90
Realization of an Eco-Friendly Solid Propellant Based on
HTPB-HMX-AP System for Launch Vehicle Applications
Rm. Muthiah*, T. L. Varghese, S. S. Rao, K. N. Ninan, and V. N. Krishnamurthy
Propellants, Polymers, Chemicals and Materials Entity, Vikram Sarabhai Space Centre, Trivandrum 695 022 (India)
Realisierung eines umweltfreundlichen Raketenfesttreibstoffes auf
der Basis HTPB/HMX/AP fuÈr die Anwendung bei TraÈgerraketen
Ein umweltfreundlicher HTPB-Hochleistungstreibstoff mit verbes-
serter Energetik wurde realisiert im Kleinmaûstab durch Einarbeitung
von 10±20 Gew.% HMX.Dieser Treibstoff mit 88% Feststoffgehalt hat
eine gute Verarbeitbarkeit, gute mechanische Eigenschaften und einen
reduzierten Druckexponenten ergeben. Die Verunreinigung durch
HCl-Rauch im Raketenabgasstrahl wurde um 20±30 Gew.% reduziert.
Dieser Treibstoff 1aÈût einen spezi®schen Impuls von 293 Sekunden
erwarten bei einem Arbeitsdruck von 70 bar und einem Quer-
schnittsverhaÈltnis von 10. Kleinmotoren mit einem Gewicht von 2 kg
wurden erfolgreich statisch getestet zur Bewertung ihrer Leistung.
Summary
An eco-friendly higher solid loaded HTPB propellant with improved
energetics has been realized in small scale by incorporating 10±20%
by weight of a high energy material namely, HMX. This propellant
with 88% solid loading has given good processability, mechanical
properties and reduced pressure index. Pollution due to HCl smoke in
the rocket exhaust is reduced by 20 to 30% by weight. This propellant
is expected to give a vacuum speci®c impulse of 293 seconds at an
operating pressure of 70 bar and an area ratio of 10. Sub-scale motors
of 2 kg size have been successfully static tested to evaluate the per-
formance.
1. Introduction
Hydroxy-terminated polybutadiene (HTPB) based com-
posite propellant is the present work horse propellant for the
solid rocket motors of the Indian Launch Vehicles. This
propellant has undergone various stages of development and
quali®cation tests and is being successfully used in the
various stage solid motors of Augmented Satellite Launch
Vehicle (ASLV) and Polar Satellite Vehicle (PSLV). The
successful scale-up and productionization of 129-tonne
booster motor of PSLV, the third largest solid booster and
the ®rst largest operational HTPB based solid rocket motor
has established ISRO's (Indian Space Research Organiza-
tion) capability in solid rocket technology.
The main constituents of this HTPB propellant are
hydroxy-terminated polybutadiene (HTPB) as binder,
ammonium perchlorate (AP) as oxidizer and powder grade
aluminium (A1) as metallic fuel along with other additives
* Paper partly presented at 4th International Symposium on Spe-
cial Topics in Chemical Propulsion, Sweden, May 1996.
# WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1998
Propellants, Explosives, Pyrotechnics 23, 90±93 (1998)
ReÂalisation d'un propergol solide de fuseÂe eÂcologique aÁ partir de
HTPB=HMX=AP pour des applications aÁ des fuseÂes porteuses
Un propergol solide HTPB hautement performant favorable aÁ
l'environnement et aÁ l'eÂnergie ameÂlioreÂe a eÂte reÂalise aÁ eÂchelle reÂduite
en incorporant 10 aÁ 20% d'une substance hautement eÂnergeÂtique, le
HMX. Ce propergol, dont la teneur en solide est de 88% s'est aveÂreÂ
facile aÁ travailler et posseÁde de bonnes proprieÂteÂs meÂcaniques et un
exposant de pression reÂduit. La pollution due aÁ la fumeÂe de HCI dans
le jet de gaz des fuseÂes a eÂte reÂduite de 20 aÁ 30%. On s'attend aÁ ce que
ce propergol donne une impulsion speÂci®que dans le vide de 293
secondes aÁ une pression de travail de 70 bar et un rapport de section de
10. Des moteurs miniaturiseÂs de 2 kg ont eÂte testeÂs statiquement avec
succeÁs pour en eÂvaluer les performances.
such as plasticizer, wetting/bonding agents, cross linker,
curatives, stabilizers, burn rate modi®ers, etc. The major
components of the propellant is AP which is present to an
extent of about 70%. During the propellant combustion,
large amounts of HCl gas and other chlorine compounds are
generated in the motor exhaust. These gases are highly
corrosive and toxic in nature and they form semi-opaque
clouds under humid conditions. During the ®ring of large
size boosters of launch vehicles such as Space Shuttle
Booster (503 tonnes) enormous quantity of HCl (above 100
tonnes) is produced and let to the atmosphere. This may
lead to ``heavy acid rain'' polluting the environment and
also cause depletion of the ozone layer. These aspects are a
subject of concern among the scientists in recent times,
eventhough the quantities of harmful exhausts from rockets
are orders of magnitude lower than that produced from
automobiles. Efforts have been made for the development
of alternative propellants which are environmental friendly
and are equally or more energetic to meet the future space
requirements.
Various alternatives have been reported(1) to reduce the
concentration of harmful exhaust products in solid pro-
pellants. The use of non-HCl generating oxidizers such as
ammonium nitrate (AN) has been thought of. The phase
change occurring at 32 C and the low oxidizing potential
leading to lesser energetics are the inherent problems with
AN. Another approach(2) is to partially substitute AP with
AN or nitramine compounds such as HMX or RDX so that
the extent of HCl pollution can be reduced. Recent literature
reports use of ADN(3) (ammonium dinitramide) and HNF(4)
(hydrazinium nitroformate) as eco-friendly oxidizers in
solid propellants.
In this paper, we report the development of an environ-
mental friendly propellant based on HTPB binder with
0721-3115/98/0204±0090 $17.50‡:50=0
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Propellants, Explosives, Pyrotechnics 23, 90±93 (1998) Realization of an Eco-Friendly Solid Propellant 91

partial substitution of AP by nitramine compound, HMX.

Incorporation of 10±20% by weight of HMX reduces the
HCl smoke by 20±30% by weight at the same time
improving the speci®c impulse. The research programme
has led to the development of high performance eco-
friendly propellant for future space applications.

2. Experimental

2.1 Materials

HTPB used in this study has been made in-house by the

free radical solution polymerization technique. Two grades
of HMX of average particle size 60 and 220 micrometer and
AP of 40 and 300 micrometer were used in the propellant
composition.
HMX is a high explosive generally used in explosive
charges. But in solid propellant, it acts as a slow explosive
as it is diluted with other propellant components. The
characteristic feature of high sensitivity to friction of HMX
is reduced by wet handling with suitable plasticizer. HMX
is a stoichiometrically balanced material constituted of C,
H, N and O and is expected to give higher energy release(5)
C4 H8 N8 O8 ! 4 CO ‡ 4 H2 O ‡ 4 N2 ‡ DH
Figure 1. Effect of HMX on (A) HCl smoke and ¯ame temperature,
(B) vacuum Isp and molecular weight.

2.2 Performance Analysis

Performance evaluation of HTPB propellant containing
HMX at concentration level up to 30% by weight has been
carried out using standard computational programme. The
effect of HMX loading on HCl smoke in the motor exhaust
and the energetics in terms of speci®c impulse, ¯ame
temperature and mean molecular weight of combustion
gases are shown in Fig. 1 (A and B).
The ®gure shows that HCl smoke in the motor exhaust
decreases with increase in HMX concentration. Flame
temperature (Tc) and mean molecular weight of exhaust
gases (Mw) show a gradual decrease as the HMX loading is
enhanced. However, speci®c impulse and vacuum speci®c
impulse (Isp) which are the indices of energy content,
increase to the maximum level at about 20±25% loading of
HMX and thereafter show a decreasing trend.
The effect of HMX loading at 0, 10, 20, 25 and 30%
levels on HCl smoke, Isp, Tc and Mw is shown in Table 1.
It can be seen that at 20% level of HMX where the ener-
getics is maximum, a reduction of 30% by weight of HCl
smoke in the motor exhaust could be realized. The lower
¯ame temperature also is advantageous in reducing the dead
weight of insulation, inhibition etc. of the rocket motor. The
reduction in the mean molecular weight of exhaust gases
also improves the motor ef®ciency. This leads to a low
pollution propellant with improved energetics, i.e. an
increase in vacuum Isp by 4.2 seconds. The increase in Isp
could be explained by the fact that HMX is a stoichiome-
trically balanced material and that the major products of
combustion are lighter molecules like CO and H2 which
contribute more towards propulsive energy.

Table 1. Effect of HMX Loading on HCl Smoke, Isp, Tc and Mw

HMX HCl content Reduction Isp at 70 Vacuum Tc (K) Mw
loading in exhaust of HCl bar (sec) Isp at 70
(wt.%) (wt.%) (wt.%) bar (sec)
0 20.6 0 265.0 288.5 3613 28.3
10 17.4 15.5 266.8 291.9 3550 28.3
20 14.6 30.0 268.0 292.7 3469 27.3
25 13.1 36.4 268.1 292.7 3417 26.8
30 11.0 46.6 267.7 292.0 3354 26.3
Solid Loading: 88% (18% AI), HTPB Binder: 12%, AP ‡ HMX: 70%.
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92 Rm. Muthiah et al. Propellants, Explosives, Pyrotechnics 23, 90±93 (1998)

Table 2. Propellant Composition

Ingredients (wt.%) 1* 2 3 4 5 6
HTPB ‡ plasticizer ‡ TDI ‡ additives 12 12 12 12 12 12
Al (15 mm) 18 18 18 18 18 18
HMX (220 mm) 0 0 10 10 0 20
HMX (60 mm) 0 10 0 10 20 0
AP (300 mm) 56 48 48 50 50 40
AP (40 mm) 14 12 12 0 0 10
* Blank (without HMX).

2.3 Propellant Processing and Characterization

An 88% solid loaded HTPB propellant formulation

containing 18% AI was selected for this study. HMX was
incorporated as a partial substitute of AP. The propellant
ingredients were mixed in a 3 litre capacity sigma mixer.
The processability of the slurry was monitored by measur-
ing the end-of-mix viscosity (EOM) and viscosity build up
for a period of 3 hours. The propellant slurry was vacuum
cast either as cartons for evaluation of mechanical proper-
ties and strand burn rate or as 100 mm diameter tubular
grains weighing about 2 kilogrammes of propellant for
static ®ring. The mechanical properties of cured propellant
samples were evaluated using dumb-bells conforming to
ASTM standards D-412-68 (Type-C) at a cross head speed
of 50 mm/minute at 25  C. The burn rate of the cured
propellant strands was determined using Acoustic Emission Figure 2. Effect of HMX loading on slurry viscosity for various
Technique at different pressures varying from 30 to compositions, j-1, r-2, e -3, m-4, d-5, u-6 (ref. Table 2).
70 kg/cm2.
coarse and ®ne, and HMX coarse and ®ne show more or less
3. Results and Discussion similar results. This shows good manoeuvrability of the
propellant formulation with different particle sizes of AP
The slurry characteristics of HMX loaded (20%) HTPB and HMX.
propellant and blank are shown in Fig. 2. HMX propellant shows slower burn rate compared to
The viscosity build-up data of the propellant slurry in Fig. blank as seen from the burn rates of 10% and 20% HMX
2 show good processability with HMX loaded propellant loaded propellant. The effect of particle size of HMX seems
and are quite comparable to those of the blank. to be negligible. The burn rate pressure index was found to
The mechanical properties of the cured propellant such as be lower with HMX propellant. This could be due to the
tensile strength, elongation, modulus, hardness, density and melting of HMX and formation of melt layer of HMX±
burn rate are listed in Table 3. HTPB binder, acting as a thick barrier between AP parti-
The mechanical properties of the blank and the ®ve dif- cles. This causes a decrease in the diffusion rate of fuel to
ferent formulations with different combinations of AP the diffusion ¯ame. The burn rate and combustion index are

Table 3. Effect of 10%±20% HMX Loading on HTPB Propellant Properties

Composition

Properties 1* 2 3 4 5 6
Mechanical
1. Tensile strength (kg/cm2) 7.6 7.4 7.2 7.5 8.0 8.2
2. Elongation (%) 33 35 37 36 36 41
3. Modulus (kg/cm2) 47 45 43 48 45 53
4. Hardness (Shore-A) 70 70 70 70 70 72
5. Density (g/cm3) 1.800 1.795 1.795 1.790 1.790 1.790

Ballistic
1. Strand burn rate at 70 bar, mm/s 6.90 6.15 5.90 5.30 5.25 5.50
2. Burn rate pressure index n 0.44 0.35 0.34 0.33 0.30 0.31
* Blank (without HMX).

Propellants, Explosives, Pyrotechnics 23, 90±93 (1998)
Figure 3. Thrust-time pro®le for PEM motors, ÐÐÐÐ standard,
Ð Ð Ð with 20% HMX.
mainly controlled by the diffusion ¯ame produced by the
decomposition products of AP and binder(6). Ballistic per-
formance of 20% HMX loaded HTPB propellant is shown
in Fig. 3. 100 mm diameter 200 mm long PEM motors
weighing 2 kilogrammes of propellant were static tested.
The thrust time curves show similar pattern with increased
burn time for HMX propellant. The smooth combustion of
HMX-based HTPB propellant has been established in this
sub-scale motor. Scale-up version of this motor is under
way. The extent of exact increase in energetics can be
assessed better with large size motors.
4. Conclusion
Development of an eco-friendly high performance pro-
pellant containing 20% HMX was realized in sub-scale
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Realization of an Eco-Friendly Solid Propellant 93
mixing. Processability and mechanical properties are quite
comparable to HTPB propellant (blank). Burn rate and burn
rate pressure index are found to be lower than those of the
blank.
This novel formulation is expected to give a 30% (by
weight) reduction of HCl smoke in the exhaust, improved
vacuum speci®c impulse by 4.2 seconds and reduction in
the ¯ame temperature by 144 K.
5. References
(1) P. A. O. G. Korting et al., ``Combustion Characteristics of Low
Flame Temperature Chlorine-Free Composite Solid Propellants'',
AIAA-Paper, 1987±1803.
(2) D. W. Doll et al., ``Low Cost Propellant for Large Booster
Applications'', AIAA-Paper, 1986±1706.
(3) Stu. Borman, ``Advanced Energetic Materials for Military and
Space Applications'', C & EN, January 17, 1994, Washington.
(4) H. F. R. Schoyer, A. J. Schnorhk et al., ``High Performance Pro-
pellants based on Hydrazinium Nitroformate'', J. Propulsion and
Power 11, No. 4, 856 (1995).
(5) Teruo Sofue et al., ``A High Performance Apogee Boost Motor
Using HMX Composite Propellants'', Tokyo Conference, 1986.
(6) Tohru Mitani et al., ``Combustion Characteristics of AP/HMX
Composite Propellants'', Tokyo Conference, 1986.
Acknowledgements
The authors are grateful to Director, VSSC for the permission to
present the paper. Thanks are also due to many colleagues who helped
in characterization and manuscript preparation.
(Received August 14, 1996; Ms 60/96)