Development of AP/HTPB Based Fuel-Rich Propellant For Solid Propellant Ramjet

49th AIAA/ASME/SAE/ASEE Joint PropulsionConference AIAA 2013-4171
July 14 - 17, 2013, San Jose, CA
Development of AP/HTPB Based Fuel-Rich Propellant for

Solid Propellant Ramjet
Jogesh Kumar Nanda1 and P. A. Ramakrishna2
Indian Institute of Technology Madras, Chennai, India, 600036
It is well known that reduction of Ammonium Perchlorate (AP) content in composite

propellant reduces the burn rate of solid composite propellants. Below a certain level of AP
content the propellant does not burn. This paper explores ways to enhance the burn rate of
fuel-rich composite solid propellant. The methods employed to enhance the burn rate of the
Downloaded by CARLETON UNIVERSITY LIBRARY on September 19, 2013 | http://arc.aiaa.org | DOI: 10.2514/6.2013-4171
propellant in the study are 1) Use of pyral 2) Recrystallization of AP, 3) Method to add
catalyst into the propellant and 4) Addition of AC with moisture. Pyral was added as a metal
fuel which resulted in propellants having higher burn rates and their density variations
along the length were absent contrary to those without pyral. Addition of AC with moisture
in these propellants increases the burn rate pressure index. The highest burn rate achieved is
3.8 mm/s at 70 bar with the propellant comprised of AP (particle size < 15 µm) and nano-
sized catalyst.
Nomenclature
AC = activated charcoal
AP = ammonium perchlorate
CC = copper chromite
DOA = di-octyl adipate
DRAP = double recrystallized ammonium perchlorate
HTPB = hydroxyl terminated poly-butadiene
IO = iron oxide
IPDI = isophorone di-isocynate
PYRAL = flake type Aluminum particle
RAP = single recrystallized ammonium perchlorate
I. Introduction
S olid propellant ramjet is an interesting concept as it utilizes the atmospheric air during its operation. It has great
advantages in terms of increment in range or payload capacity of the missile. In the present design of ramjet,
combustion takes place in two combustors. The primary combustor consists of a solid motor where this fuel-rich
propellant will burn and produce the combustion products which are rich in carbon and hydrogen. These combustion
products then burn in the secondary combustor in the presence of atmospheric air and provide overall thrust by
expanding through a convergent-divergent nozzle. Due to a change in altitude, the air density varies thus resulting in
a variation of air mass flow rate. This variation causes the oxidizer to fuel ratio (stoichiometric ratio) to change in
the secondary combustor. Hence, to provide flexibility in operation and to maintain stoichiometry in the secondary
combustor it is imperative to adjust the exhaust mass flow rate from the primary combustor. To achieve this, the
burn rate pressure index of the propellant in the primary combustor must be high. As we know, mass flow rate
depends on propellant density, burning surface area and burning rate of the propellant. As the density is a fixed
quantity for a given propellant, the other possible ways to increase the exhaust mass flow rate are either by
increasing the burning surface area or by increasing the burning rate. Increment in burning surface area reduces the
volumetric loading of the propellant in the case of port burning configuration and in case of end burning; increment
in grain diameter leads to an increment in drag as the frontal area of body increases. Hence, to avoid these it is
advisable to increase the burn rate of the propellant and also to have control on thrust a propellant with higher burn
rate pressure index is desirable.
The AP content taken in this study is 30 % by weight i.e. far away from the stoichiometry (fuel lean) of solid
composite propellant1 and results in very low/no burn rates as compared to conventional composite solid
1
M.S Research Scholar, Department of Aerospace Engineering, IIT Madras and AIAA Student Member.
2
Associate Professor, Department of Aerospace Engineering, IIT Madras and AIAA Non Member.
1
American Institute of Aeronautics and Astronautics
Copyright © 2013 by the American Institute of Aeronautics and Astronautics, Inc. All rights reserved.
propellants. The objective of present work is to develop such a propellant that contains very low oxidizer proportion
and high burn rate to increase exhaust mass flow rate from the primary combustor. It is found that propellant with
coarser AP particles, without pyral, had density variations along the length of propellant grain. Hence, development
of these propellants is restricted to use fine-sized AP particle and is beneficial as they have a higher burn rate than
coarser-sized AP propellants2. It is observed in the present work and also reported in literature3 that propellants
comprised of 30% of fine-sized AP particles have very low burn rate pressure index of around n=0.2. In order to be
able to moderate exhaust mass flow rate from the primary combustor as altitude changes, burn rate pressure index
should be high (~0.5). It is attempted to be achieved by adding AC containing moisture into the propellant based on
the work of ref.4
The burn rate of the solid composite propellant can be increased by decreasing AP particle size and addition of
catalyst2. Kohga3 reported that when IO is added, minimum percentage of AP required to burn a propellant in case
of fine AP is lesser compared to coarse AP. As reported in literaures4, 5, nano-sized aluminum enhances the burn rate
significantly as compared to micron-sized aluminum. However, Sumit and Ramakrishna6 found that pyral(a
particular form of aluminum) is a good burn rate enhancer for composite propellants as it has high surface area in
comparison to spherical particles identical in size and its burn rate falls in between that of nano-sized and micron-
sized aluminum particles. Also, the nano-sized aluminum is very expensive thus the use of pyral is adopted in this
study. Additionally, Ishita and Ramakrishna7 suggested recrystallization of AP and addition of catalyst during
recrystallization as a method to enhance the burn rate.
Table.1- Ingredients used in the propellant and their source

Ingredient Type Source
Ammonium Perchlorate (AP)
Oxidizer Tamil chlorates, Madurai
(NH4ClO4)
Thangamani Trading Company,
Aluminum (pyral) Metal fuel
Chennai
Hydroxyl Terminated Polybutadiene (HTPB) Satish Dhawan Space Center,
Prepolymer
(C4H6(OH)2)n Sriharikota
Di octyl adipate (DOA) Satish Dhawan Space Center,
Plasticizer
(C22H42O4) Sriharikota
Isophorone di-isocynate (IPDI) Satish Dhawan Space Center,
Curing agent
(C12H18N2O2) Sriharikota
Ferric oxide (IO) (less than 5 µm)
Burn rate modifier Alfa Aesar, Mumbai
(Fe2O3 ) (Micron)
Ferric oxide (IO) (4 – 5 nm)
Burn rate modifier Mach 1 Inc., USA
(Fe2O3) (nano)
Copper chromite (CC) (3 – 4 µm) High Energy Material Research
Burn rate modifier
(CuCrO4) Laboratory, Pune
Activated charcoal (AC) (5-50 µm) Burn rate modifier Merck, Mumbai
I. Experiments
A. Preparation of Propellant: Ingredients used in making the propellant along with their source are
given in Table. 1. The AP proportion is 30% by weight for all the mixes. All the solid ingredients listed in
Table.2 were kept in oven (600C) for at least one day to remove moisture before preparing the propellant.
Moisture is introduced in AC by keeping the AC into a tightly packed aluminum vessel and pouring small
amount of distilled water and kept into the oven for one day9. The moisture added into AC is about 40% by
weight. According to the method used for recrystallization of AP suggested by Ishita and Ramakrishna7, the
required amount of AP is dissolved into distilled water and then filtered through the sieve (15 µm). It is then
boiled to evaporate water content and catalyst is also added during evaporation process. In case of DRAP,
recrystallization of AP is done twice and catalyst is added during the process. Addition of the catalyst during
recrystallization ensures closer proximity of catalyst to AP particle.
2
Table.2- Composition of various Mixes
Type and size of AP AC with
Mix AP % IO % CC% pyral % Binder %
particle (µm) Moisture
1 AP (45-63) 30 ─ 3 ─ ─ 67
2 AP (less than 15) 30 3 ─ ─ ─ 67
3 AP (less than 15) 30 3 ─ ─ 10 57
4 RAP (less than 15) 30 3 ─ ─ 10 57

5 RAP (less than 15) 30 ─ 3 ─ 10 57
6 RAP (less than 15) 30 ─ 3 0.4 10 56.6
7 DRAP (less than 15) 30 3 (nano) ─ ─ 10 57
Prior to propellant preparation, appropriate amount of binder is taken in a beaker of 250 ml capacity and kept in
the oven at 60 ͦC for 6 hours for precuring10. Precuring of binder is found to be necessary for these propellants as the
solid fraction is very low. It prevents solid particles from settling down under the effect of gravity by increasing
binder viscosity at the time of mixing. All the solid ingredients are added one by one into the procured binder at
intervals of 5-10 minutes with continuous stirring. The slurry is then transferred into the sigma mixer, where it was
mixed for about an hour to provide homogenous mixing of ingredients. During the mixing, mixer was connected to
the vacuum pump to remove the trapped gases present in the slurry. Finally, it is poured into a piece PVC pipe of 60
mm diameter and 150 mm height with one of its ends covered by plastic sheet. This piece of PVC pipe is kept in the
desiccator for one day by maintaining vacuum of 700 mm of Hg for the complete removal of trapped gases from the
slurry. PVC pipe is then kept open to the atmosphere for 12-15 days in order to cure the propellant. The cured
propellant is then cut into small strands of 6 mm × 6 mm × 12 mm.
As shown in Table. 2, two different sized AP particles, one being less than 15 µm and another 45-63 µm (Avg.
54µm) are used in the study. All the propellants are prepared with the addition of pyral except for two (Mix 1 and
Mix 2). Addition of AC with moisture in the propellant (Mix 6) is been done by decreasing binder percentage in the
propellant. Binder comprises of 77% of HTPB, 15% of DOA and 8% of IPDI. Density of the propellants is
measured by volume displacement method. Samples are cut into a cubic shape and their mass is measured by an
electronic weighing machine of least count 10 mg. Knowing the weight of the distilled water (specific gravity =
1.002) displaced by the samples, density of the propellant is calculated. A minimum of five readings are taken for
each sample. The density of the propellant samples obtained is around of 1220 kg/m3, while the theoretical density is
1240 kg/m3.
B. Experimental set-up:
The Window bomb setup is used to measure the burn rate of the propellant strand. It consists of a hollow
cylindrical chamber inside which propellant strands burns. The cylindrical chamber is provided with two optical
windows made up of quartz. A xenon lamp is placed at a window of 25 mm diameter to illuminate the sample. On
the other window of 12 mm diameter a camera is placed to record the burning of the propellant sample. The camera
records the video at 25 frames per second. The cylindrical chamber has two openings, one at the top to drive out
exhaust gases and a second at the bottom to insert the propellant sample. The bottom part of the cylinder consists of
two electrodes, a strand holder and a nitrogen supply line. A commercial nitrogen cylinder is used to pressurize the
chamber. Nitrogen supply is provided with pressure regulator and pressure gauge to maintain desired pressure inside
the chamber. A D.C. power supply is connected to the electrodes through a switch. D.C. battery is set on 22 volts
and 1 ampere to provide sufficient current to ignite the propellant strand.
3
To exhaust
Exhaust valve
Cylindrical
Window for Xenon Lamp chamber
Power supply unit

D.C. power supply unit
Camera
Pressure gauge
Electrodes
Pressure regulator
Electric wires
From nitrogen cylinder
Fig. 1 Schematic diagram of Window bomb setup
C. Experimental Procedure:
The measurement of burn rate of these propellants has been a major problem during the initial period of study.
At first, the strand burner setup along with a timer circuit is used to measure the burn rates. In this arrangement, the
timer circuit gives the reading (burning time) as soon as nichrome wire is broken. It is found that nichrome wire did
not break for most of these propellants. The burning of these propellants is different from typical solid composite
propellants. It noticed that the flame shifts over the entire cross section of the propellant strand. This could be one of
the reasons for the nichrome wire not to break as sufficient amount of heat is not available. Thus the timer circuit
could not provide any reading. Finally, a window bomb setup along with a camera (Fig. 1) is used to measure the
burn rates of these propellants.
To measure the burn rate, the propellant strand (6 mm × 6mm × 12 mm) is coated with a thin layer of inhibitor
(silica grease) on its lateral surfaces to ensure the same burning surface area (6 mm × 6 mm) throughout strand
burning. On the top of the strand rubber solution is applied for uniform ignition. The nichrome wire of 0.5 mm
diameter is used to initiate burning of the propellant strand which is connected to the electrodes. The chamber is
pressurized at the desired pressure through the commercial nitrogen cylinder. A camera is used to record the strand
burning. The burn rate is obtained by running the recorded video frame-by-frame to cover a known distance on the
propellant strand.
II. Results and discussion

All the propellants contained only 30% of AP by weight, 3% catalyst and remaining metal fuel and binder
except Mix 1 and Mix 2 (without pyral). This paper discusses the effect of field particle size of AP and catalyst, use
of pyral, recrystallization of AP, addition of catalyst during recrystallization and addition of AC with moisture on
the burn rate of the propellant. The pressure range adopted for the study is 10-70 bar and the reported burn rate is
average of three propellant strands and the maximum dispersion was within 3 -7 % of the average value. Propellants
did not have density variation along the length of propellant grain except Mix 1 and Mix 2 (without pyral), since AP
particles settled down in the slurry in Mix 1 and Mix 2, during its curing period even after precuring of the binder.
4
Mix 1, having an average particle size of 54 µm and did not contain pyral, did not burn in the entire pressure
range tested. It has large density variations along the propellant grain. This is as a result of most of the AP particles
accumulating at the bottom of the propellant grain. Mix 2
comprises of less than 15 µm sized AP particle and all other
ingredients are same as Mix 1(Fig. 2). It burnt for 30-70 bar
with very low burn rates. These burn rates and burn rate
pressure index are closer to the burn rates reported in literature3.
In Mix 3 except pyral all other ingredients are same as Mix 2. It
found that 10% addition of pyral gave a tremendous increment
in burn rates of these propellants. The burn rate increased from
0.47 to 2.48 mm/s at 70 bar pressure by the addition of pyral in
Mix 2.
The next set of propellants is prepared to determine the
effect of AP recrystallization and addition of catalyst to AP

during recrystallization process. Mix 4 is prepared by the
method described earlier7. Both Mix 3 and Mix 4 were made up
of less than 15 µm sized AP, while all the other ingredients are
same in quantity. The main difference in these two mixes was Fig. 2 Burning rate characteristics of
the method of addition of catalyst in the propellant. It found that propellants with and without pyral
when IO was added to the AP particle during recrystallization, it
formed a coating, which helped in probably a faster
decomposition of AP. The difference in burn rates can be
clearly identified from the Fig. 3. At lower pressures, difference
in burn rates is more compared to that at higher pressures.
Hence, it is found that addition of catalyst during
recrystallization enhances the burn rates while deceases the
burn rate pressure index.
The final set of experiments is carried out on the
propellants prepared with AC containing moisture and nano-
sized catalyst (Fig .4). The next two mixes Mix 5 and Mix 6 are
made up of less than 15 µm sized AP particles and addition of
the catalyst is done during recrystallization. CC is used as a
catalyst for these propellants. The preparation method of these
two mixes is the same as Mix 4 described earlier. The main
difference in composition of Mix 5 and Mix 6 is the addition of Fig. 3 Burning rate characteristics of
0.4% AC with moisture in Mix 6 at the cost of the binder. The propellants prepared with and without
addition of AC with moisture in the propellant is done during recrystallized AP
the mixing of solid ingredients. It is noticed that the burn rates
of Mix 6 increased at high pressure and burn rate pressure
index increased by 0.16, i.e., from 0.24 to 0.4. These results are
similar to the results reported in literature9 that the addition of
AC with moisture increases the burn rate and burn rate pressure
index.
The final propellant (Mix 7) comprised of less than 15µm
sized AP. It underwent double recrystallization and nano-sized
IO is used as the catalyst. It is found that addition of nano-
sized catalyst in the propellant increased the burn rate
compared to micron-sized catalyst. The burn rates of Mix 7 are
higher for the entire adopted pressure range compared to Mix 5
(micron-sized catalyst). The highest burn rate recorded in the
study is 3.8 mm/s at 70 bar by the propellant made of nano-
sized catalyst. The burn rate and burn rate pressure index of
Mix 7 can be further increased by the addition of AC with
moisture in small amounts. Fig 4 Burn rate characteristics of propellants
It is reported in the literature that burn rate and burn rate with moisture AC and nano sized catalyst
pressure index is very low for propellants with 30 % AP.
5
Kohga3 reported that the propellant comprising of 30% AP (4
µm) and 1% IO have burn rates of 0.5 mm/s to 0.6 mm/s in the
pressure range 20-50 bar, beyond this pressure range, the
propellants did not burn. In present study the maximum burn
rate achieved is 3.8 mm/s at 70 bar and propellant burnt in the
entire pressure range (10-70 bar) as shown in Fig. 5. The
propellant is prepared by double recrystallization of AP and
catalyst addition during recrystallization. It comprises 30% AP
(less than 15 µm), 3% nano-sized IO (4-5 nm) and 10% pyral.
In present study, the increment in burn rate observed is
more than 600% compared to earlier studies3. Pyral plays a
very important role to enhance the burn rate for such
propellants.
Also, it is noticed that there is quite a bit of residue left

after the burning of these propellants. It is found that amount Fig. 5 Burn rate characteristics of the
of residue obtained after the burning of a propellant strand is propellants prepared in present study and
around 20 % of its strand weight. This remained nearly the those reported in literature3
same at different pressures too. This is to be expected as the
propellant is fuel rich.
III. Conclusion
The present study is carried out to enhance the burn rate of fuel-rich propellant that comprised of 30% of AP,
from existing values currently reported in literature3. The methods employed to enhance the burn rate are use of fine
AP particles, Pyral, recrystallization of AP, method of catalyst addition and AC with moisture. It is noticed that
these methods are quite effective in enhancing the burn rate for the fuel-rich propellants. The following can be
concluded based on the experiments conducted.
1) Addition of pyral is found to be necessary to avoid density variation along the length of the grain and to
enhance the burn rate significantly.
2) Fine sized AP is required to avoid density variation.
3) Recrystallization of AP and addition of catalyst during the recrystallization showed significant increment in
the burn rate.
4) Nano-sized catalyst addition increased burn rates further.
5) Addition of AC with moisture increased the burn rate pressure index.
6
References
1
Mukunda, H. S., “Understanding Aerospace chemical Propulsion”, 1st ed., Interline publishing, Bangalore, India, 2004,
Chaps 7, 253.
2
Kubota, N., “Propellants and Explosives”, 2nd ed., WILEY-VCH Verlag GmbH & Co. KGaA, weinheim, Germany, 2007,
Chaps. 7, 158,163.
3
Makoto Kohga, “Burning Characteristics and Thermochemical Behavior of AP/HTPB Composite Propellant Using Coarse
and Fine AP Particles,” Propellants Explosives Pyrotechnics, Vol. 36, No. 1, 2011, pp. 57-64.
4
K. Jayaraman, K. V. Anand, S. R. Chakravarthy, R. Sarathi, “Effect of nano-aluminium in plateau-burning and catalyzed
composite solid propellant combustion,” Combust and Flame, Vol. 156, No. 8, 2009, pp. 1662-1673.
5
Dokhan A, Price EW, Seitzman JM, Sigman RK, “The effects of bimodal aluminum with ultrafine aluminum on the burning
rates of solid propellants,” Proc Combust Inst, Vol. 29, No. 2, 2002, pp. 2939-2946.
6
Sumit Verma and P. A. Ramakrishna, “Effect of Specific Surface Area of Aluminum on the Burn Rates of Composite Solid
Propellant,” P.hd. Thesis, Department of Aerospace Engg., IIT Madras, India, 2012.
7
Kumar Ishita and P. A. Ramakrishna, “Development of a High Burn Rate Non-Aluminized Composite Propellant with Low
Burn Rate Pressure Index,” 47th AIAA/ASME/SAE/ASEE Joint Propulsion Conference and Exhibit (JPC), San Diego, CA, USA,
2011.
8
Sumit Verma and P. A. Ramakrishna, “Activated Charcoal as a Burn Rate Enhancer in Composite Propellant,” Combustion
and flame, Vol. 157, No. 6, 2010, pp. 1202-1210.
9
umit Verma and P. A. Ramakrishna, “Role of Moisture in Activated Charcoal in Composite Solid Propellant,” 47th
AIAA/ASME/SAE/ASEE Joint Propulsion Conference and Exhibit (JPC), San Diego, CA, USA, 2011.
10
SGaurav Marothiya, Rajiv Kumar and P. A. Ramakrishna, “Enhancement of Regression Rate in Hybrid Rockets,” 47th
AIAA/ASME/SAE/ASEE Joint Propulsion Conference and Exhibit (JPC), San Diego, CA, USA, 2011.
7

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49th AIAA/ASME/SAE/ASEE Joint PropulsionConference AIAA 2013-4171

July 14 - 17, 2013, San Jose, CA

Development of AP/HTPB Based Fuel-Rich Propellant for

It is well known that reduction of Ammonium Perchlorate (AP) content in composite

Table.1- Ingredients used in the propellant and their source

2 AP (less than 15) 30 3 ─ ─ ─ 67

3 AP (less than 15) 30 3 ─ ─ 10 57

4 RAP (less than 15) 30 3 ─ ─ 10 57

5 RAP (less than 15) 30 ─ 3 ─ 10 57

6 RAP (less than 15) 30 ─ 3 0.4 10 56.6

7 DRAP (less than 15) 30 3 (nano) ─ ─ 10 57

Power supply unit

Fig. 1 Schematic diagram of Window bomb setup

II. Results and discussion

effect of AP recrystallization and addition of catalyst to AP

Also, it is noticed that there is quite a bit of residue left

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