Chapter 1

Composite Solid Propellant Binders – Current Status and Advances

1.1 Introduction

All modern developments in the area of solid propulsion systems are mostly
based on composite propellants. Storable propellants (solids and liquids) are usually
employed for launch vehicle propulsion. The improvement in the performance
characteristics is the main area of research interest in the field of solid propellants.
The genesis of composite propellants which became the mainstay of today’s
propulsion systems is well known.1-3 Most of the important developments in this area
took place during the 19th century, which is marked in history as the first golden age
of rocketry.4 In 1887, Alfred Nobel patented the ballistic compound based on
nitrocellulose and nitroglycerine, which led to important development of new
propellant formulations. Composite propellant became reality by 1940 through the
pioneering work of John W. Parsons. In the early 20th century, solid propellants
based on double base systems were mostly used for weaponry and liquid propellants
were preferred for launch vehicle propulsion.5 Advantages like compactness,
simplicity, reliability, long shelf life and above all lower cost per unit thrust
developed make solid propellants very attractive for launch vehicle propulsion.
Basically the main performance parameter used for comparison of different
propellant systems is the specific impulse (Isp) which is the thrust generated per unit
mass of propellant burned. Maximizing Isp is one of the main areas of interest in
propellant research. In this chapter, a brief account of various propellant systems,
binder systems and other ingredients that are used mainly for solid propellant
applications is given.

1
 PART I

1.2 A brief survey of development of solid propellants

Solid propellant rockets were first reported to be used by the Chinese in AD

1231 for military purpose.6 Development of explosives and propellants began with
the use of gun powder.7 Detailed accounts of rockets used as weapons for war in
India by the Mughals, Marathas and the legendary Tippu sultan of Mysore are
documented. Reliable propellant systems with nitrocellulose and nitroglycerine based
double base propellants were developed and put to use by 1939. By 1940, cast
composite propellant was invented and ammonium perchlorate (AP) was used as
oxidiser, which resulted in improvement of performance of the propellant systems.
Many of the problems like brittleness, cracking, and high pressure index of burning
associated with double base propellants could be solved by using composite
propellant system. Work in the field of solid propellants started in India by mid
sixties with the launching of sounding rockets with international participation and in
1978, an indigenous all stage solid propellant based launch vehicle was tested.
Today, tremendous amount of research work has been carried out in this field with
the support of thermochemical models and simulation using advanced computing
facilities.8 This has been made possible due to the availability of data on
thermodynamic functions of large number of chemical species.9 A multitude of
scientific and technical expertise have been pooled to study, develop and build solid
rocket motors to make solid propellant systems efficient, robust and reliable. A
schematic showing the different categories of energetic materials and evolution of
modern solid propellants are shown in figure 1.1. Modern propellant systems used
can be categorised mainly into six different groups and the classifications are as
follows.10

2
1.2.1 Single Base Propellants

Single base propellants are in the form of powder or extruded grains, used
mainly as gun propellant. These are made by gelatinising soluble nitrocellulose (NC)
with nitrogen content of 12.6% in an ether-alcohol mixture, using incorporators.
After adding diphenylamine, the dough is extruded through dies of required size and
shape and then chopped and dried. As the name implies the system do not contain
any plasticiser. The horney structure of the propellant leads to poor mechanical
strength and unreliable ballistics.

Early composite propellants Nitrocellulose propellants

Hydroxylated Carboxylated Extruded double base

polymers polymers

PBAA
Cast double base
PBAN

Polyethers Composite modified

CTPB double base

LTPB

HTPB
XLDB
Advanced solid
propellants

Figure1.1 Evolution of modern solid propellant

3
1.2.2 Double Base Propellants (DB)

Double base propellants contain two bases namely, nitrocellulose (NC) and
nitroglycerine (NG), which are capable of combustion in the absence of other
materials. The propellant is a colloid of the two ingredients. The solubility and extent
of plasticisation will depend on nitrogen content. The propellant is prepared by
kneading NC and NG with stabilizers, ballistic modifiers and platonising agents etc
and then carpet rolling at elevated temperatures. Finally, the mix is extruded through
dies. The cast double base propellants also use same ingredients as mentioned above.
The process involves mixing and casting of NC and NG with inert solvents into
rocket motor case with all other ingredients. The gelling process is done at 600C. The
propellants made by this means show low elongation and high modulus especially at
lower temperature and such grains are used in the free-standing configuration.

1.2.3 Triple base propellants

Triple base propellant contains a third energetic ingredient, namely

nitroguanidine (NQ) also known as picrite, to the extent of 40% by weight along with

NC and NG. Nnitroguanidine is an aliphatic nitramine with characteristic >N-NO2

group. Homogenisation of NQ in the colloidal propellant is difficult due to poor
solubility. Ultra fine grade NQ can be used for complete homogenisation in the
propellant. Triple base propellants exhibit good mechanical properties and good
ballistic stability. Triple base propellant formulations produce less smoke and show
low flame temperature. It is prepared by solvent extrusion technique.

1.2.4 Composite Modified Cast Double Base Propellants (CMDB)

The deficiencies such as lower energetics seen in double base propellants are
solved to some extent by incorporating energetic solids like ammonium perchlorate
and aluminium in the formulation. Reduction of the condensed species in the rocket

4
exhaust leading to smokeless exhaust could be achieved by introducing nitramine
based ingredients like HMX in the propellant. Adding NG in the casting powder also
improves processability and energetics of the propellant system.

1.2.5 Elastomeric modified cast double base propellants (EMDB)

Modification of the mechanical and interfacial properties of double base

propellants is achieved by incorporating elastomeric constituents like functionalised
polyesters, polybutadienes or polycaprolactones in the formulation. Except for the
introduction of elastomeric additives, the methodology of preparation of EMDB is
same as that of DB propellant.

1.2.6 Composite Propellants

As the name implies, they are heterogeneous systems containing a

functionalised polymeric binder and a high concentration of oxidiser along with a
metallic additive. The binder forms a matrix, which is impregnated/reinforced with
solid additives and chemically crosslinked with curing agent. All over the world, the
large solid rocket boosters use composite propellant due to the many advantages like
high energetics, good mechanical and interfacial properties, processability, low cost
per unit thrust, reliability and feasibility for safe handling. The larger solid propellant
rocket boosters in the world utilise hydroxyl terminated polybutadiene or
polybutadiene-acrylic acid-acrylonitrile terpolymer as the binder, ammonium
perchlorate as oxidiser and aluminium powder as metallic fuel. Composite
propellants are ideally suited for the large booster stages of satellite launch vehicles,
which demand high thrust output during lift off. The main disadvantages of AP based
composite propellant are smoky exhaust and pollution problems. Table 1.1 shows the
largest sold rocket boosters used by different launch vehicle systems.

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 Table 1.1 Worlds largest solid rocket boosters using composite propellant system

Parameter S 139 S 200 M14 Japan P 230 ASRM SRMU

India India Europe USA USA
Diameter (M) 2.8 3.2 2.5 3.0 3.8 3.1
Length (M) 20 22 14 27 46 34
Propellant weight (T) 139 200 70 237 547 313
Propellant system HTPB/AP HTPB/AP HTPB/AP HTPB/AP HTPB/AP HTPB/AP
Isp-vacuum (s) 270 270 276 271 270 286
Number of segments 5 3 5 3 4 4

1.3 Development of composite propellants

The composite propellant was invented in 1942 at Guggenheim aeronautical

laboratory, California Institute of Technology. Asphalt based propellants were the
initial field study using potassium perchlorate as oxidiser. Soon ammonium
perchlorate replaced KClO4 as oxidiser which resulted in improved performance.
Polysulfide binder system was used by 1950, which improved the reproducibility and
mechanical characteristics. Propellants based on binder systems like ploystyrene-
polyester, PVC and polysulfide were developed during this period. The high modulus
and low elongation of the system was not quite suitable for larger propellant grains in
case bonded configuration. Hence, there was the need to develop cross linkable
binder systems, which can provide suitable mechanical characteristics for the
propellant over wide temperature ranges.

Introduction of aluminium as the metallic fuel was another major

breakthrough in the field of composite propellants. Apart from the remarkable
improvement in specific impulse, addition of aluminium also helped to suppress
acoustic oscillation related combustion instability problems.11 A search for more

6
energetic metallic additives ensued, which lead to a comparative study of various
possible candidate metallic fuels like beryllium, boron, and magnesium.

Processability aspects of composite propellants were another field of

thorough investigation due to the large scale processing requirement for heavier solid
propellant booster stages. Solid propellant slurry containing large amount of solid
additives could be handled with considerable ease due to the contemporary
developments in the field of polymer rheology. The relationship between particle
size, shape, viscosity of slurry and mechanical properties could be modeled to predict
optimum process parameters.12 The models for kinetics of polymer network build up
developed by Paul. J. Florry was of great help in the study of composite propellant
processing.13

1.4 Constituents of composite solid propellants

In general, composite propellants used in case bonded configurations are

based on functionalised thermosetting binder. The binder provides a matrix to
incorporate solid oxidiser, metallic fuel and other ingredients like plasticiser, burn
rate modifier and antioxidants etc. Compatibility of the systems in terms of chemical,
physical and interfacial characteristics is of prime importance. The different
ingredients added to the system modify or introduce characteristics which together
make the system fit for end use. The different additives and their respective functions
are detailed in table 1.2.

1.4.1 Oxidiser

The oxidiser is the major constituent of composite solid propellant system.

The oxidiser accounts for 68 to 70% by weight. Table 1.2 shows conventional and
new oxidiser materials employed for propellant applications.

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 Table 1.2 Oxidiser systems used for composite propellant applications

Material Molecular Density Oxygen Heat of Merits and demerits

formulae (g/cc) balance formation
(%) (kJ mol-1)
Ammonium NH4 NO3 1.73 19.5 -367.8 Low cost, hygroscopic
nitrate (AN) nature and phase
transition at 32.50C.
Naturally available.
Sodium
NaNO3 2.256 28.2 -446.0 Smoky combustion
nitrate(SN)
products
Naturally available.
Potassium 2.109
KNO3 39.5 -497.1 Smoky combustion
nitrate(KN)
products and difficult
to ignite.

Ammonium Widely used. Large

NH4ClO4
perchlorate 1.949 34.0 -289.1 amount of HCl and
(AP) smoke in the exhaust.
High burning rate.
Potassium KClO4 2.519 46.2 -415.0 Solid particles in the
perchlorate exhaust and difficult to
(KP) ignite.
Lithium LiClO4 2.428 60.1 Highly hygroscopic
-444.0
perchlorate and costly.
(LP)
N2H5ClO4 1.940 -293.3
Hydrazinium -- Highly hygroscopic
perchlorate and incompatible with
(HP) common binders.

Nitronium Highly hygroscopic

NO2ClO4 2.220
perchlorate 66.2 +37.1 and incompatible with
(NP) common binders.

Apart from the energetics, the oxidiser has got major influence on other
propellant properties. Primarily, the requirement of oxidiser is that it should easily
decompose as and when required to produce necessary oxidising elements to
maximise the energy release from the reaction. The oxidiser should have high

8
oxygen content, high heat of formation, high density, good thermal stability, low
hygroscopicity, low cost and should not undergo phase transition. Compatibility with
other ingredients is another important requirement. Among various candidate
materials, ammonium perchlorate is the most commonly used oxidiser. It meets
many of the important requirements satisfactorily. Detailed account of mechanism of
decomposition and combustion of AP is available in literature.14, 15 The oxidiser also
acts as reinforcement and strongly influences the rheological, viscoelastic,
mechanical and interfacial properties of the propellant. The particle size distribution
and shape of the oxidiser require effective control, as it affects the processing and
performance characteristics of the propellant. The packing of the oxidiser crystals
and adhesion to the binder play vital role in the rheological characteristics of the
propellant. A major disadvantage of AP based propellant is the large quantity of HCl
produced in the exhaust. Requirement of more environmentally safer system leads to
evaluation of ammonium nitrate (AN). However, the phase transitions associated
with AN is a major problem. Phase stabilised AN is found to be a solution for this
problem. Other energetic perchlorates investigated include NOClO4, NO2ClO4,
N2H5ClO4, N2H6(ClO4)2 and NH3OHClO4. The requirement of improved
performance of solid propellants, environmental and safety considerations prompted
synthesis and evaluation of more energetic oxidiser systems.16 Attempts were made
to use nitramine compounds like HMX and RDX along with AP to reduce HCl
emission. Realisation of a safe propellant system with specific impulse exceeding
300 seconds and density 2 g/cc along with environmentally benign characteristics is
considered to be the dream of the propellant scientist. Hydrazinium nitroformate
(HNF), ammonium dinitramide (ADN), hexanitrohexazaisowurzitane (CL-20),
octanitrocubane (ONC) and trinitroazetidine (TNAZ) are considered energetic
oxidiser systems, which could help achieve the higher performance characteristics.
The structure and important performance characteristics of advanced energetic
oxidiser systems are given in table 1.3. Among the prospective high energy oxidisers,

9
ADN and HNF are found to have positive oxygen balance. CL-20 has got great
advantage in terms of high density and it is one of the most powerful explosives with
caged nitramine structure.17, 18

Table 1.3 Structure and properties of important high energy oxidizers

Heat of Oxygen
formation balance Density Melting
Material Chemical structure
(kJ mol-1) (%) (g/cc) Point (0C)

ADN NH4N(NO2)2 -150.6 25.8 1.82 92

HNF N2H5C(NO2)3 -72 13.1 1.87 122

CL-20 381.2 -10.9 2.05 167

O2NN
TNAZ NO2 33.64 -16.6 1.84 101
NO2

O2N NO2
O2N NO2

ONC NO2 413.8 0 2.10 275

O2N

O2N NO2

10
 In octanitrocubane, all the hydrogen of cubane is replaced by nitro groups,
resulting in water free combustion products.19 TNAZ is a stable compound with
hetrocyclic ring.20 ADN was first synthesised in Russia at Zelinsky institute.21, 22

Different synthetic routes were invented and patented for organic and inorganic
dinitramides by Bottaro. J. C. et.al.23, 24 ADN combines all the advantages like high
density, high oxygen content and low negative heat of formation. HNF was invented
in 1950’s.25, 26 HNF was found to have compatibility problems with polybutadiene
type binders. With the advent of energetic binders like GAP, compatibility problems
have been addressed satisfactorily.

1.4.2 Polymeric binders used for composite propellants

The binder is an essential ingredient of composite solid propellants. Nearly

10 to 15% of the composite solid propellant is comprised of binders. The binder
largely determines the mechanical properties of the propellant. Binders used for
composite propellants are organic polymers containing mostly carbon and hydrogen.
It is also a fuel, which is chemically and physically compatible with all other
ingredients. The decomposition of the binder should lead to large volume of stable
molecules of carbon monoxide, carbon dioxide and water vapour. The most essential
requirements of an ideal solid propellant binder can be summarised as follows.

i. The binder should have reactive functional groups which can chemically
bond with curing agents and form elastomeric network which can provide a
compatible matrix system.

ii. The binder should be hydrocarbon type, such that it can provide stable low
molecular weight combustion products.

iii. The processing requirement with respect to rheology of the system should be
met by a workable viscosity of the binder.

11
 iv. Low glass transition temperature is preferred for the binder, so that it can
withstand large spectrum of stress transients in operation.

v. High heat of formation is an important requirement to maximize the energetic

output.

vi. Physical and chemical compatibility of the binder with other ingredients and
stability of the binder system are important attributes which lead to good
ageing characteristics for the system.

The modern binder systems, which can satisfy these requirements, are
discussed in latter part of this chapter. Modern crosslinkable binder systems used for
solid propellant formulations are listed in table 1.4.

Table 1.4 Modern crosslinkable binders and curatives for solid propellant systems

Polymer resins used as binders Curatives and crosslinkers

Unsaturated polyester based on phthalic acid,

Styrene or vinyl monomers
maleic acid and propylene glycol

Polysulfide (thiokols LP-3) based on Paraquinonedioxime or lead

dichlorodiethyl formal and sodium polysulfide dioxide

Polypropylene glycol (PPG) Diisocyanate and triol

Polyester (diacid and excess diol) Diisocyanate and triol

Hydroxyl terminated polybutadiene (HTPB) Diisocyanate and triol

Hydroxyl terminated natural rubber (HTNR) Diisocyanate and triol

Copolymer of butadiene and acrylic acid (PBAA) Di/Triepoxy and aziridine

Terpolymer of butadiene, acrylic acid and acrylo

Di/Triepoxy and aziridine
nitrile (PBAN)

12
1.4.3 Metallic fuels

Metallic fuels improve the energetics of the propellant by virtue of the

increase in chemical energy released due to the exothermic oxidative combustion
reaction. Aluminium powder is the most widely used metallic additive in composite
solid propellant formulations. Aluminium content of 18 to 20% in the propellant is
found to improve the specific impulse by 20%.2 Aluminium particles in the size
range of 10 to 30 µ are used in most of the compositions. Presence of metallic
element reduces water content and increases the hydrogen content in the exhaust. It
also improves the density of the propellant. Presence of aluminium oxide particles
helps to attenuate the undesirable acoustic oscillations of the combustion products
and thereby eliminate combustion instability.27 Other important metallic fuel choices
include magnesium, boron and beryllium.

Disadvantages like poor energetics of magnesium, difficulties in ignition and

combustion of boron and toxicity associated with beryllium, made aluminium a
better choice. Metallic hydrides are considered promising additives, though many
difficulties are yet to be solved. Metallic wires of aluminium, silver and copper are
also used to enhance burn rate of the propellant.

1.4.4 Plasticisers

The processability of the highly solid filled propellant slurry is made easy by
employing plasticisers which are compatible with all ingredients. Plasticisers are
high boiling, nonvolatile, low viscous, low molecular weight substances. The
modification of the flow characteristics of the propellant slurry is very important for
realising defect free propellant grains.28 Plasticisers are of different types and the
most widely used ester type plasticisers are dioctyladipate, dioctylphthalate and
hydrocarbon plasticisers are mineral oil and paraffin oil. To improve the energetics
of the propellant, plasticisers with energetic groups like azido, difluoronitramino and

13
nitro have been used with azido and nitrato polymers.29 For double base propellant
applications, non-functional GAP has been used as plasticiser.30

1.4.5 Curatives

The curatives react with the functional groups of the binder and forms
crosslinked polymeric network structure. The number of crosslinks in the network
decides the mechanical behaviour of the polymer. Selection of the curing agent is
done based on the type of functional groups of the polymer. A number of curing
agents have been used for propellant application. Curing agents like toluene
diisocyanate, isophorone diisocyanate etc. are widely used for polyurethane matrices.

1.4.6 Other ingredients

Propellant formulations utilise a crosslinking agent, which reacts with the

curatives and helps to form three dimensional network structures. Trifunctional
material like trimethylol propane is an example. The crosslinking agent has the same
functional group as the binder. Burn rate modifier is another important constituent,
added in relatively small concentrations to modify the ballistic properties of the
propellant. The selection and quantity of burn rate catalyst shall depend on the
specific burn rate profile required for the propellant. Ferric oxide, ferric acetyl
acetonate, ferrocene and copper chromite31 are usually used in propellant
formulations for this purpose. Anti-oxidants are added to propellant formulations to
improve the ageing characteristics by preventing oxidative degradation.
Phenyl-β-napthylamine, paracresol are some of the anti-oxidants used. Certain
propellants also use catalysts like dibutyl tin dilaurate and ferric acetyl acetonate as
curing aids.

1.5 Basic performance requirements for solid propellants

Conservation of mass and momentum are the fundamental principles based

on which the performance relations are derived for solid propellant rocket motors.

14
The basic performance parameters include thrust, ideal exhaust velocity, specific
impulse, burning rate, flame temperature and temperature sensitivity. The initial
conditions of propellant composition, temperature, oxidizer-fuel ratio and operating
pressure determine the properties of combustion products or the propulsive elements
exhausted through the nozzle. The thrust (F) developed by the rocket is given by the
following expression
F = mve+ (pe-pa) Ae (1.1)

Where m is the mass flow rate through the nozzle, ve is the exhaust velocity
of combustion products, pe is the exit pressure, pa is the ambient pressure and Ae is
the cross sectional area at nozzle exit.

The most commonly used propellant performance parameter for comparison

of different propellant systems is the specific impulse (Isp), which is defined as the
thrust generated per unit mass of propellant per unit time and generally expressed in
seconds. Maximising Isp or Density x Isp (product of density and Isp) is the prime
motive of the research work in this field. The Isp is related to thrust by the following
relationship

Isp = F/mg (1.2)

Where g is the gravitational constant. Isp is also related to the properties and
conditions of combustion products and the relationship is given by the following
expression

Isp = Tc M*
(1.3)
*
Where Tc is the flame temperature and M is the mean molar mass of
combustion products.

The mean molar mass is given by M* = Σ (ximi) for i = 1 to n (1.4)

Where i represent the component, xi is the mole fraction of the component

and mi is the respective molecular weight. From the relationship, it is clear that the

15
maximum Isp shall result when combustion temperature is highest and molecular
weight of the combustion product is minimum. The heat of reaction is given by the
following expression

∆H = Σ[∆Hf] of products - Σ[∆Hf] of reactants (1.5)

where Hf is the heat of formation.
The favorable chemical bonds in propellants and in combustion products are listed in
Table 1.5.

Table 1.5 Favourable chemical bonds in propellants and in combustion

products and associated bond energies

Propellants Combustion products

Bond energy Bond energy
Bonds (kJ mol-1)
Bonds
(kJ mol-1)
N-S 112.1 B-O 564.8
O-O 140.6 Mg-O 502.5
Cl-O 154.4 O-H 463.6
N-N 158.2 Si-O 460.2
Cl-N 191.6 H-Cl 431.4
N-O 238.5 Al-O 431.4
N-H 390.8
C-O 350.6
H-S 346.9
C-N 336.4
Al=O 862.7
B=O 861.1
C=O 711.3
Mg=O 569.4
N=N 945.2

16
 The heat of formation of a substance depends on the bond energies between
atoms of the substance. For maximising energy release, the propellant component
should consist of molecules with low bond energies and the combustion products
should consist of molecules with large bond energies. Hence, elements with low
atomic mass and low bond energies are preferred in the reactants. Nitrogen single
bonded to sulphur, oxygen or nitrogen and oxygen single bonded to oxygen or
chlorine are favourable combinations for propellant formulations. Though the
combustion products are of high molar mass, combustion of carbon and hydrogen
release large quantum of energy. These factors imply that hydrocarbon based fuels
are suitable for energetic binder application. The energy output of hydrocarbons can
be improved by incorporating N, NO, NO2 or NO3 groups in the molecule. By
substituting hydrogen with energetic groups like azido, nitro, nitrato and nitramino
groups in the molecules, bond energy of the substance can be reduced and during the
combustion of such compounds, large amount of heat is released with the formation
of nitrogen. The important hydrocarbons developed in this fashion include
polyglycidyl azide (GAP), poly 3-3 bis (azidomethyl) oxetane (P-BAMO),
polyglycidyl nitrate (PGN), polynitratomethyl methyl oxetane (P-NIMMO),
polyazido methyl methyl oxetane (P-AMMO).

Burning rate is an important factor influencing the performance of the solid

propellant. The burning surface of a propellant recedes in a direction normal to the
surface. It is functionally dependant on various parameters. Some of the parameters
affecting the burning rate are combustion chamber pressure, initial temperature of the
propellant, combustion gas temperature and velocity of gas flow parallel to the
burning surface. The empirical equation used to represent the burn rate pressure
relationship is shown in the following expression.

r = a pn (1.6)
where r is the burn rate, p is the pressure, a is a constant which depends on
ambient grain temperature and n is the burning rate pressure index which is

17
characteristic of a specific propellant formulation. Other important parameters of
interest are temperature sensitivity of burning rate and pressure sensitivity of burning
rate.

Apart from the energetics, solid propellant formulation and design should
address the structural strength requirements. The polymeric binder matrix possesses
time dependant properties arising from viscoelastic nature. From the time a
propellant grain is cast, it is subjected to a large spectrum of induced stresses,32, 33
until it is burned away in the performance of it’s mission. These include forces of
gravity, loads arising from propellant curing and temperature variation, shock and
vibration due to handling and captive flight and finally acceleration that accompany
ignition, launch and flight. A successful propellant grain design is the result of
comprehensive assessment of grain structural integrity in close co-ordination with
ballistic performance. The propellant mechanical properties are strongly dependant
on both time and temperature. The viscoelastic characteristics of propellant cause
large variation in the mechanical properties due to changes in temperature during
processing and curing. At lower temperature (below glass transition temperature) or
at high frequencies, the polymer exhibits high young’s modulus and could break up
at higher strains. The same polymer behaves like rubbery material at high
temperatures or at low frequencies. The binder plays an important role in the
viscoelastic behaviour of the propellant. Hence, evaluation of the time-temperature
dependence and also the effect of ageing on the mechanical properties of the
propellant are important requirements. The mechanical properties to be determined
for carrying out structural analysis of solid propellants fall into three groups. These
are (i) the properties necessary to compute the temperature and thermally induced
volume changes in the propellant, (ii) mechanical properties necessary to compute
body forces due to acceleration and to define relationship among stress, strain and
temperature and (iii) failure properties necessary to characterise the conditions at
which failure will occur and to evaluate susceptibility to failure. The simplest form

18
of viscoelastic behaviour is the linear behaviour in which the ratio of the stress strain
is a function of time, which can be used to compare various systems.

Density of the propellant is another important parameter of interest. A denser

propellant means more energetic material mass loading in the same chamber volume.
The product of density and specific impulse (density specific impulse) comprises the
most important parameter for comparison of propellant systems for launch vehicle
applications. The main advantage of solid propellants lies in the higher density
specific impulse compared to that of other propellant systems.

From the discussion, it is clear that the performance parameters of solid

propellants that are to be taken into account are of varied types. These parameters are
influenced by the ingredients used in the propellant. The binder used in the
propellant plays a vital role in this respect. The polymeric binder systems currently
used for solid propellants for operational launch vehicles satisfy these requirements
to some extent. In order to improve performance, a solid propellant with Isp greater
than 300 seconds and density greater than 1.8 g/cc could be considered as a target
level of performance parameters. Development of safe (hazard free) and reliable
propellant systems which can meet this requirement calls for use of ingredients
which are more energetic. New energetic binders which can be used in advanced
solid propellant systems incorporate azido, nitrato, and nitramino groups in the
molecular structure. Examples are GAP, P-BAMO, PGN, P-NIMMO, P-AMMO etc.

1.6 Composite solid propellant binders- Present status

Different types of polymeric resins were studied and employed for composite
solid propellant applications in the past. The present day binder systems evolved
through endeavors spread over many decades. Today, polymeric binder based
composite propellants have become the mainstay of large solid rocket boosters all
over the world. In this section, a brief description of various polymeric binders used
for composite propellants is presented.

19
1.6.1 Polysulfide binders

Polysulfides were the first liquid functional prepolymers to be used to

evaluate semi-elastic binders crosslinked by chemical condensation with a
multifunctional agent. Polysulfides were first prepared by Joseph C Patrick by the
condensation of ethylene dichloride with sodium polysulfide. The first case bonded
propellant system was made using polysulfide based liner and propellant creating a
pathway for the production of large solid rocket motors. A detailed account of the
chemistry of polysulfide curing and propellant formulation is available in the
literature.34 Low Isp of polysulfide based propellant was a major disadvantage which
lead to search for better systems. Chemical structure of polysulfide binder is shown
below.

HS- CH2-CH2 -O-CH2-O-(CH2 )2 -S-S-(CH2 )2-O-CH2 -O-CH2-CH2 -SH

n

1.6.2 Polyester polyols

Polyesters like ISRO polyol with a molecular weight of 2000 is one of the
resins used in this category. It is synthesised by the self condensation of 12-hydroxy
stearic acid, followed by condensation with trimethylol propane.

O CH2-OH O
HO- CH-(CH ) C -O -CH -C-CH2- O-C-(CH2)10CH -OH
n
2 10 n 2
(CH2) 5 CH2 (CH2)
5
CH CH 3 CH3
3

Polyester propellants also suffer from lower Isp compared to polybutadiene

and polyurethane propellant systems. Higher viscosity of the resin was also a
disadvantage in this respect.

20
1.6.3 Polyethers

Mainly three different types of polyethers are used. Polyoxypropylene glycol

(PPG) is the most commonly used resin. Lower viscosity of resin, higher energetic
output and low cost are the main advantages of polyethers. Pick up of moisture on
storage and gas evolution during curing reaction are the main disadvantages.
Chemical structure of polypropylene glycol is shown below.

H-O-CH2-CH-OH
n
CH3

1.6.4 Polybutadiene binders

The polybutadiene binders are originally the result of research work carried
out at Thiokol nearly 60 years ago.35 Polybutadiene-acrylic acid (PBAA) is the first
of this kind to be used. It is a copolymer of butadiene and acrylic acid. It is prepared
by emulsion polymerisation, initiated by free radical mechanism using quarternary
ammonium salts as emulsifier and azo bis (isobutyrontrile) as the initiator. The ratio
of the monomers can be varied to meet specific polymer structural requirements and
in general, there is an average of two carboxyl groups per molecule.

Polybutadiene acrylic acid acrylonitrile (PBAN) was synthesised by using

acrylonitrile as a copolymer in the above system. In PBAN, there is an average of 6%
by weight of cyano groups in the polymer. Substitution of PBAA with PBAN
resulted in increased tear resistance for the propellant. Chemical structure of PBAN
is shown below.

R-CH2-CH=CH-CH2- -CH2-CH-x- CH2-CH- R

n y
COOH CN

PBAN is used in large quantities today for heavy solid rocket boosters like
the systems used for space shuttle boosters by NASA.36 PBAN has low viscosity and

21
low cost of production. A combination of polyaziridines and polyepoxides are used
as curing agents.

Carboxyl terminated polybutadiene polymer (CTPB) was developed in order

to achieve greater flexibility for the polymer network. CTPB showed higher
mechanical strength, which helped to make case bonded grain configuration with
mass fractions as high as 0.94. CTPB is made by free radical polymerisation of
butadiene gas using azocarboxyl initiator like azo bis (cyanopentanoic) acid. Nearly
difunctional polymer with molecular weight in the range of 3500-5000 could be
developed. CTPB uses aziridines and epoxides for curing reactions. A major
disadvantage of aziridine and epoxide curing system is the possibility of side
reactions at different temperatures and related uncertainty in the property of polymer
network on ageing. The chemical structure of CTPB is shown below.

HOOC-R-CH2-CH=CH-CH2-R-COOH
n
Hydroxyl terminated polybutadiene (HTPB) combines high specific impulse
with clean stoichiometric urethane reaction yielding propellant with good mechanical
properties. HTPB can be produced by free radical polymerisation of butadiene gas as
well as ionic polymerisation. Usually free radical polymerisation is followed. In the
free radical solution polymerisation, 1,3-butadiene gas is used as the monomer.
Chemical structure of HTPB is shown below.

HO-CH2-CH=CH-CH2-OH
n

Hydrogen peroxide is used as initiator and isopropyl alcohol is used as the

solvent. The polymerisation reaction is carried out at specified temperature and
pressure as this step strongly influences the properties of the polymer. Other
parameters include ratio of monomer to initiator concentration and solvent to
non-solvent ratio. The polymer formed is precipitated in methanol and is washed and

22
vacuum dried. The polymer has unsaturation in the backbone and therefore, it is
susceptible to oxidation. Hence an anti-oxidant like butylated hydroxy toluene is
added in small quantities.

The anionic polymer is made by living polymerisation technique using

organo lithium initiator. The living polymer end is converted to hydroxyl groups by
reaction with ethylene oxide. Anionic HTPB is found to have narrow molecular
weight and functionality distribution. Ionic polymerisation also leads to different
microstructure for the polymer. Microstructure is the arrangement of the backbone
around the double bond formed during the course of polymerisation. In this case, the
different microstructure results due to the arrangement of butadiene backbone around
the double bond formed during polymerisation either by 1, 2 or 1, 4 addition. The
microstructure of the binder plays an important role on the processability and
mechanical properties of the propellant. The microstructure shows up in the form of
cis, trans and vinyl forms. The various arrangements around the double bond are
depicted below.

CH CH2
CH2
CH2 CH2 HC CH CH
HC CH CH2 CH2
Cis 1,4 addition Trans Vinyl 1,2 addition

Low viscosity, higher hydrocarbon content of 98.6% (CTPB and PBAN are
97% and 92%), good reproducibility and easy availability are advantages which
make HTPB the most versatile propellant binder available today. Low viscosity of
HTPB helps to have solid loading up to 89% in the propellant formulation. Clean
stoichiometry of curing reaction is another important advantage of HTPB. Free
radical HTPB exhibits functionality close to 2.3 and requires 75 to 80 equivalence of
curatives per 100 equivalence of hydroxyl groups to achieve the required properties.
In the case of PBAN and CTPB, 140 equivalence of epoxy-aziridine curatives
23
combination is required for 100 equivalence of carboxyl groups for curing. Side
reactions are also found to occur in the case of epoxy-aziridine reactions leading to
requirement of higher equivalence of curatives. Due to the clean stoichiometric
curing reaction of HTPB, the optimum curing is achieved in less time compared to
other binder systems. HTPB can be crosslinked at relatively lower temperature
(500C) compared to PBAN or CTPB (60 to 750C). HTPB propellant exhibits low
glass transition temperature and good ageing characteristics over long periods of
storage. All such superior characteristics make HTPB the workhorse binder for
composite propellant application. Table 1.6 shows comparison of different binder
systems.

Table 1.6 Physical and chemical properties of different binders

Property PBAA PBAN CTPB HTPB

Heat of combustion (kJ mol-1) 43 41.8 42.6 41.8

Average mol. wt. (Mn) 2500-4000 3500 3500-5000 2500

Average functionality 2 1.9 2 2.3

Viscosity at 250C (poise) 275-325 300-500 180-350 40-60

Density (g/cc) 0.9-0.92 0.93 0.92 0.92

HTPB-isocyanate curing reaction leads to urethane structure, which

contributes to good mechanical characteristics for the propellant. Stable and
reproducible propellant properties could be achieved for HTPB binder based
systems. The ester linkages formed by carboxyl groups of PBAN and CTPB are
comparatively inferior in this respect. Pot life, which is the processing time available
for the propellant slurry after curative addition is an important parameter for
propellant processing for case bonded configuration. For realising defect free

24
propellant grains, the propellant slurry should have a pot life of minimum 4 to 5
hours.

The cohesive strength and structural integrity of propellant depends primarily

on the mechanical behaviour of the crosslinked binder, which is related to the
crosslink density of the polymer network. The crosslink density is controlled by
varying the content of trifunctional crosslinker and NCO/OH ratio in the formulation.

1.7 Energetic binders for composite solid propellants

Increased performance requirements, environmental impact, hazards, costs,

life cycles and dual use became guiding factors in the direction of propellant
development. Research in the field of energetic materials lead to development of new
formulations of propellants. Large scale emission of HCl is a major problem for AP
based propellant systems.37 Replacement of AP with energetic oxidizer systems
requires use of compatible energetic binder systems to fully accomplish the
advantages in terms of energetics.

Organic azides are a unique class of energetic compounds. Over the last three
decades a lot of research works have been carried out to investigate different
polymeric binders substituted with energetic groups like azides.38 The unsaturation in
the inert binder systems like HTPB leads to incompatibility with energetic oxidisers
like HNF. In this context, development of binder systems, which are energetic,
stable, compatible and hazard free, became imperative. Substitution of energetic
groups into polymers poses number of difficulties. Introduction of polar groups
affects the low temperature properties like glass transition temperature. Processing
and handling problems associated with sensitive systems, hygroscopic nature, ageing
characteristics and above all cost were issues that had to be addressed. Substituent
groups in the polymer are found to affect the physical, chemical, mechanical,
rheological properties and influence the thermal decomposition in a substantial way.

25
Double base and AP based composite propellants with azido and nitrato substituted
polymer binders have shown promising results. Azido compounds liberate about
685 kJ per azide unit during decomposition. Clean burning propellants based on
AN/RDX/HMX in combination with energetic binders and oxidisers have shown
potential to improve Isp above 300 seconds. By introducing cage like structure
containing sufficient quantities of nitrogen, oxygen or fluorine in the formulation,
energetic content and density of the propellant can be improved.

After GAP was introduced and investigated, a number of polyazido oxetanes

were studied. These include polyBAMO, polyAMMO, polyNIMMO and nitrato
polymers like PGN. Nitrated HTPB was another development in this area. Table 1.7
shows structure of different high energy binders developed and studied.

Table 1.7 Chemical structure of high energy binders

Polymer Chemical structure

GAP HO CH2 CH O H
N3 n

CH2N3
PolyBAMO
HO CH2 C CH2 O H
CH2N3 n

CH2N3
PolyAMMO HO CH2 C CH2 O H
CH3 n

CH2ONO2
PolyNIMMO HO CH2 C CH2 O H
CH3 n

PGN HO CH CH2 O H
n
CH2ONO2

26
 High heat of formation is an attractive feature of azido polymers. The heat of
formation of the polymer becomes positive when azide group is attached to the
molecule. GAP contains as much as 40 weight percent nitrogen in the molecule. The
release of nitrogen during thermal decomposition increases the gaseous content of
the combustion products along with the exothermic release to the tune of 685 kJ/mol.
However, lower glass transition temperature of the binder is a disadvantage.
Copolymers of the energetic binders have been investigated to modify many of the
properties.39 Energetic polymers with hydroxyl functional groups could use
isocyanate curatives to form polyurethane structure for the propellants, and thereby
matched the advantages of HTPB binder system in terms of mechanical properties.
Table 1.8 shows the important properties of high energy binder systems.

Table 1.8 Important properties of high energy binder systems

Properties GAP Poly- Poly- PGN

BAMO NIMMO
Pale yellow Amber Amber
Appearance White solid
liquid liquid liquid
Density (g/cc) 1.3 1.3 1.26 1.45

Mol. weight 2000 2200 1700 4510

Viscosity (cps)
2000 -- 1600 2360
at (300C)

Heat of formation
+117 + 413 -334.7 - 284.5
(kJ mol-1)

Glass transition
-55 -45 -30 -35
temperature

A large number of organic azides that can find application in smokeless

propellant formulation have been synthesised.40-43 These include azido polyether,
azido ester, azido nitramine, azido nitro compounds, azido alkenes and azido ether.

27
Nitrated HTPB synthesised by nitration of HTPB combines the advantages of HTPB
binder and energetic nitro groups. However, a compromise is to be made with respect
to mechanical properties and low temperature properties. The nitration is to be
optimized at around 10% to minimise the impact on mechanical properties. Glass
transition temperature of HTPB is increased from –750C to –580C by nitration due to
the loss of flexibility resulting from presence of nitro groups.

1.8 Energetic material formulations with azido compounds

GAP is a unique high energy polymeric material which contains CH2N3 moiety
at pendant positions in the polymer back bone. GAP was first reported by
Vandenberg.44 A comparison of heat of formation of ethanol (-278.5 kJ/mol) with
2-azido ethanol (+104 kJ/mol) demonstrates the effect of azide group. The three
nitrogen atoms in the form of N3 are attached linearly by ionic and covalent bonds.
The different resonance structures of nitrogen bonds in N3 group are shown below.

The initial research work on azido compounds were carried out to investigate the
feasibility of utilizing 1,7-diazido-2,4,6 trinitrazaheptane (DATH) as oxidizer and
1,3-diazido-2-nitrazopropane (DANP) as energetic plasticiser for advanced
propellants. This paved the way for development efforts for hydroxyl terminated
azido polymer in 1976.45 The polymer synthesis was initially carried out by
polymerisation of glycidyl azide (GA) obtained by reacting epichlorohydrin with
hydrazoic acid followed by cyclisation of resulting product. Due to the low
reactivity of the monomer, a two step process was later developed involving
polymerisation of epichlorohydrin to polyepichlorohydrin followed by azidation of
the prepolymer with sodium azide and finally converting it to GAP. Most of the
operational solid propellants use AP as the oxidiser to the extent of 70%. The
burning of conventional propellants contributes to serious impact on environment

28
 such as ozone layer depletion and effect on stratosphere in general due to noxious
chemicals such as HCl and reactive chlorine compounds. Azido and azido oxetane
polymers could be used with energetic oxidizers like ADN, HNF and CL-20 to solve
such problems. The advanced new generation propellant formulation could also lead
to elimination of unburned fuel species and toxic materials in combustion products,
which pollutes the environment. Since the azido binders do not have carbon-carbon
double bonds in the polymer backbone, no compatibility problems were noted when
used along with oxidisers like HNF.

The performance parameters of the propellant formulations with energetic

polymers and advanced oxidiser systems have been theoretically predicted using
computational methods. The theoretical estimation shows that considerable
improvement could be achieved by utilising combination of energetic binders and
oxidisers. Table 1.9 shows comparison of important performance parameters of a
number of energetic binder systems with advanced oxidisers.

Table 1.9 Comparison of energetic propellant compositions

Propellant AP/Al/ ADN/Al/ ADN/Al/ ADN/Al/ HNF/Al/ HNF/Al CL-20/

HTPB GAP BAMO NIMMO GAP BAMO Al/GAP
Composition
68/18/14 64/18/18 58/18/24 66/18/16 66/18/16 66/18/16 72/18/10
(wt %)
Peak Isp (s) 265 275 277 274 280 282 266

Density (g/cc) 1.76 1.79 1.75 1.79 1.84 1.84 2.01

Isp x Density
466 492 485 490 514 518 535
(s g/cc)
Combustion
3485 3787 3819 3786 3985 3936 3746
temperature(K)
Mol. wt of
combustion 28.0 28.4 30.9 29.2 29.3 28.2 29.3
products

29
 The data indicates that AP/Al/HTPB system gives a maximum density
specific impulse of 466 s g/cc at 86% solid loading. ADN/Al/NIMMO, ADN/Al/
BAMO and HNF/Al/GAP propellants provide density specific impulse values of
490, 485 and 492 s g/cc at 84, 76 and 82% solid loading whereas HNF/Al/BAMO
and HNF/Al/GAP give 518 and 514 s g/cc respectively at 84% solid loading. The
maximum density specific impulse of 535 s g/cc is given by CL-20/Al/GAP system
at 90% solid loading. The performance level can be further improved by properly
tailoring the metallic fuel content. However, 90% solid loading posses a number of
processing problems. So far no operational propellant system with these
combinations is available in launch vehicle technology. Though HNF and CL-20 are
found to show better performance, ADN is found to be advantageous in terms of
feasibility and processing hazards.

The promising binder systems are BAMO followed by GAP. However,

BAMO is to be used as a copolymer as it is in solid state. GAP is found to meet
many of the requirements of an energetic propellant binder. Further improvement in
Isp of GAP-ADN propellant can be achieved by incorporating metallic hydrides in
the formulation. Aluminium hydride (AlH3) is an attractive candidate for this
purpose. Propellant formulation of GAP/ADN/AlH3 with 25% AlH3 could increase
Isp by 18 seconds more than that of GAP/ADN/Al combination. However, lower
density of AlH3 lowers the density specific impulse of the system. Also AlH3 has the
inherent problem of high reactivity. Hence, stabilized form of AlH3 (α-alane) or
encapsulated AlH3 is to be used. Table 1.10 shows the effect of AlH3 in energetic
propellant formulations

30
 Table 1.10 Effect of AlH3 on specific impulse of propellant formulations

Propellant AP/Al/HTPB ADN/AlH3/GAP ADN/AlH3/GAP ADN/Al/GAP

Composition
68/18/14 66/20/14 61/25/14 64/18/18
(wt %)
Isp (s)
265 288 293 275

Density x Isp
466 458 457 492
(s g/cc)

PART II

1.9 Synthetic routes of GAP and other polymers with energetic groups

Introduction of exothermically decomposing azido groups or oxygen rich

energetic nitro and nitrato groups in pre-polymers result in realisation of formulation
with superior performance characteristics with relatively lower oxidizer loading
levels leading to better structural integrity. GAP was the first of this kind to be
developed, followed by a series of azido oxetanes, nitrato and nitramino polymers.

1.9.1 Different routes of synthesis of GAP

1.9.1.1 Azidation of epichlorohydrin

Glycidyl azide prepared by azidation of epoxides46 was used as starting

material initially. In this route, epichlorohydrin is treated with hydrazoic acid to
convert it to 1-azido-3-chloro-2-propanol. This is then cyclised with a base as per
scheme 1.1.

Scheme 1.1 Conversion of epichlorohydrin to glycidyl azide

31
 This route was discontinued as glycidyl azide monomer is unreactive and
difficult to polymerise.

1.9.1.2 Carbo cationic route for polymerisation of epichlorohydrin

Azides exist in different forms and are considered as pseudohalogens.45 As an

alternative method, a two step procedure was found to be successful. In this
epichlorohydrin is converted to polyepichlorohydrin (PECH) by cationic ring
opening polymerization.47, 48
PECH is then converted to GAP by nucleophilic
displacement of chloride by azide in polar aprotic medium. The polymerisation of
epichlorohydrin is carried out by cationic mechanism in which different types of
initiators and co-initiators are used. Polymerisation of PECH is done with Lewis
acids such as BF3O(C2H5)2, SnCl4, SbCl5 or FeCl3. Other initiators like water,
aluminium alkyl salts and trialkyl oxonium salts like triethyl oxonium
tetrafluoroborate and esters and hydrides of super acids like CF3SO3R or FSO3R (R
for alkyl groups) are also used for polymerisation of epoxy compounds.49, 50 Detailed
discussion on the mechanism and procedure for polymerisation of epichlorohydrin
and conversion to GAP by this route is presented in chapter 3.

By using triol as a reactant with the initiator, it is possible to get trifunctional

PECH as shown in scheme 1.2.

CH2- CH(CH2 Cl) + HO-C H2-CH-CH2-OH H- OCH(CH2Cl)CH2- OC H2CHCH2O- C H2CH (CH2Cl)-O- H

O OH
O- CH2-CH(CH2Cl)-O- H

Scheme 1.2 Formation of PECH triol

The polymer formed is converted to GAP by reaction with sodium azide in

aqueous or organic solvent medium.51, 52
Lithium, sodium or potassium azides in
molar excess can be use for azidation reaction. Complete conversion of PECH to
GAP takes place in dimethyl sulphoxide medium with sodium azide within 12 to 18

32
hours. The aqueous process utilises a phase transition catalyst like methyl tricapryl
ammonium chloride and the reaction is reported to be completed in seven days. The
conversion process of PECH to GAP is monitored by infrared spectroscopy.53
Detailed discussion on the mechanism of conversion of PECH to GAP is presented in
chapter 3.

1.9.1.3 Direct conversion of epichlorohydrin to glycidyl azide polymer

Direct conversion of epichlorohydrin to GAP is carried out by gradually

mixing ECH with sodium azide (mole ratio of 1:1) in presence of DMF and ethylene
glycol.54 The reaction is done initially at 700C followed by reaction at 900C for 15
hours. This route leads to GAP with low molecular weight (~500) which could find
application as energetic plasticiser.

1.9.1.4 Simultaneous degradation and azidation of PECH

Degradation and azidation of commercial rubbery PECH with sodium azide
and a basic cleaving agent like sodium methoxide, in the presence of a triol using
polar aprotic medium like DMSO or DMF has been reported for synthesis of GAP.55

1.9.1.5 Synthesis of GAP with azido terminal groups

Azide terminated polymer has been synthesised by tosylation of hydroxy

terminated polyepichlorohydrin with paratoluene sulfonyl chloride in presence of
pyridine. Azidation is done by replacement of chlorine and tosyl group by azide by
reaction with sodium azide in DMF medium. The reaction is as per scheme 1.3.

33
 Scheme 1.3 Synthesis of azide terminated GAP by tosylation

Azide terminated GAP finds application as energetic plasticiser in composite

propellants. Azide terminated GAP can also be prepared by nitration of PECH
followed by azidation.56 The nitration is carried out using HNO3-H2SO4 mixture
which leads to nitro terminated epichlorohydrin. Azidation is carried out by reaction
with NaN3 in DMF or DMSO medium.

1.9.2 Synthesis of azido methyl oxetanes

Polymers and copolymers of oxetanes containing azido groups, such as

3-methyl-3-azido methyl oxetane (AMMO) and 3,3-bis-azido methyl oxetane
(BAMO) are considered promising energetic binders like GAP.57 BAMO is
synthesised in two stages. Bis (chloromethyl) oxetane (BCMO) is first prepared by
chlorination of penta erithritol followed by cyclisation of the trichloride. Azidation of
BCMO with sodium azide is done in DMF medium at 850C. The bis (azidomethyl)
oxetane is then homopolymerised by carbo cationic ring opening polymerization
using BF3O(C2H5)2 as catalyst in presence of butanediol as initiator at -50C. Scheme
1.4 shows synthesis of polyBAMO.

Scheme 1.4 Synthesis of polyBAMO

34
 Azidomethyl oxetane (AMMO) is synthesised by reacting NaN3 with chloro
methyl oxetane (CMMO) or the tosylate, 3-hydroxyl-3-methyl oxetane in presence of
a phase transfer catalyst. Chloromethyl oxetane readily reacts with sodium azide in
aqueous medium to yield AMMO. AMMO easily undergoes homopolymerisation to
form polyAMMO. The reaction sequence is shown in scheme 1.5.

Scheme 1.5 Synthesis of polyAMMO

1.9.3 Nitrato polymers

Polynitrato methyl methyl oxetane (polyNIMMO) and polyglycidyl nitrate
(PGN) are considered promising energetic polymers due to their favourable physical
and chemical properties. NIMMO is synthesised by nitration of hydroxyl methyl
methyl oxetane (HMMO). Nitration can be carried out using dinitrogen pentoxide or
acetylnitrate.57 Higher yield of NIMMO (97 to 99%) is possible when N2O5 is used
for synthesis. Scheme 1.6 shows the synthesis of poly NIMMO.

Scheme 1.6 Synthesis of polyNIMMO

Glycidyl nitrate monomer is synthesised by reacting PECH with KNO3 in

nitric acid medium for 4 hours at room temperature, followed by addition of sodium
hydroxide.58 Polymerisation of glycidyl nitrate to PGN can be done using
BF3etherate and 1,4-butanediol combination as initiator in CH2Cl2 medium at 200C
for 6 hours. The polymerisation proceeds by activated monomer mechanism. The
reaction is shown in scheme 1.7.

35
 Scheme 1.7 Synthesis of PGN

1.9.4 Energetic azido copolymers

Block copolymers of BAMO with other cyclic ethers have been synthesised
for use as energetic binders with high molar mass, low polydispersity index, low
glass transition temperature (Tg) and good energetics. THF-BAMO copolymers have
been prepared by using trifluoro anhydride (CF3SO2)2O as a bifunctional initiator.59
Copolymer of THF and BAMO with a 50:50 ratio is a liquid polyol with Tg of
-600C, molecular weight ~7000 and functionality 1.9.

Triblock copolymers of BAMO, AMMO and bis (ethoxy methyl) oxetane

with BAMO-AMMO block in the centre have been reported.60 1,4-butanediol and
BF3etherate (1:2 ratio) is used as initiator for the copolymerisation. The reaction is
carried out at -100C by adding a solution of the first monomer to the catalyst slowly.
When 95% conversion is over, the second monomer is added. Synthesis of BAMO
and nitrato methyl oxetane (NIMMO) block copolymers has been reported.
1,4-butanediol and BF3etherate initiator is used for the polymerisation61 with
methylene chloride as reaction medium.

New energetic copolymers based on BAMO-GAP, GAP-PGN and

BAMO-AMMO has been reported. GAP-ethylene oxide (EO) polymer has also been
prepared by copolymerising ECH with EO. Similarly GAP-THF based copolymers
have been synthesised. BAMO-GAP based copolymer is found to have moderately
high density, high heat of formation and high burning rate.

36
1.9.5 Azido polyesters and polyallyl azide

Energetic polyesters with functionality close to 2 are prepared from

2,3-dibromosuccinic acid and 1,2-propanediol or 3-chloropropanediol and succinic/
malonic acid. These halogenated polyesters are reacted with sodium azide for
conversion to azido polyesters.62 These polymers could be crosslinked by TDI.
Polyallyl azide is synthesised by azidation of polyallyl chloride. Polyallyl chloride
with molecular weight in the range of 2000 is obtained through cationic
polymerisation using Lewis acid catalyst like TiCl4/FeCl3/AlCl3 and aluminium
powder.63 The polymer obtained through this route is found to be branched.64 The
azidation of poly allyl chloride is carried out using sodium azide in DMSO medium
at 1000C for 12 hours and the conversion is monitored by IR spectroscopy.

1.10 Studies on azido polymer propellants

Thermal decomposition studies of azide polymers show that heating rates and
pressure do not significantly change the products of azide decomposition and
decomposition of azide moiety occurs prior to that of polymer backbone.65, 66 In the
case of PolyBAMO simultaneous decomposition was reported.67 Combustion of the
propellant is strongly influenced by the decomposition of polymer binder.68 Though
azide polymers contain relatively small amount of oxygen, the heat release is due to
the decomposition of the azide. Azido copolymers based on BAMO/NIMMO/
polyester (PE) and GAP/THF are reported to improve the low temperature
mechanical properties of propellant significantly.68, 69
Theoretical estimations
showed that, GAP/AP propellant could deliver a specific impulse of 2 seconds higher
than that of HTPB/AP preopellant.70 Studies reported on the burning characteristics
showed that trimethylol ethane trinitrate (TMETN) and triamino guanidine nitrate
(TAGN) are very effective in increasing the burning rate of GAP/AN propellant.68, 71
Komai et.al.70 reported that a burn rate of the order of 40 mm/s at 100 ksc could be
achieved for GAP/AP propellant by increasing the fine AP content.70 Zhao et.al72

37
reported that the exothermic peak temperature of AN is closely related to the burning
rate of GAP/mixed nitrate ester (NG, BTTN)/AN propellant and the exothermic
temperature may serve as an effective burning rate modifier for GAP/MNE/AN
propellant. A physico-chemical model for GAP/RDX pseudo propellant presented by
Liau et.al73 showed reasonably good agreement between prediction and measured
burning rate characteristics under atmospheric pressures. Studies on GAP based
propellants for ram rocket application were reported by Panda et.al.74, 75

1.11 Conclusions and scope of study

This chapter brings out a brief account of importance and development of

solid propellant systems. Different categories of propellants, different ingredients
used and their functions in composite propellants are discussed. The importance of
new generation oxidisers, binders and their advantages are discussed and compared.
Synthetic routes of energetic polymers are discussed. GAP, polyBAMO,
polyNIMMO and PGN are found to be promising as energetic binders. Based on the
comparison of important attributes with respect to physical, chemical and energetic
characteristics, GAP is found to be a strong candidate material for application as
energetic binder for composite propellant applications.

Various synthetic routes for GAP and experimental techniques required for
charcterisation of GAP are to be surveyed and a suitable method for synthesis is to be
selected. Study of the mechanism of polymerisation of epichlorohydrin (ECH) to
PECH and conversion of PECH to GAP by azidation reaction are planned. It is
aimed to synthesise PECH by different routes and to do a parametric study of the
polymerisation followed by detailed characterisation. Process parameters that control
the properties are to be identified and evaluation of kinetics of conversion of PECH
to GAP is envisaged. It is also aimed to scale up the polymerisation process of ECH
and synthesis of GAP.

38
 The investigation encompasses a detailed mechanical, morphological and
structure property study of GAP. Detailed thermal analysis to study the kinetics of
thermal decomposition of GAP and compounds of GAP. Detailed studies on the
glass transition characteristics and phase morphology of GAP and GAP-HTPB
blends are also planned for this investigation by calorimetry (DSC) and dynamic
mechanical analysis (DMA).

We have undertaken a comprehensive evaluation of the performance

parameters to study the suitability of GAP based propellant formulations. It is
planned to find a correlation between viscosity build up and curing reaction of GAP
from kinetic data generated by viscometry and FTIR spectroscopy studies. It is also
planned to investigate the effect of different plasticisers on GAP. Evaluation of GAP
based propellant formulations for mechanical, ballistic and rheological properties is
also envisaged.

1.12 References

1. Price, E.W., AIAA Paper 98–3978, (1998).

2. Hunley, J. D., AIAA Paper 99–2925, (1999).

3. Caveney, C. H., Geister, R. L., Ellis, R. A., and Moore, T. L., J. Prop. Power,
19, (2003), 1037.

4. Winter, F. H., The first Golden Age of Rocketry, Smith Sonian Inst. Press,
Washington D.C, (1990).

5. Davenas, A., J. Prop. Power, 19, (2003), 1128.

6. Bose, T. K, History of Solid Propellants, Solid Propellant Technology, Notes of

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