Journal of Scientific & Industrial Research

Vol. 6 1 , November 2002, pp 899-9 1 1

Solid Propellant B inders

S R J ai n *
Department of Aerospace Engineering, Indian Institute o f Science, Bangalore 560 0 1 2
Solid propellants are widely used i n modem rockets and missiles. Although the h istory of solid rockets could be traced
to the di scovery of gunpowder over a thousand years ago. the technology could be perfected only by the later half o(the 20l h
century. The fai lure of gunpowder rockets was largely due to the unknown consolidating technique of the powder
composition. The emergence of large solid propellant motors had to await the dawn of polymer science and
technology(S&T). Specific syntheses of functionally terminated polymers having cross-linking capabi l i ty led to the
emergence of casting technology of solid composite propellants. This review describes the various polymeric fuellbinder
systems used or considered for use in solid propellants. It includes a brief background, advantages, and shortcomings of the
valious systems. an account of the cUITently used binders and a critical survey of the advanced polymers envisaged for future
usage. Special emphasis h as been laid on recently synthesized polymers having N-N bonds in their structures, and on the
feasibility of developing smokeless propellants based on ammonium nitrate.

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Introduction

Historical Background

Chemical propellants are the main source of

propul sion energy of rockets and missiles. The
enormous amount of energy needed to launch a space
vehicle is provided by the controlled combustion of a
chemical combination of a ' fuel ' and an 'oxidizer' ,
known as propellant. A rocket fuel is basical l y a
reducing agent, which when oxidized, would release
high heat energy and gaseous products. Of the various
fuel/oxidizer combinations, depending on their
physical
states,
solid
composite
propel lants
comprised a powder oxidizer embedded in a matrix of
a fuel , are the ones used very widely. The solid
propel l ant rockets are easier to handle and in ready
to-use condition all the time. Initially, the solid
propellants were meant for combat rockets only, but
their simplicity and availab i lity in al most unlimited
size have led them to be used as the main, sustainer or
booster charge for many types of rockets and
missiles. The immense progress in solid rockets may
be noticed by comparing the size of the solid
boosters. The first booster charge developed for
JATO (Jet-Assisted Take-Off) aircraft weighed only
28.2 kg, while the giant size booster used in Space
Shuttle, e.g., is a 3.7 m diam and 3 8.47 m long grain ,
having 504 t o f propellant.

Hi storicall y the fi rst sol id rockets were

projecti le launchers in war, based on gunpowder (also
known as blac k powder) comprising a mixture of
potassium n itrate (oxidizer), charcoal and sulphur
(fuel/binder). The compressed mixture contained in a
metal tube with a hole on one end formed the crude
rocket. Tippu Sultan, the king of Mysore in the late
1 8ti1
century. used them profusely i n his battles. In
those days, military rockets were not in use in
Europe, but they were in existence i n India. They
were borrowed by the British after having been
themselves
exposed
to
rocket
attack
near
Seringapatam in 1 799 in wars against Tippu. I These
were, however, crude rockets lacking range, safety
and accuracy, and l argel y unreliable.

*Professor Emeritus

The gunpowder sticks (grains) made simply by

compressing the charge to a reasonably high density
to make it uni form, cannot be defect-free as
compressing makes the grain excessively brittle.
Brittle charges develop hairli ne cracks invisible to the
eye on temperature change during storage or whi le
transporting from one place to another. The
combustion of propellants having cracks or holes i s
erratic, and often results i n explosion .
This inherent flaw of the gunpowder rockets,
however, was not understood till the later part of the
1 9 th century. It i s thus obvious that l arge size rocket
grains could not be made by the c harge compression
technique.

900

J SCI IND RES VOL 61 NOVEMBER 2002

The next i mportant step in combat rockets was

the introduction of smokeless powder compri sing
nitrocell ul ose (NC) and nitroglycerine (NG) by A
Nobel in 1 890. The so-called, 'double base' (two
explosive components) or 'homogeneous' prope l lant
was a plasticized mass of NC and NG. The propel l ant
sl urry made by using a solvent could be given a shape
either by extrusion process or by casting into
containers. The homogeneous propellants are
essentially defect-free and, therefore, more reliable.
They have been extensively used in sounding rockets
and as ' sustainer' grains for mi ssiles. Propel lant grain
sizes varying from 60 to 200 mm (outer diam) and
weighing 5 to 200 kg have been developed for
different appl ications. However, it i s difficult to make
very large size grains by the hydraulic extrusion
process or by the gel casting techn i que since the
propel lant mass becomes porous w h i le driving away
the residual solvent.
The technology of making large size grains
emerged along with the basic understanding of
polymer science. The so-cal led composite solid
propel lants came into existence largely because of the
significant advances made in devel oping polymer
casting techniques soon after WW II. It was indeed a
clever idea of chemists to use functionall y terminated
organic polymers which could be used both as h igh
energy fuel s, and also as binders to consolidate the
powder oxidizer. It was envisaged that viscous pre
polymers could be mixed with solid powder
composition to form a slurry that could be cured in
situ after casting i n suitable moulds.
Energetics
The power of a propel lant i s often expressed i n
terms of specific impul se (Isp). It i s defined a s the
impulse (thrust x time) per unit weight of prope l lant.
The equations relating Isp w ith the chemical
parameters are described as follows:
Isp

Fx

T I W; Isp ex: (11H) 1I2 ; Isp ex: (Te l Me) 112,

where, F thrust, T time, W weight, W

heat release (heat of combustion) per unit weight of
propel lant, Te
chamber temperature, and Me
average molecular weight of combustion products.
=

It is obvious that h igh heat of combustion and

low molecular weight products are the bas ic
requirements for achieving higher Isp. S ince the heat
of combustion is dependent upon the heats of
formation of the propel lant constituents (fuel and

oxidizer), it is desirabl e that they have high heats of

formation . Fuels and oxidizers having positive or low
negative heats of formation are, therefore, preferred.
Simi larly, low molecular weight product spec ies help
in i mproving the Isp. Hydrogen for that matter i s not
only a good fue l but also a des i red exhaust product.

Solid Oxidizers
Like the gunpowder, a composite propel l ant is a
heterogeneous mixture of bas ical ly a powder
inorganic oxidizer and a fue l (bi nder). Usually, a
metal l i ke powder aluminum and other ingredients are
added to improve the performance characteri stics.
Since the main criteria of a propel lant compos ition i s -.--
to produce high heat of combustion and low
molecular weight gaseous products, solid oxidizers
producing completely gaseous products are therefore
preferred. A quick survey of the various inorganic
oxidizers, centered usuall y around the nitrate and
perchlorate
salts,
revealed
that
ammOnIum
perchlorate (NH4CI04) and ammoni um nitrate
(NH4N0 3 ) could be the right candidates. Unlike
potassium nitrate and potassium perchlorate, used i n
gunpowder and asphalt propellants, respectively,
these oxidizers produced totally gaseous products.
Besides, ammonium perchlorate (AP) had very
favourable other properties, l ike h igh available
oxygen, high density, non-hygroscopicity, easy
storabil ity, and low sensitivity. These characteri stics
have made AP the workhorse oxidizer of solid
propel lants. Indeed, it has been the monopoly
oxidizer of virtual l y a l l the large-size solid prope llant
rockets, worldover for the past 50 y or so.
Ammonium nitrate (AN) also produces
completely gaseous products, which are even
smokeless. It is also relatively very cheap but i ts
inherent
characteristics,
l i ke
low
energy,
hygroscopicity, an awkward phase change around
room temperature and very low burning rate
(discussed later) have been deterrents to its large
2
scale use in soli d propel lant compositions, so far .
Other non-metal li c oxidizers have also been
examined but have not been found suitable for use for
one reason or the other. Nitronium perchlorate
(N02CI04), investigated extensively in 1 970s, e.g.,
has a positive heat of formation and a highly
favourabl e oxygen balance but was discarded because
of its instabil ity in the presence of moisture.
Ammonium dinitramide (ADN) also has high
avai lable oxygen and a relatively low negative heat of

._

--",,'

JAIN: SOLID PROPELLANT BINDERS

formation but its synthesis i s hazardous and

complicated, and reported to be exorbitantly costly in
the US. Unconfirmed reports suggest that the
Russians have used ADN in certain missiles, and a
way has been found to synthesize this material
cheaply. Hydrazinium salts, l i ke the nitroformate,
mono- and di-perchlorates, have also been examined,
but either they have l i ttle available oxygen or are
highly sensitive to explosion.
Polymeric B inders

If '

- ""- -

After having selected ammonium perchlorate as

the oxidizer of choice the emphas is of research was
shifted to evolving the right type of fuels (binders).
Here again the chemical composition of the fuel
should be such that basical ly it gives high combustion
energy (calori metric value) with AP and low
molecular weight products. A careful consideration of
the combustion energies of the elements revealed that
the only elements that produced relati vely high
combustion energy, and also produced gaseous
products, are hydrogen and carbon. Although many
l ight metals, like Li, Be, B, Mg and Al have higher
combustion energies but they produce condensed
(solid ash) products. It thus fol lows that the search for
solid propel lant fuels has to be foc used primaril y on
compounds of hydrogen and carbon or simply stated,
hydrocarbons. Further, since hydrogen has higher
combustion energy per unit weight than carbon, a
hydrocarbon with high HlC ratio is preferred.
A processed solid propel lant grain must possess
good mechanical strength. In order to provide the
structural integrity to the powder oxidizer, it was felt
that the fuel used should necessari ly be a long chain
molecule, which could form a cross-l inked matrix on
curing. Organic polymers, made of long chain
hydrocarbons, thus became the prime contenders of
propellant formulations, as they could serve the dual
purpose of a high-energy fuel as well as a matrix
forming binder.
The main idea behind the use of pol ymers in
propel lant formulation was to evol ve a casting
technology of large-size, defect-free grains. As stated
earl ier the idea was to mix the powder oxidizer with a
. viscous pre-polymer having suitable end-groups and a
curing agent, to form a pourable slurry which could
be cast in a container of a pre-determined s ize and
geometry. The curing reaction (process of cross
linking) would be so chosen that the end-groups link
with the curing agent without l i berating any smal l

90 1

molecules, l i ke H 20, CO2, S02 , etc., since the

liberation of small molecules and/or their subsequent
removal makes the grain porous and hence is
undesirable. The slurry would solidify (cure) simply
on raising the temperature or on standing for a while.
The mix would then contain an oxidizer embedded in
a matrix of polymer (fuel). Such a grain would be free
of voids, and form a monol ithic structure. It would
also possess the desired mec hanical strength because
of the cross-linked polymer-matrix structure.
Early Systems

The h istory of solid composite propel lants could

be traced back to the pioneering work of Von
Karman, Frank Mal i na, John Parsons and Edward
Foreman
at
the
Guggenheim
Aeronautical
Laboratory, Cal ifornia Institute of Technology
(GALCIT t USA, while developing a solid fuel
rocket for J ATO aircraft in 1 939. The charge for
JATO consisted of ammonium nitrate as the oxidizer,
with black powder and cornstarch as the fuel and
3
inhibitor, and glue as the combustible binder.
Another formulation, GALCIT 5 3 , was introduced i n
1 942. I t consisted o f potassium perchlorate a s the
oxidizer, di spersed in melted asphalt (as both fuel and
binder) and poured while hot into cylindrical moulds.
When cooled down the "cured" propel lant cylinders
were inserted into the rocket casing. This was the first
"cast" solid propellant that permitted the production
of solid rockets of any size or shape. However the
asphalt composites were found to have poor physical
properties, such as poor tensile strength and cracking
under normal temperature cycl ing .
Based o n the experience with the asphalt
compositions, it soon became evident that better
physical properties could be achieved by the use of
cross-linked thermosetting polymers. Polysulphide
rubber as a castable fuellbinder was adapted in 1 945
4
by Bartley at GALCIT . Propel l ant compositions
having potassium and/or ammonium perchlorate were
cast with Thiokol LP-3 polysulphide l iquid polymr.
This became the basis for the most modern large
scale cast solid-fuel rockets. The polymer, ethyl
formal polysulphide, was prepared from dichloro
ethyl formal and sodium polysulphide using a small
amount of trichloropropane cross-linker. Many
#The GALCIT work eventually led to the formation of the Aerojet
Engineering Corporation in 1 942 and to the establishment of
Caltech's Jet Propulsion Laboratory in 1 944.

902

J SCI I N D RES VOL 6 1 N O V E M B E R 2002

variations in the polymer formulation were fol l owed

subsequently. Studies of these materials in propel lant
formulations carried out at JPL, Thiokol Chemical
Corp. and .at other propel lant companies, let to a
significant understanding of the chemistry of solid
propel lants. The presence of heavy sulphur atoms in
the polysuphide rubbers, however, decreases the
performance, hence these rubbers were subsequently
replaced by hydrocarbon (CHNO) polymers.
By this period the chemistry of sol id propel l ants
was fairly well understood. Chemi sts knew the basic
requirements a polymer should have in order to cast
large-size high-energy grains having good mechanical
properties. Several polymeric binder systems were
evolved, almost simul taneou sly at JPL, Aeroj et
General, Thiokol, and General Tire, and Rubber
chemical corporations.
Unsaturated Polyesters

One of the earliest polymer systems avai lable

and considered for propellant formulation was the
unsaturated polyesters. Polyester systems, in general,
have higher fuel val ues than the polysulphides and
could be manufactured to spec ific molecular weights
and viscosity. The unsaturated polyesters are usually
prepared by condensing a dicarboxylic acid with a
dihydric alcohol , one or both of which contain the
olefinic bonds. These bonds are uti l i zed in cross
li nking via simple vinyl monomers, l i ke styrene and
methylacrylate. The addition of the low molecular
weight olefin fluidizes the propel lant mix . The cross
linking process could be initiated by peroxides and
controlled by the number of unsaturated sites in the
polyester pre-polymer. Additional p lasticizers could
be used to adj ust the propel lant mix properties.
Several acceptable propel lant formulations were
developed, particularly by the Aerojet company
around 1 946. The grains made with styrene/polyesters
had good aging characteristics, but had hard structure
and could not bond to aluminum or steel wal ls, thus
were unsuitable for case bonding. They were also
smoky and not high performing. The polyester
propellants have now been replaced by high
performing polybutadiene compositions.
Plastisol Propellants

The p lastisol prope llants (also known as PVC

propellants), di ffer from composite propel lants i n the
technique of sol idifying the mass. While i n composite
prope llants the solidification (curing) is accomplished

by cross-l inking the pre-polymer using a tri

functional curative or opening-up of vinyl bonds, in
plastisol propel l ants it is achieved through solvation
( solution) of the resin powder in a non-volati l e l iquid,
which also acts as a p lastici zer for the resin.
Usually, polyvinyl chloride (PVC) powder is
used as the resin and an ester l ike dioctyl phthalate, as
a plastic izer. Finely d ivided PVC powder is mixed
with the plasticizer in al most equal amounts. To the
resulting sl urry an oxidizer l ike AP, sufficient to
oxidize both PVC and the pl asticizer is added along
with other ingredients, such as a metal powder and
stabil izers. The mix is poured i nto mou lds and heated
D
to about 1 70 C so that PVC dissolves into the
plasticizer. The mi xture on cool ing to room
temperature solidifies into a homogeneous mass
having good tensile strength and smooth s urface.
Used widely in sounding rockets and tactical
missiles, the PVC propel lants are not case-bondable.
Heating the PVC at high temperature causes it to
decompose paltially splitting HC\ . Modifications in
composition and processing procedure of PVC
s
propel lants have been recently reported. However the
plastisol process is unsuitable for making large grains.
Polyurethanes

A binder system, capable of many vanatlOns

results from the reaction of difunctional alcohols
(diols) with diisocynates to form polyurethanes. The
noteworthy feature of this reaction is that no small
molecules are spl it out when the two moieties are
joi ned together, unlike the condensation reaction. The
hydroxyl terminated pre-polymer backbone may be
varied; it could be a polyester, polyether or
polybutadiene. U sually, toluene dii socyanate i s used
as chain extender for polyurethane formation. The
new pol ymer has diisocyanate end-groups, which
could be subsequently cross-li ked using a triol, l ike
glycerol. Of the three types of pre-polymers the
polyesters (e.g. neopentylglycolazelate) are not
desirable because of their relati vely high viscosity
and low spec ific impulse (lsp) with AP oxidizer. The
hydroxyl terminated polyethers, like poly(oxy
ppropylene)glycol, are easi ly available, have low
viscosity, and adequate rate of cure and good aging
characteristics, but give lower performance.
Hydroxyl Terminated Polybutadiene (HTPB)

The HTPB polyurethane binder system gi ves the

h ighest specific i mpulse with AP oxidizer. A

JAIN: SOLID PROPELLANT BINDERS

relati vely late comer, HTPB i s the only pre-polymer

which was specifical l y synthesized for its use as a
propellant binder. It i s usually produced by the free
radical solution polymerization of 1 ,3 -butadiene
using hydrogen peroxide i n itiator. The pre-polymer
has molecular weight in the range, 2500 to 2800;
average functional ity, 2.2 to 2.4; and viscosity, 65 P

at 30 C. Originally marketed by Atlantic Richfield

Company, USA, under the trade name ARCO R-45 ,
in India i t was synthesized and developed at V SSC
(lSRO), Trivandrum, and the process know-how
transferred to MIs NOCIL, India, for production .
Besides HTPB the ISRO has also developed two
more hydroxyl terminated binders, namely the ISRO
Polyol and a hyroxyl terminated natural rubber,
6
(HTNR). The ISRO Polyol , based on castor oil, is a
saturated ester with low molecular weight (-2000),
nearly bi-functional, having a viscosity of about 20 P
at room temperature. The hexyl pendant groups
impart good low temperature properties in addition to
making it a self-plasticized system. It is cured with
isocyanates and trihydroxy compounds, simi lar to
HTPB . Copolyurethanes of HTPB and ISRO Polyol
made
with
dii socyanates
of
toluene
and
hexamethylene have also been studied 7. The ISRO
Polyol propel lants have been used in sounding
rockets.
Many favourable properties of the polyurethane
system, like high density, rapid burning rate, high
tensile strength, excellent fuel value, etc. , makes i t a
binder of-choice . As a matter of fact the most widely
used bi nder system used c urrently is based on HTPB
polyurethane.
Polyurethane binders for solid propellants were
independently developed by chemists at Aeroj et in
1 948, and at JPL in 1 95 3 (ref.8). The first successful
use of the propellant based on polyurethane with AP
as oxidizer, was made by Aerojet for the Hawk
surface-to-air missile system in 1 954. It was a highly
successful propellant; the Aerojet suppl ied over
40,000 Hawk motors to the US Army from 1 954 to
1 990 (ref.4). Minuteman was America ' s first all
sol id-fuel ICBM, whose development started i n 1 95 8 .
The propel lant used in its second stage was
polyurethanelAP/aluminum powder. The HTPB
polyurethane is the most s uitable and widely used
binder system for large solid boosters. For example
the giant Delta and Titan IV rockets, the Arian strap
on boosters and the Japanese H-II, all use HTPB
based propel lants. In India the solid boosters of the

903

satellite launch vehicles, ASL V, PSLV and GSLV are

based on HTPB propellants. The main first stage of
the PSLV consists of a 2.8m diam core motor having
1 40 t of HTPB/AP/AI propellant providing over 500 t
of thrust. In addition, the Rohini series of sounding
rockets ranging from RH-75 to 560-mm diam motors
also contain HTPB propellants.
Carboxyl Terminated Polybutadienes

Carboxyl groups condense easi l y with epoxides

and aziridines without liberating any small molecules.
This reaction has been the basis of evolving pre
polymers based on carboxyl terminated polybutadiene
(CTPB) . Liquid polybutadiene pre-pol ymers and i ts
copolymers with acrylic acid and acrylonitrile having
carboxyl groups have been synthesized and used
extensively in produc ing very large size propel lant
grains. Being composed of almost a pure hydrocarbon
chain, polybutadienes have h igh calorimetric values,
and are preferred fuels. As binders they provide h igh
sol id loadings and sati sfactory mechanical properties
to the grain over a wide range of temperatures.
Polybutadiene-acryl ic acid (PBAA) was the first
butadiene copolymer to be used in a rocket motor
app l ication. Owing to the method of preparation the
liquid polymer is a mixture of non-functional, mono-,
di- and polyfunctional segments. As a result the
epoxide-cured systems show poor reproducibil ity of
mechanical properties and therefore, PBAA I S no
more used as a binder.
The terpolymer, polybutadiene-acrylic ac id
acrylonitri le (PBAN) provides much better storage
and mechanical characteristics to the propel lant grain .
The introduction o f acrylonitrile moiety i mproves the
spacing between the carboxyl species and provides
better control of curing process. S ince its i ntroduction
in 1 957, more solid rockets were produced with
PBAN than any other polymer till 1 975. S ince then
PBAN has been largely replaced by more energetic
polymers, CTPB, and HTPB . The Space Shuttle
boosters are based on PBAN propel lants. The first
Indian Satellite Launch Vehicle (SLV -3), launched
successfully i n 1 980, also used the PBAN/AP
propel lants.
Both, in PBAA and PBAN the carboxyl groups
appear as pendent groups. The random location of the
carboxyl groups was leading to open chain ends that
were not effective in providing good physical
properties.
Ultimately,
polybutadienes
were
developed with carboxyl groups i n the termination
position to take full advantage of the entire length of

904

J SCI IND RES VOL 6 1 NOVEMBER 2002

the polymer chain. These pre-polymers marketed as

Thiokol HC434 and B utarez CTL, were synthesized
by a free radical or l ithi um i nitiated technique to an
average molecular weight of 3500-5000, and had
nearly a bi-functional structure, i .e., one carboxyl
group at each end of the polymer chain. The curing
(cross-linking) of CTPB is ach ieved by reacting with
trifunctional epoxides (e.g. Epon X-80 l ) or aziridi nes
(e.g. MAPO). These attributes of CTPB helped i n
achieving
substantially
improved
mechanical
behavior of highly loaded sol id propel lants,
particularly at low temperatures. The CTPB based
propel l ants provide very high spec ific i mpulse,
j ust about I s less than the HTPB/polyurethane
system.
A pre-polymer akin to CTPB , cal led REF 20,
has been developed by ISRO . It is a l actone
terminated polybutadiene, having a molecular weight
of about 3000 and a vi scosity in the range 200-300 P.
It gives superior mechanical properties as compared
to CTPB at the same solid loading. It was used
in the upper stages of SLV-3 and ASLV rockets
and as apogee kick motor to put the 'Apple' satellite
into orbit.
Epoxy Resins

Resins having epoxy end-groups have been used

as propellant binders, as they exhibit good
processabil ity, low cost, excellent case-bonding
nature and good mechanical properties. Fairly high
Isp could be achieved with epoxy binders. V arious
types of epoxy resins are avai l able commerc i al l y the
most common being the one based on bi sphenol-A.
The epoxides can be easily con verted to
thermosetting polymers by reacting with curing
agents l ike pri mary or secondary amines, and
dicarboxylic acids. One of the important advantages
of the epoxy resins is that there is virtually no change
in
volume (shrinkage) after cUring. Lately,
diglycidylamine epoxy resins, based on bis
hydrazones having N-N-bonds in the backbone
(di scussed later) have been prepared specifical l y for
9
their use i n solid propel l ants.
ders
Energetlc B 111
.

1 0 1 3

Of the many i ss ues relating to the rocket

performance, maximizing the speci fic i mpulse ( Isp)
has remai ned the major criterion, so far. Most studies
have been aimed to achieve higher Isp by opting for
more energetic oxidizers and fuels (binders).

Approaches to i mprove the energetics of the binder,

i nvolves the i ntroduction of explosophore groups, l i ke
-N02, -ON02 , -NF2 and N 3 in the polymeric chain.
These groups contribute to i ncrease in the heat of
formation (making it more positive) of the polymer,
and hence enhance the overa l l heat of combustion.
The density of the polymer i s also i ncreased which
means higher amount of the oxidizer could be loaded
per un it vol ume. The presence of an oxidizing
elements i n the binder could be advantageous as it
reduces the amount of loading of the powder
i norganic oxidizer (AP) required for complete
combustion), thereby making the mixing of the
i ngredients easy. This is i ndeed beneficial from both
the processing and performance aspects. For AP/CH
propellants the stoichiometric (oxidizer/fuel) ratio
being, 90.5/9 . 5 , it is not poss ible in practice to
process grains having such a high oxidizer loading
with adequate mechanical strength. The upper limi t of
loading being about 86 per cent, most AP-based
propel l ants are fuel-rich and hence give less than the
expected theoretical spec ific impu l se.
Another approach is to introduce metal elements
into the polymer backbone. Since l ight metals have
h igher heats of combustion, their i ntroduction in the
pol ymer itself, i nstead of adding as powder, (a metal
powder is usually added to the propel l ant mix to
increase the Isp) would result i n enhanced energy.
With thi s view, several polymers containing AI,
Mg, and Boron i n the backbone were synthesized in
the 1 960s.
While many of these options look attracti ve,
there are several assoc iated inherent problems. For
instance the use of energetic binders often causes
stabil i ty and compatibil ity problems. The energetic
material contai ning oxygen and fl uorine groups,
which are introduced at the expense of hydrogen,
lower the Isp to some extent. The rheological
properties are also adversely affected in most cases.
Moreover the i n troduction of both the oxidizer and
fuel groups i n the same molecule makes it overly
sensitive and hazardous to handle. Spec ial
precautions have to be taken particularly in
synthesizing s uch materials. B eside, there are many
other considerations that have assumed greater
significance in recent years. These are, cost, safety,
rel i ability, environmental i mpact, transportation, long
self-li fe , etc . Any new binder produced must prove to
be better performer with respect to these aspects too.

JAIN: SOLID PROPELLANT BIN DERS

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Azide Polymers

The most prominent among the energetic

polymers are the ones containing the azido groups.
The hydroxyl terminated polymers of azidomethyl
oxirane (epoxide) and oxetane have been prepared for
their use as binders. Of these the most widely studied
is the glycidyl azide polymer (GAP) of the oxirane
family. It is a un-crosslinked polyol, and is a vi scous
liquid at room temperature. It has an average
functionality of 2.7 hydroxyl groups, and molecular
weight, 700. This polymer has been prepared at
various propellant researc h laboratories by reacting
polyepichlorohydrin with sodium azide, varying in
functionality as well as molecular weight. GAP is
now commercially available, marketed by the Special
Chemicals Division of 3M company. GAP cured with
a d i isocyanate by i tself sustains combustion and
hence has been examined as a fuel for i ntegrated ram
14
rockets. When used as a plasticizer, it is found to
IS
enhance the burning rate of AP/epoxide propellants.
AP/GAP
propel lants
have
poor
mechanical
properties, especially the elongation at low
temperatures.
Other promising azide polymers are the poly
(bis-azidomethyl)oxetane
(BAMO)
and
poly
(azidomethylmethyl)oxetane (AMMO). Poly B AMO
i s a stiff solid, while poly AMMO is a soft elastic
polymer. Copolymers of B AMO and AMMO, have
been successfully synthesized at Thiokol, which 'are
13
thermoplastic
i n nature.
The
thermoplastic
elastomers (TPEs) having ' hard' and 'soft' segments
are useful since their co-crystallization itself forms
the necessary three-dimensional network of inter
linked soft unsymmetrical polymer blocks. No cross
l inkers are used in the sol idification process.
The concept of using the TPEs, having hard and
soft segments as binders i s relatively new. It
essentially evolved because of the i mmense difficulty
faced i n di sposing the solid propel lant grains, which
are actual l y
thermosetting
type
cross-linked
composites. The only way to destroy such a mass
(after its useful life) is by burning, which causes
pollution if carried out in open atmosphere.
Degrading the grain chemically and disposing in a
closed cycle reactor i s very expen sive and not an easy
task. In fact, more efforts are being made in finding
efficient ways to disposing a solid propellant grain
than to produce a new one ! The TPE b inder systems
are preferred because they can avoid this destruction

905

process. The physical cross-l i nks formed on co

crystall ization between the hard and soft segments are
reversible and di sappear above the melting point of
the crystalline hard block. The propellant i ngredients
could thus be reclaimed by simply melting the
propellant grain, and subjecting them to recovery
processes. It is a wonderful concept, if it works.
Oxetane thermoplastic elastomers have the potential
to play a maj or role in the next generation of
propellants, explosives, and pyrotechnic systems,
13
according to Mil ler .
Mixed Polymer Networks

Although
the HTPB -polyurethane system
provides the highest specific i mpulse for AP-based
propel lants, in certain situations adjustments of the
combustion and mechanical characteristics are needed
depending upon the mission requirement. Mixed
binder network systems, composed of two co
polymers, or interpenetrating polymeric chains, have
been proposed to improve these properties. Studies on
AP propel lants with interpenetrating polymer chains
of HTPB and polystyrene or polymethylmethacrylate
as binder, have proven the usefulness of this
concept. 1 6 It helps in fine tuning the propel lant
characteristics. Similarly the co-polyurethanes made
of HTPB and ISRO Polyol have been examined in
detail . It i s noticed that by varying the ratio of the two
hydroxyl pre-polymers, chain extenders, and cross
l inkers, copol yurethanes having a wide range of
7
tensile strength and elongation could be obtained .
When these copolyurethanes are used as a binder,
they are shown to alter the burning rate and
l7
mechanical properties of AP propellants . A detailed
study pertaining to characterization and modeling of
network parameters of co-polyurethanes has been
18.
carried out
l9 27
N-N-Bonded Polymers -

Polymers having n itrogen-nitrogen (N-N) bonds

in their structures are relatively new comers. The self
igniting (hypergolic) nature of N-N bonded
compounds, l i ke the hydrazi nes and even solid
hydrazones on coming into contact with l iquid
oxidizers like nitric acid and n itrogen tetroxide, is
wel l known. It was considered worthwhile to
synthesize polymers having N-N bonds, i nitially as
fuels for hypergolic hybrid rockets. For the first time,
epoxy terminated hydrazones resins were prepared i n
the author' s laboratory a t the Indian Institute of
I9 22
Science - . These polymers are low molecular

906

J SCI IND RES VOL 6 1 NOVEM BER 2002

weight viscous resins of carbono- or thiocarbono

hydrazones having diglycidylamine epoxy end
groups. The synthesis of these resins is s i mple, non
hazardous and cheap. The overall attractive
characteristics of these polymers led to examination
of their role as binders for solid composite
propel lants. Several new digl ycidylamine epoxy
terminated
dicarboxyl
bis(hydrazones)
were
23 24
prepared .
subsequently, and a detai led study
fol lowed. It is i nteresting to note that a variety of
resins could be synthesized simply by changing
backbones and also the substituent groups but using
the same procedure. The much desired alteration i n
their properties t o suit specific propel lants
characteri stics could thus be made by simply
choosing the most suitable polymer. Of late the
hydroxyl terminated N-N-bonded res ins have also
25
been synthesized .
Characterization data of some of these
26 27
resins . , l isted in Table 1 , reveal that they have
adequate viscosity for h igh solid loading and
relatively high density. A h igher density of these
resins means that the density specific i mpulse (Isp.d)
of propellants could be much higher than those based
9 26
on polybutadiene binders . .
Table I

The main role of a binder i s to provide adequate

structural i ntegrity to the propellant grain . The
polybutadiene binders are much preferred because of
their rubbery nature. In general the propel lant grains
processed w ith carbono- or thiocarbono-hydrazone
based resins have hard structures. However, typical
26
compression strength data
of the AP based
propel lants, shown in Table 2, indicate that it could
be varied considerably. Apparently the mec hanical
strength of the dicarboxyl hydrazone resins based
systems depends upon the n umber of the spacer (CH2)
groups in the parent molecule. Propellants processed
w ith the resin having eight spacer groups (e.g.
DESBuH) have mechanical properties quite close to
26 28
those based on CTPB , .
A general weakness of any propel lant system
concerns its burning rate. The control of BR is an
i mportant aspect of sol i d propel lant formulations.
Propel lants having different BRs are needed
depending on the miss ion requirements. Since the BR
essential l y depends on the chemical composition, i.e.,
oxidizer, fuel, and their ratio, (at a particular
pressure), i t i s fixed once the composition i s decided.
The variation required i s usuall y effected by using
catalysts, although they are least des i red as they
adversely add to the dead weight, and also affect the

Properties of some N-N-bonded resins and CTPB

Viscosity at 3 5 C
(poise)

Heat of combustion
(kcal/g)

Density
(g/ce)

Diepoxide of bisfurfuraldehydeearbonohydrazone (DEFCH)

404.7

5. 74

1 .3 7

Diepoxidc of bisfurfuraldchydethioearbonohydrazone (DEITCH)

467.4

6.00

1 .37

Diepoxide of sebaeoyl bisfurfuraldehydehydrazone (DESFH)

1 00

6.45

1 .22

Dicpoxide of adipoyl bisbutanonehydrazone (DEABuH)

1 57

6.64

l.15

Diepoxide of sebacoyl bisbutanonehydrazone ( DESBuH)

75

7. 1 3

1.12

- 1 50

9.70

0.92

Resin

Carboxyl Terminated Polybutadiene (CTPB)

Table 2 - Compression strength data of AP propellants based on N-N-bonded resins and CTPB
Per cent compression

Modulus
(kg/em2 )

400

7.5

8280

DEABuH

250

1 1 500

DESBuH

1 20

10

1 400

CTPB

98

15

1 300

Binder

Ultimate compression

(20 per eent)

Strength (kg/cm2 )

DESFH

"'-.

J A I N : SOLID PROPELLANT B I N DERS

aging characteri stics. The BR of AP propel l ants could

also be enhanced to some extent by using the ul tra
fine particles of AP. B ut making and storing of ultra
fine powder is a difficult task. Instead, altering the
BR by changing the fuel (bi nder) is a highly desired
proposition as it is used as a minor component 1 4
per cent). I t thus makes sense to develop new binders
when a significant increase in the BR is required. In
this context, it is interesting to note that the N-N
bonded pol ymers when used as binders, increase the
burning rate significantly (Table 3 ) . For AP
propel lants, an almost three-fold increase the burn ing
rate over that processed with polybutadiene (CTPB )
28 29
binder . is noticed. This is significant, as increment
of this magn itude in the BR is not normal ly possi ble
with the hydrocarbon (CHO) binders . It is the
presence of the N-N bonds in these binders which i s
responsible for the high combustion reactivity i n
these propell ant systems.
Besides the enhancement in the BR the presence
of ni trogen in the polymer affects the stoichi ometric
OIF ratio favourably. It becomes much lower, which
means that a higher amount of the binder could be
used to process the propellant. In other words, while
the amount of HTPB/CTPB required for processing
stoichiometrically balanced AP prope llant is merely
9.46 per cent, the amount needed for the new N-N
bonded polymer is nearly 14 per cent, which i s
Table 3 - Burning rates o f A N , PSAN and A P based prope l l an t
compositions
Prope l l an t composition

Burning rate
at 70 atm

(oxidizerlbinder=80/20)

(mm/s)

Pressure
index

AN/DEFCH

2.78

0.33

PSAN ( K N 03)IDEFCH

4.28

>0. 8

PSAN ( K F)IDEFCH

5 .9 8

>0. 8

P S A N ( KF)lDEFTCH

5.39

>0. 8

P S A N ( K2Cr207)IDEFTCH

4.04

0.52

P S A N ( KF)/CTPB

2 .70

0.7 1

AN/CTPB

2. 1 1

0 . 68

AP/DES B u H

20.8

0 . 63

APIDESFH

21.1

0 . 64

8 2

0.44

AP/CTPB

907

sufficient to cast a practical 86 per cent solid l oading.

These considerations make the N-N-bonded polymers
very attractive binders for AP propel lants.
Drawbacks of APIHTPB Propellants

As cited earl ier the AP/HTPB is an excel lent

system incorporating many desirabl e features like
h igh energy, strong binding characteristics, safety,
easy handling, fairly high burn rate, and rel atively
low cost. It has been the most widely u sed solid
propell ant world over. Perhaps, the only serious
drawback is that its products of combustion, which
incl ude gases l i ke HCI and ch lorine, cause
atmospheric pol l ution and smoke. This has been a
cause of concern i n recent years, particularly at the
l aunch cites, for l arge motors. For example, in each
l aunch of the space shuttle, its solid propel lant
boosters exhaust 1 62 . 9 t of HCI and 24. 1 t of chlorine
in the atmosphere. Similar is the case with Ariane-5
with i ts two solid boosters each holding 237 t of
propel l ant. Increasing concern for clean atmosphere
in recent years cal l s for a compel ling need for
developing eco-friendly clean propel l ant systems.
Apart from pol lution concerns, smoky propel lants are
undesi red for mil itary appl ications. Dense smoke
clouds, produced by AP propel l ants could lead to
easy detection of the l aunch sites. Yet other reasons
against AP propellants is their corrosive exhaust
products (chlorine and HCI ) and high flame
temperature, which make them unsuitable as gas
generators, used to start and drive gas turbines.
S mokeless AN-based Propellants

Ammonium n itrate is being reconsidered

seriously as an oxidizer for solid propel lants in recent
years to overcome the problems associated with AP.
It is a very cheap material and avai l able i n-plenty, as
it is commonly used as a fertilizer, and in civil
explosives. Its combustion products are totally
innocuous and smokeless. A lthough AN-based
propel lants have been used as gas generators, AN has
some unfavourable characteristics to suit as one-to
one substitute for AP. It is hygroscopic, and
undergoes a crystal phase change accompanied by a
volume change (expansion) at room temperature, due
to which propel lant grains develop cracks during
storage. Al so, AN propell ants bum very s lowly and
have low energetics. Efforts made in recent years to
improve these c haracteristics to make it a suitable
propel l ant oxidizer, however, have l argely been
successfu l .

908

J SCI IND RES VOL 61 NOVEMBER 2002

The near-ambient temperature phase (IV -III)

transition, e.g., is no more a serious problem. In fact
the crystal transformations of AN have been studied
by numerous investigators using a variety of
experimental techniques, as cited in our recent
review. 2 Our own observations have proved beyond
doubt that the awkward phase (IV -III) transition
could be arrested completely by co-crystall izing AN
2
with an appropriate amount of a potassium salt. . 30
Interestingly the propel lant samples having 80 per
cent solid loading of the phase stabi l i zed ammonium
nitrate (PSAN) using potassium dichromate show
9 22 Similarly, potassium
almost nil expansion. .
dinitramide (KDN) is reported to have a dramatic
phase-stabi lizing effect. Moreover, AN phase
stabilized with KDN is believed to give i mproved
ballistic performance - increased thrust per unit time,
reduced variabi liy. and better predictability compared with AN without KDN. 1 1 Interestingly the
hygroscopicity of AN is also reduced on co
crystall izing with K + salts.
The problem of low burning rate of AN
propellants has been tackled by d ifferent approaches.
These incl ude the use of catalysts, such as chromium
compounds, addition of metal s l i ke Mg, use of a fast
burning oxidizer like AP, and use of energetic
binders, such as, azide polymers. Of these the
approach based on energetic binders is most
promising. However, many problems, like poor
ignitability, combustion instabi lity, thermal stability,
inadequate mechanical properties, and high friction
sensiti vity associated with the azide polymer systems,
.
.
.3 1 3
. - h as to be overcome pnor to th ell' use.
Interestingly, as shown in Table 3 the N-N
bonded resins have a significant influence on the
burning rate of AN propel l ants. A substantial
enhancement in the BR is observed when PSAN
instead of AN is used. 9.22 B urning rates close to the
AP/CTPB system could be achieved when AN phase
modified with potassium fluoride, and an N-N
bonded binder were used. These results paral lel those
obtained by Menke et at. 3 1 on propel lants based on
PSAN having the azide binder. It is sign ificant to note
that the phase modification not only prevents the
un wanted volume change around the ambient
temperature, but also helps in enhancing the burning
rate of AN propel lants. Indeed the very significant
enhancement in the BR has paved way for the
feasibility of PSAN propellants in actual usage.

The last issue remaining pertains to the poor

energetics of AN propellants. Seemingly, there is no
way AN propel lants ' energetics could be made at par
with those based on AP, simply because i t has higher
heat of formation, density and oxygen balance than
AN. However, choosing the right kind of binder can
make some improvements possible. For example,
CTPB or HTPB is not a suitable binder for AN
propellants at least for two reasons. First the
CTPB/AN propellants burn very slowly - at about
one-fourth the rate of CTPBIAP propellants.
Secondly, because of the low available oxygen in AN
the
amount
of
oxidizer
needed
for
a
stoichiometrical ly balanced composition i s 94. 2 per
cent, which is too high a loading to cast in a grain
shape. As a result the AN/CTPB propel lant grains are
al ways highly fuel-rich, giving much lower than the
theoretical Isp. Recent investigations on AN
propellants cast with N-N-bonded binders reveal that
not only the burning rate is i mproved signifi cantly as
mentioned earlier, but the cast grains could be made
that have an almost oxygen balanced compos ition,
since a l ower amount of AN (-85 per cent) is needed
for complete (stoichiometric) combustion.
A comparison of the theoretical performance
parameters of various propel lants having different
27
oxidizers, 26. is made in Table 4. It is evident that the
Isp of AN prope llants processed with N-N-bonded
binders is significantl y higher. For example, at a
practical 85 per cent AN loading, the theoretical Isp
with CTPB binder is only 205 . 5 s; it cou ld be
enhanced to 222 s by using an N-N-bonded binder.
The chamber temperature (Tc) and the chacteristic
velocity (C*) are also apprec iably higher. Even at
equi valence ratio, cD, 1 (stoichiometric balance), the
N-N-bonded resins give superior parameters than
CTPB for AN systems . It is thus evident that the Isp
of the AN systems can be i mproved upon by using
appropriate binders. To sum up, these results clearl y
show that AN could be made to work, by using
appropriate binders and phase modifiers, as a
potential oxidizer for solid propel lants.
=

Propellant composi tions based on AP and ADN

also give superior performance parameters with N-N
bonded binders at 85 per cent soli d loading. Although
better performance could be achieved with the
polybutadiene binders at stoichiometric loading, it is
not possible to achieve i n practice without adversely
affecting the mechanical properties. At practical sol id
l oading the N-N-bonded resins give higher Isp than

909

JAIN: SOLID PROPELLANT B I NDERS

Table 4 - Performance parameters of propellants at 85 per cent, and stoichiometric solid loading

Binder

Oxidizer
(per cent)

DEFCH

<I>

[sp (s)

Tc ( K )

Mc

C* (m/s)

AN ( 85)

1 .\0

2 1 9.2

2 1 56

22. 9 1

1 35 8

DEFTCH

AN (85)

1.10

222.0

2 1 97

23.0 1

1 37 1

CTPB

AN (85)

1 .60

205 . 5

1 622

1 9.45

1 266

DEFTCH

AN (89.8)

1 .0

228.3

2370

23.93

1 407

DESFH

AN (9 1 .0)

1 .0

225 . 6

2296

23.59

1 393

23.26

1 384

CTPB

AN (94.2)

1 .0

223 .6

2249

DEFTCH

AP (85)

0.9

244. 1

2992

28.2 1

1 475

DESFH

A P (85)

1 .03

245.2

2952

27.46

1 484

DES BuH

AP (85)

1.11

24 1 . 1

2868

26.36

1 482

CTPB

AP (85)

1 .3

242.6

2770

24. 1 2

1 504

DEFTCH

AP (83.7)

1 .0

247.4

3027

28.06

1 488

DESFH

A P (85.6)

1 .0

245. 1

294 1

27.59

1 479

DESBuH

AP (87. 1 )

1 .0

244.7

2990

29.09

1 48 1

CTPB

AP (90.0)

1 .0

253.0

3046

26.78

1 528

DEFTCH

ADN (85)

1.1

259.4

3079

25.0

1 585

CTPB

ADN (85)

1 .6

248. 6

2625

2 1 .26

1 549

DEFTCH

A D N (87.2)

1 .0

260.6

3058

25.27

1 574

CTPB

A D N (92.7)

1 .0

265 . 1

3061

24.42

1 602

that could be obtained with CTPB i rrespective of the

oxidizer (AN, AP or ADN) used. This emphasizes the
overall scope and usefulness of the N-N-bonded
polymeric bi nders in sol id propellants.
Other Considerations
Aging

Aging is one of the prime areas of concern. A

solid propel lant, particularl y a combat rocket grain
has to be stored for several years before an event
occurs when it has to be fired. Yet it must be kept in
readiness all the time retaining its pre-determined
characteristics, like the burning rate and pressure
index, mechanical properties and structural integrity,
unaltered. This is particularly difficult because the
oxidizer and the fuel are in physical contact all the
time and there is every l ikelihood they would undergo
slow reaction between themselves, which could be
further catalyzed by the additives like the B R

modifiers, during storage. The grain could become

porous if acted upon by moisture, or it could even
change its characteristics by oozing out some of the
p lasticizer, if used. Thus, there are many factors that
contribute to aging. B ut the first and foremost is that
the proposed new binder must be least reactive with
the oxidizer in the solid state.
There is no sati sfactory method to evaluate a
priori the safe life of a sol id propel l ant grain.
Accelerated aging studies are carried out by
monitoring BR or mechanical properties periodicall y
a t elevated temperatures, b u t they hardly correlate
with the room temperature aging data. The only
reliable way is to conduct a comprehensive study
under storage conditions over a n umber of years and
evaluate the safe life but it is time consuming, and so
conveniently forgotten . As a consequence the
reliabi lity of the system becomes questionable. Very
often , a new or modified propell ant system performs
as per the specifications in the initial testing stage but

9 10

J S C I I N D R ES VOL 6 1 NOV E M B ER 2002

i ts burn ing rate e.g. , i s changed drastica l l y j ust i n a

few months storing time. In other words, a prope l l ant
meant to be good for 15 y may fai l after, say 1 5
months only. For this reason, although several new
energetic polymers have been evolved they have
hard l y been used in practice. Engineers put much
faith in a proven system l i ke the AP/AIIHTPB or
CTPB, in view of the uncertain aging characteri stics
of the new system. Also, from the manufacturers'
point of view it is not beneficial to i nvest in a new
system unless it i s vastly superior. hazard-free and at
the same time cost-effective.
Pot Lile

For casting large solid boosters the propell ant

ingredients mixing (sl urry mak i ng) is carried out i n
large batches using one o r two ton mixers. I t i s
i mperati ve that the sl urry after adding the curatives
does not start setting in the mixer i tself, but do so
only after casting i nto the mou lds. The t i me taken to
gel ling (pot l i fe) should be long enough to permit the
operations of proper mixing, de-aerating and vacuum
casti ng. Methods avai lable to lengthen the pot
l i fe inc l ude, choosing proper curat i ves and/or
chain extenders, binder/curati ve ratio, mixing
temperature, etc .
Solid Loading

Oxidizers l i ke AP have j ust enough avai lable

oxygen to OY idize completely about 10 per cent of a
hydrocarbon (CH 2 ) polymer ( fuel). W ith so l i ttle
amount of the binder it i s very d i fficult even to make
a uniform mix with nearly 90 per cent solids, leave
aside a flowable sl urry required to cast the propel lant
mix, in normal c i rcumstances. This seemingly
i mpossible task i s made feasi ble to some extent, by
using bi modal or even tri modal particle s i ze mix. The
s ieved powder having fine and course particles,
mixed i n a fixed ratio, is added to the mi xer i n
batches t o ach i eve the max i mum loadi ng. To ach ieve
maxi mum Isp, however, it is desirable that e ither the
binder backbone should have ' reacti ve' (in
combustion mode) l in kages l i ke N-N bonds, or
groups that do n ot need extra oxygen for combustion,
or the oxidizer must have h igher available oxygen .
Oxidizers l ike n i troni u m perc h lorate and hydrazi n i u m
diperchlorate having much better oxygen balance are
highly suited but they have their own drawbacks.

Conclusions

The emergence of spec i fically synthesized

polymers has played a key role in casting large s i ze
solid propel lant motors. Grains having desi red
structural strength and combustion characteristics
could be successfu l ly cast using functionally
terminated v i scous polymers. Efforts to develop
propel lant compositions giving h igh spec i fic i mpulse
ulti mately led to the synthesis of hydroxyl termi nated
polybutadiene, a binder used currently worldover, i n
casting very large-size solid boosters. Continued
search for binders suitable for spec i fic purposes has
resulted in several i nteresting systems. Of these the
thermoplastc elastomers seem to be promising as
these could also he lp in easy disposal of the aged
propel lants. The newly developed N-N-bonded
polymers appear to be appropriately suitable for
enhanc ing the performance parametres, and the
burning rates of both ammoni u m perchlorate and
ammonium nitrate based propel l ants . These binders
seem to have particularly h igh potential for
develop i ng s mokeless prope l l ants based on phase
stabi l i zed ammoni u m nitrate.
Acknowledgements

The author is grateful to the Uni versi ty Grants

Commission, New Del h i , for awarding an Emeritus
Fel lowship during the course of this research.
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