nd

Proceedings of the 2 National Propulsion Conference

NPC-2015
23-24 February 2015, IIT Bombay, Powai, Mumbai

NPC2015-Paper no.25
Reducing Ammonium Perchlorate content and Residue in Solid Fuel Ramjet
Nikunj Rathi P.A. Ramakrishna
Ph.D. Scholar, IIT Madras Professor, IIT Madras
Chennai, Tamil Nadu, India Chennai, Tamil Nadu, India

Abstract Introduction

Fuel-rich propellants (FRP) have been prepared with
motivation of higher density specific impulse compared to
typical kerosene based ramjets. Specific impulse (Isp_ram)
equivalent to that of boron based FRP and 1.5 better than
magnesium based FRP has been achieved. One of the key
issues addressed in this paper is the unburnt fuel or residue
which was reduced to 10-13% from 20% achieved in a prior
study with similar fuel rich propellants . Burn rate obtained
was 2 mm/s at 50 bar and an acceptable burn rate pressure
index of 0.67. It has also been shown that density of fuel plays
a key role in the overall system performance.
Nomenclature
FRP – Fuel-rich propellant
Isp – Specific Impulse
SFRJ – Solid Fuel Ramjet
AP – Ammonium Perchlorate
AC – Activated Charcoal
IO – Iron oxide
ε or A/F – Air-fuel ratio
Isp_air – Specific Impulse when atmospheric air is oxidizer
Isp_ram – Ramjet Specific Impulse
Ramjets have been in use for quite some time for military
application in missiles due to their high specific impulse (Isp )
compared to a rocket engine as they carry only the fuel and
utilize the air available in the atmosphere as oxidizer. This
increases the range of the missile with a ramjet compared to
that with a rocket of the same weight. Typically, ramjets use
liquid fuel kerosene and air as oxidizer. Mukunda1 has shown
that the Isp of a kerosene based ramjet is in the range of 14000-
17000 Ns/kg depending upon the operating conditions, but
kerosene has very low density. On the other hand, though,
with a fuel-rich propellant the Isp is slightly lower compared to
kerosene (as will be shown later), but gives density at least
twice that of kerosene based system. Therefore, the key here is
the higher density of fuel which reduces the system size or
packs more fuel in same volume. Different compositions with
boron and magnesium2 as metal fuels have been used in past
for making fuel-rich solid propellant for Solid Fuel Ramjet
(SFRJ) application.
Figure 1 shows the schematic of SFRJ with two combustion
chambers. The fuel-rich solid propellant burns in the primary
combustor and ejects fuel-rich gases which burns completely
with air in secondary combustor and provides thrust.

Primary Combustor
Fuel-rich propellant grain

Secondary Combustor

Air

Fig. 1 Schematic of a Solid Fuel Ramjet with two combustion chambers.

For long time boron has been a preferred metal fuel for SFRJ
due to its high heat of combustion 3 . However, it has certain
disadvantages like high melting and boiling point, ignition and
combustion problems at higher boron content 4 . Also, from
economical point of view, it is around 300 times costlier than
aluminum (boron -1300-1500 USD/kg and aluminum- 3.2-
6.35 USD/kg 5 ). Thus, in the present study propellants have
been made with aluminum.
Earlier, Jogesh and Ramakrishna 5 prepared fuel-rich solid
propellants with aluminum, ammonium perchlorate (AP) and
HTPB. The propellants had comparable energetics as that of
boron based fuel-rich propellants (FRP) but were extremely
cost effective. However, the residue left or the unburnt
propellant was of the order of 20-25%.
Aluminum is added as a metal fuel to increase the Isp as well
as the density of the propellant. The propellant burn rates can
be increased by having higher surface area of aluminum in the
propellant. Nano sized aluminum has a very high surface area
compared to micron sized aluminum6 and therefore composite
solid propellants making use of them are known to have
higher burn rates, but it increases the viscosity of the
propellant slurry drastically and makes it difficult to mix as
observed by Son et.al.9, 10 and Sumit and Ramakrishna 6 .
Further Sumit and Ramakrishna6 have proposed the use of
micron sized flake aluminum (pyral) with very high surface
area and heat of combustion higher than nano sized aluminum
to increase the burn rates of composite solid propellants . In
this study, as in Jogesh and Ramakrishna5 it is intended to
make use of pyral for making the fuel rich propellants.
Fluorination of aluminum leads to very high (volumetric and
gravimetric) heat release as compared to its oxidation 9 .
Therefore when aluminum is coated with a fluorine compound
such as polytetrafluoroethylene (PTFE), commonly known as
teflon is known to result in high burn rates. It has been shown
by Son et.al.9, 10 that the fluorination reaction occurs in
condense phase and results in possibly high temperatures very
close to the burning surface, therefore increasing the burn
rates. In this study, it is intended to make use of teflon coating
on pyral for making fuel-rich propellants.
Ishitha and Ramakrishna 7, 8 have used various catalyst coated
on AP to increase the burn rates of composite solid
propellants. They have carried out a detailed study to
understand how various catalysts when coated on AP results in
much higher burn rates as compared to when they are just
mixed in a solid propellant. Activated charcoal (AC) coating
on AP prevents AP from absorbing moisture and avoids AP
agglomeration. All the moisture absorbed by AC coated AP is
present in AC pores and this enhances the propellant burn
rates. This study also uses the doping of AP with potassium
along with iron oxide (IO) coating on AP to achieve higher
burn rates. This study will make use of these techniques in
preparing fuel-rich propellants.
Higher residue percentage due to low oxidizer content has
been a problem in FRP and this prevents the reduction of AP
content. Propellant with composition similar to those prepared
by Jogesh and Ramakrishna 5 in terms of binder, aluminum and
AP content have been prepared with an aim of reducing the
residue and attaining a burn rate pressure index greater than
0.5. The present study employs the use of above mentioned
techniques in combination or individually.
Propellant composition and I sp calculations
Equilibrium calculations were carried out using NASA SP273.
The Isp obtained from these calculations for different air-fuel
ratios assume that air is carried on board the system as an
oxidizer. As ramjet uses atmospheric air, Eq. 1 has been used
by Kubota and Kuwahar11 to convert this Isp value to Isp_air
where atmospheric air is used as an oxidizer and hence is not
carried on board.
( ) (1)
Where, ε is air-fuel ratio.
Ramjet takes in air as oxidizer and therefore air is coming into
the engine with a certain momentum which needs to be
considered. This has been accounted for in Eq.28 which is an
expression for the theoretical specific impulse for a ramjet.
These calculations consider combustor and nozzle efficiencies
to be unity.
[( ) ] (2)
Where, is air flow velocity at inlet.
The input conditions for the equilibrium calculations were at
an altitude of 10 km (Ambient pressure, Pa = 0.262 bar
Ambient temperature, T a= 223 K), flight Mach no. of 3 (v a=
898 m/s), 75% diffuser efficiency (Chamber pressure, Pc = 6
bar), nozzle area ratio 3.5 and inlet temperature of air is 600
K.
Figures 2 and 3 show the Isp obtained from NASA SP273 and
calculated Isp_ram respectively for the propellant compositions
made in the present study and typical FRP compositions as
mentioned in Table1 and 2 for comparison. Propellant
compositions were similar to those prepared by Jogesh and
Ramakrishna5 in terms of binder, aluminum and AP content.
They differed in the additives, which were chosen so as to
reduce the amount of residue observed by Jogesh and
Ramakrishna5 . They also have to have good burn rates and a
desirable burn rate pressure index of greater than 0.5.
 Table. 1 Propellant compositions made in the present study.

Moisture Teflon Pyral Binder Density Residue

Mix AP (% ) IO (% ) AC (% )
(% ) (% ) (% ) (% ) (kg/m3 ) (% )
0.3
1 29.7 10 60 1195 18
(coated)

1.765
2 30 10 58.235 1190 18
(coated)
29.73 0.27
3 10 60 1224 18
(4CR) (coated)
29.73 0.27 1.765
4 10 58.235 1212 13
(4CR) (coated) (coated)

0.3 0.12 1.765

5 29.7 10 58.115 1162 13
(coated) (40% of AC) (coated)

Table. 2 Typical Propellant compositions for FRP.

Carbon Napthelene Sodium Boron

Mix AP (% ) Mg (% ) Binder (% )
(% ) (% ) Nitrate (% ) (% )

6 35 30 35

7 49 2 24 25

Fig. 2 Specific impulse (Isp ) obtained from NASA SP273 for various compositions at different air/fuel ratios.
 Fig. 3 Specific impulse for ramjet (Isp_ram) obtained using Eq2 for various compositions at different air/fuel ratios.
It can be seen from Figures 2 and 3 that the Isp and Isp_ram for
propellant compositions proposed in this study are around 1.5
times that of the typical Mg based FRP at A/F of 25 and this
gap further increases at higher A/F values. Also, it can be seen
that boron based FRP deliver a slightly higher Isp_ram compared
to mixes prepared in this study. This increment in Isp_ram comes
at a much higher cost of boron based FRP as explained earlier
and therefore not considered in this study.
Propellant Preparation
All the propellants made in the present study used an AP of
particle size 25-45 μm. Only in mix2 teflon coated pyral
particle size was 43-63 μm and mix4 and mix5 used teflon
coated pyral of particle size less than 300μm. Binder (77%
HTPB, 15% DOA, 8% IPDI) was pre-cured for 4 hours to get
an appropriate viscosity such that the solids do not settle down
at the bottom while curing and the trapped gases can come out
of the slurry while degassing.
All the solids were crushed and sieved to their appropriate
particle size as indicated earlier. The procedure used for
doping AP with K+ and coating it with IO and AC coating on
AP is similar to what had been used by Ishitha and
Ramakrishna7, 8, 12 . AP and AP coated with IO were kept in
oven at 60o C for at least 24 hrs before being used so as to
remove any moisture present in it. AP coated with AC was
kept in ambient conditions for around 5 days so that it can
absorb moisture (40 % by weight of AC) from the surrounding
air. Once the binder pre-curing was done solids where mixed
one at a time in required quantities .
After hand mixing all the ingredients for around 5 minutes , the
propellant slurry was transferred to a sigma mixer where it
was mixed for another 45 minutes. Then, the propellant slurry
was taken out of the mixer and poured into a PVC pipe with
one end sealed with plastic, which acted as a casing. The
casing was then kept in a desiccator connected to a vacuum
pump maintained at a pressure of 160 mm of mercury for 24
hours to ensure that all of the trapped gases have been
removed from the slurry. After this, the slurry was left for
curing at ambient conditions for 14-15 days.
The cured propellant is taken out of the casing and cut into
samples of dimension 5 mm × 5 mm × 10 mm using a
surgical knife for determining the burn rate of the propellant.
Experimental Setup and Procedure
Window bomb was used in conjunction with a video camera
to record the burning of samples . A window bomb is a high
pressure vessel, which can withstand pressures up to 200 bar.
It has two quartz windows of diameter 25 mm and 12 mm. A
xenon light source is placed at the 25 mm window and a video
camera which can record at the rate of 25 frames per second
was placed at the 12 mm window to record the propellant
burning. The base plate of the window bomb consists of a
stand where propellant sample is placed, two electrodes for
ignition and a porous plate from where the inert gas enters the
chamber. At the top end of the vessel, an exhaust pipe is
placed to expel the burnt gases. Figure 4 show the schematic
of the window bomb.
The propellant sample was coated with an inhibitor on four
sides (each with area 10×5 mm2 ) so that it burns only in one
direction i.e. from top to bottom. Inhibitor coated propellant
sample was then placed on the stand and a nichrome wire of
0.5 mm diameter used for ignition is connected between the
two electrodes. It passes over the top surface of the propellant
sample. An in situ propellant with fine sized AP and HTPB
was applied on the top surface of the propellant sample to
ensure that the ignition is uniform throughout the cross -section
 Exhaust Valve
Pressure vessel
Window for Xenon lamp Camera
Electrodes
DC power
supply
Pressure gauge
Pressure regulator
Fig. 4 Schematic of Window Bomb.
Time
Fig. 5 Burning propellant sample images .
of the propellant. The vessel was then pressurized with
nitrogen and the exhaust valve was kept open slightly to purge
the combustion products.
A one ampere current was supplied to the electrodes
connected from a DC power supply at 22volts to ignite the
propellant sample. The video camera recorded the burning of
the propellant through the window. Since the sample length is
known it is possible to obtain the burn rate of the propellant by
replaying the recorded video frame by frame, where 1 frame
corresponds to 0.04 seconds. Figure 5 shows the images of the
burning propellant.
Results
Among the 5 propellant mixes made as shown in Table 1, only
mix 4 and mix 5 had residue of 10-13%, all other mixes
resulted in higher residue of the order of 18%. Though the
residue of 18% was marginally lesser than reported by Jogesh
Exhaust
Computer
Nitrogen
Cylinder
and Ramakrishna 5 of around 20-22%, still it was considered
high and hence not considered for burn rate tests. It has been
an effort in this study to make propellants similar in
composition to that reported by Jogesh and Ramakrishna5 , but
with the additives being added in a different way so as to
reduce the residue.
It can be seen in Table 1 that addition of teflon as a coating on
pyral in mix4 reduces the residue to 13% from 18% in mix3
where only pyral is used. This reaffirms the fact that coating
of teflon on pyral increases its reactivity as reported by Son
et.al.9, 10 . As stated in that paper, due to thermite reaction of
aluminum and teflon which could take place at the propellant
burning surface or in the gas phase, the heat feedback to the
propellant is large leading to higher burn rates and lower
residue.
Also, when AP coated with AC and moisture absorbed in AC
pores is used along with teflon coated pyral in mix5 it reduces
 Fig. 6 Burn rate comparison for Mix4 and Mix5.
the residue to 13% from 18% where only AP with teflon
coated pyral is used in mix2. This is similar to what is
observed between mix2 and mix4 where IO coated AP doped
with K+ along with teflon coated pyral results lower residue of
13%.
A very interesting aspect that comes out of this study as
explained above and can be inferred from Table1 is that only
when teflon coated pyral and catalyst coated AP (be it AC or
IO) are used in conjunction, residue can be reduced up to 13%.
Also, this was something that Jogesh and Ramakrishna 5 have
not tried in their studies. In the present study, 15 % of teflon
(by weight of aluminum and teflon) was used to coat the
aluminum, in future studies this could be increased further to
reduce the residue to a lower value.
Burn rates measured for mix4 and 5 are shown below in Fig.
6. Mix5 exhibits a high burn rate pressure index of 0.82 which
is quiet high to be used, but burn rate pressure index of 0.67 in
case of mix4 is a reasonably good one for SFRJ and gives a
better control on changing the fuel flow rates on command.
The highest burn rate recorded was 2 mm/s for mix4 at 50bar.
Mix4 has a higher burn rate pressure index of 0.67 compared
to the similar propellant composition studied Jogesh and
Ramakrishna5 , reason for this higher burn rate pressure index
seems to be the addition of K+ and teflon coating on pyral.
Also, mix5 has given a very high burn rate pressure index of
0.82, this is due to the addition of moisture in AC pores which
removes the binder melt as reported by Sumit and
Ramakrishna13 and the thermite reaction taking place between
teflon and pyral.
Conclusion
Propellant has been designed in the present study which has
resulted in residue as low as 13%, a burn rate pressure index
of 0.67 and burn rate of 2 mm/s at 50 bar. Using the same
propellant in hybrid mode where air flows through the port
can further reduce the residue to a much lower value. The
further aim would be to bring down the residue to 5% for the
actual system. The density of this propellant is 1245 kg/m3 , if
one considers 85% volumetric loading (port burning) the
density comes down to 1058 kg/m3 . The density of kerosene is
around 650 kg/m3 (accounting for pressurization system and
combustion chamber) and the Isp_ram for kerosene at A/F of 30
is 19259 Ns/kg and that for mix4 is 13884 Ns/kg and
therefore, it gives around 17% higher density specific impulse
than a kerosene based ramjet. Therefore, density plays a very
important role as a whole and further efforts could be made in
future to make higher density propellants with I sp_ram
comparable or higher than propellants made in the present
study.
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