting into the preprepared JANAF
(dumbbell-shaped) mold which left to be cured for 5 days at
properties of CSRPs containing CM
60 C. The tensile stress–strain relationship was measured Figures 3 to 5 illustrate the effect of the crosslinking addi-
experimentally for each of the prepared samples using tives on the tensile strength and elongation which determined
LLOYD universal test machine (AMETEK STC), for carry- as a function of curing ratio NCO/OH (R value) at different
ing out all the tensile mechanical tests. The tensile test was triol to diol ratios (TMP:BD ¼ 1:1, 2:1, and 1:2), respectively.
4 High Performance Polymers XX(X)

Table 3. Mechanical properties of propellant samples with differ- Table 4. Binder compositions and mechanical properties of pro-
ent CM at NCO/OH ¼ 0.8. pellants without CM at different NCO/OH.
Tensile strength Tensile
Sample CM (TMP:BD) CM (wt%) Strain (%) (kgf/cm2) HTPB DOZ MAPO HMDI Strain strength
Sample NCO/OH (wt%) (wt%) (wt%) (wt%) (%) (kgf/cm2)
S19 1:1 0.15 23.8 8.1
S20 0.3 28.1 10.4 S28 0.7 10.54 2.64 0.3 0.52 27.5 6.1
S21 0.5 30.9 14.2 S29 0.75 10.51 2.63 0.3 0.56 20.9 7.0
S22 2:1 0.15 18.2 11.5 S30 0.8 10.48 2.62 0.3 0.6 16.0 7.6
S23 0.3 21.0 13.8
S24 0.5 24.0 15.7 CM: crosslinking mixture; HTPB: hydroxyl-terminated polybutadiene;
S25 1:2 0.15 28.2 7.8 DOZ: dioctyl azelate; MAPO: tris(1-(2-methyl)aziridinyl)phosphine oxide;
S26 0.3 31.8 9.7 HMDI: hexamethylene diisocyanate.
S27 0.5 34.1 13.2

CM: crosslinking mixture; TMP: trimethylolpropane; BD: butanediol.

Figure 3. Variation of the tensile strength and strain with different curing ratio for CM ( 1:1). CM: crosslinking mixture.

Figure 4. Variation of the tensile strength and strain with different curing ratio for CM (2:1). CM: crosslinking mixture.

Figure 5. Variation of the tensile strength and strain with different curing ratio for CM (1:2). CM: crosslinking mixture.
Boshra et al. 5

Figure 6. Variation of the tensile strength and strain with CM content at NCO/OH ¼ 0.7. CM: crosslinking mixture.

Figure 7. Variation of the tensile strength and strain with CM content at NCO/OH ¼ 0.75. CM: crosslinking mixture.

Figure 8. Variation of the tensile strength and strain with CM content at NCO/OH ¼ 0.8. CM: crosslinking mixture.

The triol/diol ratio was maintained constant for each figure to
evaluate the impact of R value on the tensile properties.
A regular rise in the strength and a reduction in the strain
were observed with increasing NCO/OH for all the
various triol to diol mixtures because of the important role
that NCO/OH plays in generating the crosslinking and
binding between chains of the binder polymeric matrix.
Mechanical properties were sensitive to triol/diol ratio and
CM content.
Using CMs leads to a wide range of mechanical charac-
teristics of the propellant compared to propellants without
those additives over various NCO/OH ratios. For CM (1:1),
the tensile strength increased and varied from 6.9 kgf/cm2
(CM 0.15%) to 14.2 kgf/cm2 (CM 0.5%) instead of 6.1–7.6
kgf/cm2 with CM 0%, while the strain was in the range of
23.8% (CM 0.15%) to 38.0% (CM 0.5%) instead of 16.0–
27.5% with CM 0%.
The same trend observed in CM (2:1) to give strength
range of 8.2 kgf/cm2 (CM 0.15%) to 15.7 kgf/cm2 (CM
0.5%) and strain of 18.2% (CM 0.15%) to 34.0% (CM
0.5%), while CM (1:2) shows strength of 6.4 kgf/cm2
(CM 0.15%) to 13.2 kgf/cm2 (CM 0.5%) and strain of
28.2% (CM 0.15%) to 40.7% (CM 0.5%).
Effect of CM weight percentage on the mechanical
properties of CSRPs
Figures 6 to 8 demonstrate the tensile strength and strain
variation with CM content (CM%) at curing ratio NCO/OH
0.7, 0.75, and 0.8, respectively. Generally, using CM
6 High Performance Polymers XX(X)

Figure 9. Variation of the tensile strength and strain with CM triol % at NCO/OH ¼ 0.7. CM: crosslinking mixture.

50 20
NCO/OH = 0.75 18 NCO/OH = 0.75
45
0.15% 0.30% 0.50%

Tensile strength (kgf/cm²)

0.15% 0.30% 0.50% 16
40 14
Strain (%)

12
35
10
30
8

25 6
4
20
2
15 0
30 35 40 45 50 55 60 65 70 30 35 40 45 50 55 60 65 70

TMP vs BD (%) TMP vs BD (%)

Figure 10. Variation of the tensile strength and strain with CM triol % at NCO/OH ¼ 0.75. CM: crosslinking mixture.

increases both tensile strength and strain compared to sam-
ples prepared without CMs over the whole range of R value
because of the higher degree of crosslinking induced by the
triol and more strain capability achieved by the chain exten-
der; for that reason, both strength and elongation are
improved as CM content increases. With the R value of
0.7, for the propellant samples containing CM with
TMP:BD ¼ 2:1, with the increase in CM content, the rising
rate in tensile strength is increasing giving the highest
strength of 12.6 kgf/cm2 at 0.5% CM content compared to
the other mixtures added due to its higher triol (TMP) ratio
which causes more crosslinks between chains and three
dimension polymeric matrix.
While CM (1:2) shows almost the same trend as the CM
content increases, this time the rate of increase of strain is
increasing resulting in highest strain of 40.7% at 0.5% CM
content as a result of the high chain extender (BD) content
in the mixture leading to higher elongation capabilities of
the extended chains; at the same time, CM (1:1) achieves
higher strength than (1:2) mixture with moderately higher
strain than samples containing (2:1) mixture.
At R value of 0.75 and 0.8, an expected increase was
observed in the tensile strength following the same behavior
regarding triol/diol ratios and CM content. As a result for
both NCO/OH ratios, samples containing 0.5% CM (2:1)
have the highest strength of 14.1 kgf/cm2 and 15.7 kgf/
cm2, respectively, while samples with 0.5% CM (1:2) have
the highest strain of 37.1 and 34.1%, respectively, and with
the same trend, samples containing CM (1:1) show moderate
mechanical properties among propellants based on the other
two mixtures.
Effect of TMP:BD ratio on the mechanical properties
of CSRPs
The variation of mechanical properties with triol/diol ratio
in terms of TMP wt% at different NCO/OH is illustrated in
Figures 9 to 11. It was observed from the figures that the
tensile strength is low at the beginning due to the low triol
content while higher elongation was obtained due to the high
percentage of the chain extender diol, then strength starts to
increase as a result of increasing triol content at the expense
of diol leading to a decrease in the strain.
The propellant surface at higher triol/diol ratios was
shown to be more brittle and the strain results obtained were
the minimum with maximum stress resulting from the high
triol/diol ratio (2:1) over all the different CM percentages
(0.15, 0.3, and 0.5%). The reason for this result was that with
the increase of triol/diol ratio, the propellant gets harder
resulting more CLD with high stiffness in the propellant,
and at the same time, the strain capability is remarkably
reduced at higher levels of TMP.
Boshra et al. 7

Figure 11. Variation of the tensile strength and strain with CM triol % at NCO/OH ¼ 0.8. CM: crosslinking mixture.

Effect of both CM wt% and TMP:BD ratio on the 18

NCO/OH = 0.7
mechanical properties of CSRPs 16
TMP : BD
14

Tensile strength (kgf/cm²)

(1:1)
The overall stress–strain results for the propellants of CMs
12 (2:1)
of various triol/diol ratios with wt% of 0, 0.15, 0.3, and
10 (1:2)
0.5% at three different constant NCO/OH values (0.7, 0.75,
8
and 0.8) are shown in Figures 12 to 14, respectively. Form
6
the figures it is clear that, generally in all cases of triol/diol (CM = 0 %)
4
ratios over all the CM percentages, both stress and strain
2
were increased in the direction of the CM content increase, 10 15 20 25 30 35 40 45
and all mechanical properties were enhanced after the addi- Strain (%)
tion of CM compared to propellants with no crosslinking
additives. Compared to CM (1:1) and because of the equal Figure 12. Strength–strain relation of all propellant samples
prepared at NCO/OH ¼ 0.7.
content of the crosslinker (TMP) and the chain extender
(BD), propellants with CM (2:1) showed higher strength
18
with lower elongation, while on the other side CM (1:2) NCO/OH = 0.75
16
showed the opposite behavior. TMP : BD

Those diagrams show us a full image of how the mechan- 14 (1:1)

Tensile strength (kgf/cm²)

(2:1)
ical properties of the propellant at various curing ratios have 12
(1:2)
been improved by the addition of CMs with different triol/ 10

diol ratios over various mixture percentages. 8

6 (CM = 0 %)

4
Conclusions 2
10 15 20 25 30 35 40 45
Both tensile strength and elongation were sensitive to the Strain (%)
existence of triol crosslinker and chain extender. Overall
mechanical characteristics were enhanced by the addition Figure 13. Strength–strain relation of all propellant samples
of CMs. The influence of TMP on the strength was clear as prepared at NCO/OH ¼ 0.75.
observed in CM (2:1) while the strain capabilities was
affected by the presence of BD in the CM which was noted 18
NCO/OH = 0.8
in CM (1:2). The inclusion of both TMP and BD in the 16
TMP : BD
propellant composition gives the binder matrix a balanced 14
(1:1)
Tensile stress (kgf/cm²)

structure between soft and hard segments. The desired 12 (2:1)

(1:2)
mechanical behavior needs the practical balance between 10

crosslinker and chain extender through the variation of 8

curing ratio NCO/OH. The different ratios of NCO/OH 6 (CM = 0 %)

used enabled us to obtain a wide range of mechanical prop- 4

erties by using different CM content (0.15, 0.3, and 0.5%). 2

10 15 20 25 30 35 40 45
Propellant samples with NCO/OH ¼ 0.7 yield tensile
Strain (%)
strength of the order 6.4–12.6 kgf/cm2 and strain of 28.6–
40.7% for different content and TMP:BD ratio of the CM. Figure 14. Strength–strain relation of all propellant samples
While NCO/OH ¼ 0.75 imparts expected higher strength in prepared at NCO/OH ¼ 0.8.
8 High Performance Polymers XX(X)
the range of 7.2–14.1 kgf/cm2 and lower strain of 24.3–
37.1%. Finally with the same trend as NCO/OH increases,
samples with NCO/OH ¼ 0.8 show strength of 7.8–15.7
kgf/cm2 and for the strain 18.2–34.1%. Consequently, this
wide range of mechanical characteristics achieved from
this study is so helpful for making the decision regarding
the kind of application will be performed to the grain and
which scale could be suitable for the propellant formulation
by the diversity of results provided from this investigation.
Declaration of conflicting interests
The author(s) declared no potential conflicts of interest with
respect to the research, authorship, and/or publication of this
article.
Funding
The author(s) received no financial support for the research,
authorship, and/or publication of this article.
ORCID iD
Ahmed Elbeih https://orcid.org/0000-0001-9143-0804
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