Combustion and Flame 221 (2020) 326–337

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Combustion and Flame

journal homepage: www.elsevier.com/locate/combustflame

Effect of metal additives on neutralization and characteristics of

AP/HTPB solid propellants
Uma Vellaisamy, Shelly Biswas∗
Department of Space Engineering and Rocketry, Birla Institute of Technology, Mesra, Ranchi 835215, Jharkhand, India

a r t i c l e i n f o a b s t r a c t

Article history: Conventional ammonium perchlorate (AP) based solid propellant system has been used in rocket boosters
Received 3 June 2020 and most tactile missiles. But the toxic chloride emissions from the combustion of AP during the rocket
Revised 4 August 2020
launch increase the air pollution by 1%. For the conversion of conventional AP based propellant into
Accepted 5 August 2020
Green propellant there approaches can be used. These are scavenging propellants, Neutralizing propel-
Available online 21 August 2020
lants and Non-chlorine propellants. In present study an attempt is made to investigate the characteristics
Keywords: of neutralizing propellant with the help of different metal additives such as Al, Mg, and combined Al–
Solid propellant Mg. The investigations were theoretically and experimentally carried out and the results compared with
Ammonium perchlorate base composite solid formulation (AP/HTPB). Theoretical investigation on that addition of metal addi-
HTPB tives clearly indicated helps in the reduction of toxic HCl without the compensation of performance. The
Metal additives burn rate study was carried out using Crawford strand burner setup in inert atmosphere under different
Burn rate
pressure conditions ranges from 0.689 MPa to 4.136 MPa. A considerable enhancement in the burn rate
HCl reduction
of AP based solid propellant by 14.02% using pure metals as additives and by 54% using binary metal
mixtures as additives was observed. Studies on HCl reduction of AP based propellant samples using gas
bubbling setup shows that addition of Mg-15% to the base propellant enhances the HCl reduction by 47%
but the propellant was porous in nature and addition of Al–Mg(15%) to the base propellant enhances the
reduction by 37%. Thus, the binary metal mixtures in AP/HTPB based solid propellant resulted in better
reduction of toxic HCl without reduction in performance than the sample without metal additives.
© 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

1. Introduction chloric acid. Ammonium Perchlorate is a dominant oxidizer over

other oxidizers because of its unbeatable ballistic performance and
Rocket launch is considered as prominence of the country. Solid mechanical properties over other oxidizers [6]. Because of its ad-
propellants rockets are mainly used for generation of the thrust re- vantages it occupies a position as workhorse oxidizer in compos-
quired for these launches. The hot gases produced from the com- ite solid propellant. It found application in missiles and boosters.
bustion of the solid propellant are ejected through a convergent Ammonium Perchlorate (AP) based solid propellant system releases
divergent nozzle to generate the required thrust. Several investiga- toxic products like Hydrogen chloride gas (HCl) to the atmosphere;
tions have been carried out to understand the combustion mech- one launch releases around 100 tons of HCl to the upper atmo-
anism and ballistic properties of the solid propellants [1–4]. The sphere due to the combustion of AP based propellant. Accumula-
ejected hot gases constitute the toxic emission of rocket launches. tion of these toxic products in the atmosphere leads to the ozone
Toxic rocket emissions elementally affect the upper atmosphere depletion, acid rain, climate changes and side effects to human
and also the flora and fauna present near the vicinity of the rocket [7,8].
launch site [5]. Ammonium Perchlorate based composite solid pro- Toxic rocket emissions contribute 1% increase in the air pollu-
pellant is conventionally used solid propellant system for more tion for every launch. Pellett et al. [9] affirmed that from a space-
than five decades. Inorganic Ammonium Perchlorate is a powerful shuttle launch using a solid composite propellant, the rocket ex-
oxidizer in solid propulsion application with the formula NH4 ClO4 . haust contained 60 tons of HCl. In the eight Titan III rocket, the
It is a white crystalline solid and is easily soluble in water. Am- total range of peak HCl concentrations for the exhaust clouds was
monium Perchlorate is prepared by combining ammonia and per- 25–0.5 ppm (for 3–300 min) [9]. Another example for the toxic
emission of HCl is the European Space Launcher Ariane-5 which
contains 476 tons of AP based solid composite propellants, and on
∗
Corresponding author. combustion it gives 270 tons of concentrated HCl [10]. This toxic
E-mail address: shellybiswas@bitmesra.ac.in (S. Biswas).

https://doi.org/10.1016/j.combustflame.2020.08.006
0010-2180/© 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
 U. Vellaisamy and S. Biswas / Combustion and Flame 221 (2020) 326–337 327

mentioned the use of another technique to increase the burn rate

Nomenclature of metal additives by using pseudo alloy of mutually non soluble
metals i.e., embedding high melting point metals in low melting
Isp(s) specific impulse point metal matrix (Li–Be) [24]. A complete holistic study on the
C∗ (m/s) characteristic velocity effect of metal addition has not been carried out. There is no liter-
Tad(K) adiabatic flame temperature ature available which describes the burn rate enhancement along
Mw(g/mol) molecular weight with HCl reduction with the addition of metals to the conventional
Cl− (ion) chloride ion AP solid propellants. The need of today is to attempt at a solution
ṙ(mm/s) burn rate for the toxic exhaust without compromising on the performance
ρ th (g/cm3 ) theoretical density of the solid rocket. Thus, the proposed research attempt at a so-
ρ a (g/cm3 ) actual density lution to the above problem associated with toxic exhaust product
by studying the effect of metal additives on burn rate of AP based
solid propellant at different pressures along with the tendency of
HCl issue can be solved by using Green Propellants and it is the fu- metal additives in neutralizing toxic HCl.
ture of propulsion. Therefore three approaches to convert conven-
tional Ammonium Perchlorate based propellant into Green propel- 2. Experimental procedures
lant are by using Scavenging propellants, Neutralizing propellants
and Non-chlorine propellants. Many new replacements have been 2.1. Formulation of composite solid propellants
developed for Ammonium Perchlorate like non chlorine oxidizers
such as Sodium Nitrate (NaNO3 ), Ammonium Nitrate (AN), Potas- The solid composite propellant consists of several ingredients
sium Dinitramide (KDN) [11], Ammonium Dinitramide (ADN) [5], with oxidizer being the major component having 65 to 80% weight
Hydroxyl Ammonium Nitrate (HAN) [12–15], Hydrazinium Nitro- of the propellant. The others components are fuel binder, plasti-
formate (HNF) [16] and 2,2,2-trinitroethyl-formate (TNEF) [17] but cizer, curing agent, cross linking agent.
these oxidizers lack in mechanical properties, ballistic properties,
ease of production and safety [18]. Scavenging and Neutralizing 2.1.1. Oxidizer
propellants are the promising approaches to convert AP based Ammonium Perchlorate, supplied by Pandian Chemicals Ltd,
composite solid propellant to green propellant. Scavenging pro- Madurai (India), was used as the oxidizer. A bimodal system with
pellant is made by replacing a portion of Ammonium Perchlorate a coarse to fine ratio of 2:1 has been adopted in this work. The
(NH4 ClO4 ) with Sodium Nitrate (NaNO3 ). It will scavenge the HCl AP was ground in a pulveriser and sieved to obtain the required
by forming Sodium Chloride (NaCl) by the scavenging mechanism particle size of 250 μm for coarse and 75 μm for fine.
which takes place in combustion chamber. Addition of chlorine
free oxidizer sodium nitrate and metal additives (Mg) scav- 2.1.2. Fuel binder
enged/neutralized HCl by 1–10%. [19]. The main advantage of us- The binder system used in this study is hydroxyl terminated
ing NaNO3 as a HCl scavenger is due to its high density, ease polybutadiene (HTPB) HTPB supplied by Propellant Fuel Complex,
of availability and operability [20]. But addition of NaNO3 re- Vikram Sarabhai Space Centre, Trivandrum (India) HTPB/AP propel-
sults in low performance and poor mechanical properties. Spe- lant system is the conventional propellant system used in launch
cific Impulse (Isp) can be compensated by the addition of high vehicles and missile system. It constitutes of 75% of the fuel por-
energy materials like HMX, RDX. Neutralizing propellant elimi- tion of the propellant.
nate HCl emission by neutralizing it in the exhaust plume, the
neutralization mechanism is achieved with an infusion of metal 2.1.3. Plasticizer
additives in base composite solid propellant formulation. The Dioctyl adipate (DOA) was the plasticizer used is procured from
advantages are, neutralizing propellant possess good mechanical Sigma-Aldrich. The basic function of a plasticizer is to provide
properties, robust, versatile and reliability [20]. a viscoelastic character to the propellant and DOA works ideally
Researchers experimentally studied the effect of Mg in neu- with HTPB/AP systems. DOA used in this study was procured from
tralizing the HCl in the exhaust products of AP based solid pro- Sigma-Aldrich. DOA constitutes of 25% of the fuel portion of the
pellants. HCl exhaust analysis is done using three methods 1.Wet propellant.
bomb titration 2. Dry bomb with FTIR analysis 3.Motor exhaust
collection. The study concludes that the Mg propellant is more re- 2.1.4. Curing agent
liable than TP-H1148 (HTPB based Thiokol Propellant). It was re- Curing agent used in this study is Toluene diisocyanate (TDI)
ported by the researchers that Mg has better end-of-mix viscosi- procured from Merck. The role of a curing agent in a propellant
ties are lower at all shear rates for the Mg propellant, potlife is formulation is to enhance the inking between its organic (HTPB)
longer, safety hazards is minimal, same Isp efficiency, lower volu- and inorganic (AP) ingredients and enable proper curing. The per-
metric solid loading and also ability to eliminate the HCI from the centage of the curing agent is 6% for all the propellant samples
local launch site as compared to TP-H1148 (Space Shuttle propel- prepared. Glycerol (0.4%) as the cross linking agent is added for
lant) [21]. Many studies reveals that incorporation of metal addi- providing cross linking between the binder matrix and the oxidizer
tives in composite propellant showed a promising results in reduc- particles.
tion of HCl percent in the combustion exhaust products [22–24].
Theoretical performance studies on metal and metal alloys pre- 2.1.5. Additives
sented that the binary metal mixtures shows better Isp than pure The metal additives used in this study are Aluminium (Al), Mag-
metal composed solid propellant. Experimental studies on burn- nesium (Mg), and combination of aluminium & magnesium. The
ing characteristics of metal additives by Flame Morphology showed main function of additives is to enhance the enthalpy and per-
that binary metal mixtures establishes good burning characteristics formance of AP/HTPB based composite solid propellant and also
by increasing the distance between the reaction zone and the liq- helps in the reduction of toxic HCl in the combustion products.
uid metal which results in higher burn rate and it is advantageous The particle size of the metal additives is 150 μm for both Al and
to use binary metal mixtures because it requires lesser ignition Mg. Aluminium particles are spherical powders whereas flakes of
source due to the formation of eutectic alloy. The investigators also magnesium used in the present study. During the processing of the
328 U. Vellaisamy and S. Biswas / Combustion and Flame 221 (2020) 326–337

Table 1
Composition of AP based solid propellant samples.

Sample no. Oxidizer (AP) % Binder (HTPB) % Aluminium % Magnesium %

1 65 28.48 – –
2 65 23.48 5 –
3 65 18.48 10 –
4 65 13.48 15
5 65 23.48 – 5
6 65 18.48 – 10
7 65 13.48 – 15
8 80 13.48 – –
9 65 18.48 5 5
10 65 13.48 5 10

propellant a physical mix of both the metal particles is used for the
bimetallic samples. Total weight of the propellant for each sample
is 200 g.

2.2. Processing of propellant slurry

Prior to the processing of the propellant, AP is dried in the oven

at 60 °C for about an hour to remove any existing moisture. The
ingredients used to prepare the propellant stands with the compo-
sition and percentage of oxidizer and metal loading is presented in
Table 1.
The propellant ingredients (Table 1) are then weighed using a
digital balance (least count 0.2 g). The first step of the propellant
preparation process is to dehumidify DOA. The ratio of HTPB and Sample number Sample name Sample number Sample name
DOA in the Fuel binder portion is 75% and 25% respectively. HTPB 1. AP/HTPB(65:35) 6. AP/HTPB/Mg(10%)
and DOA are taken in a stainless steel beaker and mixed till homo- 2. AP/HTPB/Al(5%) 7. AP/HTPB/Mg(15%)
geneity is achieved. AP is added in 3–4 instalments and hand mix- 3. AP/HTPB/Al(10%) 8. AP/HTPB(80:20)
ing is done at room temperature. In case of metal additive based 4. AP/HTPB/Al(15%) 9. Mg (10%)
AP/HTPB/Al-Mg
propellant formulations, AP is added after all the additives have 5. AP/HTPB/Mg(5%) 10. Mg (15%)
AP/HTPB/Al-Mg
been added. TDI (6%) is added at last and mixed for about 15 min.
Fig. 1. The photograph of the prepared propellant sample strands.
TDI is the curing agent added for the achievement of cross linking
in the propellant matrix between HTPB and inorganic AP so that
the desirable strength of the propellant is obtained. Specific impulse (Isp), C∗ , Tad and exhaust HCl concentration of
Ammonium Perchlorate (AP) based solid propellant with and with-
2.3. Casting out metal additives are carried out. NASA CEA program is used to
calculate the performance parameters and moles of HCl of all the
The propellant slurry thus obtained after mixing process is im- propellant samples. The HCl reduction percentage of each sample
mediately casted. The propellant slurry is then casted into rectan- is obtained by molarity relationship. The exit pressure for the the-
gular metal moulds having a depth of 6 mm. The casted propellant oretical calculation is ambient pressure or 1 bar for all the sam-
is kept under vacuum condition for about 30 min to one hour for ples. The shifting equilibrium condition has been used for the the-
degasifying the propellant slurry and for removal of any blow holes oretical calculations. Based on the identified theoretical studies the
which may be formed in the prepared propellant. metal additives for experimental studies are selected.
The following shows the input conditions for theoretical perfor-
2.4. Curing mance calculation.
NASA CEA program:
The casted propellants are placed in a hot air oven maintained
at a temperature of 65± 2 °C for 6 days. After the completion of INPUT CONDITIONS:
Problem type Rocket (rkt)
six days of the curing process under constant temperature, the pro-
O/F mixture 1.86 & 4
pellant is allowed to cool down in the oven itself till it cools down Chamber pressure (psi) 14.2–20 0 0
to the ambient temperature. The propellant samples are then ex- Supersonic (Ae/At) 6.3
tracted from the moulds and stored in a desiccator to prevent it Combustion chamber Equilibrium
from accumulating any moisture. The next phase of the work is to Combustion temperature Estimate (3800 K)
prepare the propellant stands out of the block of the propellant. HCl concentration in the combustion exhaust of AP based com-
The Propellant block samples are then cut into strands of dimen- posite solid propellant:
sion 100 mm × 6 mm × 6 mm as shown in the Fig. 1 for carrying
out the burn rate studies in the Crawford strand burner setup. No o f moles o f (C l − )
Mole f raction =
T otal number o f moles o f the mixture
2.5. Theoretical performance calculation
 
mol Moles o f the solute
The identification of the metals additives for the sample prepa- Molarity =
l litre o f Solution
ration is finalized by analyzing the theoretical performance char-    
acteristics. The theoretical performance characteristics such as P P M value = Molarity ∗ Atomic weight o f C l − ∗ 10 0 0
 U. Vellaisamy and S. Biswas / Combustion and Flame 221 (2020) 326–337 329

2.7.1. Procedure for obtaining the density of the propellant samples

The mass of all prepared propellant samples are weighed be-
fore performing the density measurement. The measuring cylinder
was filled with distilled water up to 50 ml. Propellant samples are
wrapped in polythene bag to prevent the penetration of water into
the sample. Now polythene wrapped propellant sample is com-
pletely immersed into the distilled water with the help of thread.
The volume rise in the measuring cylinder is noted down in order
to find the volume of a propellant. The procedure was repeated
three times to get the average value.

volume o f a propel l ant = New water l evel − Original water l evel

Fig. 2. Schematic of high pressure crawford bomb setup. mass o f a propel l ant
Density o f the propel l ant =
vol ume o f a propel l ant

2.6. Crawford strand burner setup The surface morphology of the samples is determined with the
help of Scanning Electron Microscope (SEM). Scanning Electron Mi-
The burn rate study is carried out using Crawford strand burner croscope (Jeol, Japan), model: JSM-6390LV, magnification range: 5X
setup under different pressure conditions (Fig. 2). The study is - 3,0 0,0 0 0X, Coating unit: Au or Pt metal was used in the present
carried out in an inert atmospheric condition using nitrogen as study. A beam of high energy electrons is focused on the solid
the inert gas as well as the pressurizing gas. The burn rate study specimen. The electrons react with the sample and emit variety
was carried out under different pressure conditions ranges from of signal. For surface morphology and topology secondary elec-
0.689 MPa to 4.136 MPa. Total number of runs conducted for all trons (SE) are used. The samples were coated with platinum to
the 10 propellant samples is 120 runs [12 runs/sample]. The size make them electrically conductive. SEM is operated at low pres-
of the strands used for the burn rate studies in the Crawford high sures and at acceleration volts of 10KV & 20KV. The images were
pressure strand burner setup is 100 mm × 6 mm × 6 mm. How- taken at two magnifications X200 and X1500 to analyze the sur-
ever a length of 60 mm is considered for calculating the burn rate face morphology. Interface surface of samples is analyzed to un-
of the propellant. The propellant strands are inhibited by silicone derstand the internal texture of propellant. In order to get the
grease on all sides baring the top and bottom surface, so that the interface top surface of the sample is removed and coated with
flame does not spread to the sides of the strands and a linear burn- platinum. The heat content of propellant samples is determined
ing may be achieved. The bomb has four terminals namely, Com- by using Parr 6200 bomb calorimeter in nitrogen atmosphere. The
mon (C), Fuse I (F1), Fuse II (F2) and Igniter (I). The ignition source heat content is determined by evaluating the heat release to the
is a DC supply externally connected to the terminal I. A digital water using VNC viewer software by giving weight of the sample
timer (least count = 0.001 s) is also connected externally to the as input.
terminals F1 and F2. A coiled nichrome wire (dia 0.4 mm) which
acts as the igniter is inserted through the propellant strand at a
distance of about 1 cm from the top. Two fuse wires, 6 cm apart, 2.8. HCL reduction measurement setup
are inserted through the strand with the 1st fuse wire being 1 cm
below the igniter wire. The external parts of the terminals are con- HCl concentration in the exhaust of each combusted sample
nected to DC supply and timer as discussed above and the internal is determined by gas bubbling setup followed by Mohr’s titration
extensions of these terminals have the following connections: The method. Mohr’s method was used to analyse the concentration of
common terminal (C) is connected to one end of the igniter wire, the dissolved HCl from the bubbled gas setup used in the present
1st fuse and 2nd fuse. The other ends of these wires are connected study. The gas bubbling method has been used by Doll and Lund,
to their respective terminals. The external end of the common ter- 1991 and 1992 [21,25] in which they have used a wet bomb and
minal is grounded. When the strand is ignited, the flame travels the researchers have analysed the dissolved HCl content of the
down the strand and burns the 1st fuse and this triggers the timer water from the wet bomb where the combustion of Mg metal-
ON. The flame reaches the 2nd fuse and triggers the timer OFF. lized propellant was burnt. Mohr method is a standard analyti-
The output of the timer gives us the burn rate by the following cal method used for estimation of chloride ion in a given solution
logic, [26,27]. Figure 3 shows the schematic setup for collecting the ex-
haust gases from the combustion of propellant samples.
distance between the f use wires(length o f the strand ) This experiment was carried out to study the effect of metal
r˙ = mm/s
out put o f the timer (burn time ) additives in the reduction of toxic HCl exhaust from Ammonium
Perchlorate (AP) propellant. HCl reduction percentage is obtained
by measuring the chloride concentration in the exhaust products
2.7. Density, surface morphology and heat of combustion of all samples by Mohr’s method. Rubber tube connection is made
from the exhaust pipe of Crawford Bomb setup to the lid of 2 L
Water displacement method is generally used to determine the Glass bottle. The glass bottle with 0.8 L of distilled water was used
density of solid matter of irregular shapes. This simple method is to bubble the exhaust gases in to the water. Around 0.3 m glass
used in this present study, to obtain the density of the propellant tube is immersed in the distilled water for bubbling of the exhaust
due to unavailability of solid density meter. gas. The exhaust gas collection experiments were carried out in
Materials required: Prepared propellant samples, measuring inert atmosphere and ambient pressure conditions. After the bub-
cylinder(100 ml), distilled water, weighing machine, polythene bag, bling of exhaust gases, the water sample is titrated to obtain the
thread. chloride content of the exhaust gases.
330 U. Vellaisamy and S. Biswas / Combustion and Flame 221 (2020) 326–337

Fig. 3. Schematic of exhaust gas bubbling setup.

2.8.1. Mohr’s method of titration for estimation of chloride ion

content
Preparation of the required solution: Silver Nitrate solution (0.1
ML−1 ): Around 5 g of silver nitrate is dried in an oven at 100 °C
for 2 h to remove the moisture content. 4.5 g of AgNO3 is then dis-
solved in 250 ml of distilled water, and then the solution is stored
in a brown bottle to get the 0.1 molar silver nitrate solutions.
Sodium Chloride solution (0.01 ml−1 ): 0.584 g of NaCl powder
is dissolved in 100 ml of distilled water for preparing 0.01 molar
sodium chloride solutions.
Potassium Chromate solution (0.25 ml−1 ): K2 CrO4 solution used
as an indicator. 1 g of potassium chromate was dissolve in 20 ml of
distilled water to obtain the required indicator solution of strength
0.25 molar.
Instruments used determination of chloride concentration in wa-
ter sample: The instrument and accessories such as burette with
stand (50 ml), conical flask (250 ml), measuring cylinder (100 ml),
beaker (250 ml), dropper and funnel are utilized to determine the
strength of silver nitrate solution as well as determination of chlo-
ride concentration in water sample.
Fig. 4.1. Water sample. (For interpretation of the references to color in this figure,
2.8.2. Determination of strength of silver nitrate solution the reader is referred to the web version of this article.)
For determining the strength of the silver nitrate solution, the
burette was first filled with 50 ml of silver nitrate solution using a
glass funnel. Then 10 ml of NaCl solution was taken in conical flak 2.8.3. Determination of chloride concentration in water sample
and 2–3 drops of potassium chromate solution as an indicator was The procedure followed for the determination of the chloride
added to it. The next step was the titration of the NaCl solution concentration in water sample was as follows. The first step was
with silver nitrate solution by adding the solution drop wise from the filling up of the burette with 50 ml of silver nitrate solution
the burette to the NaCl solution. Appearance of orange red precip- using a glass funnel. Then, 10 ml of water sample was taken in
itate was the end of titration and the volume level of silver nitrate conical flask (Fig. 4.1) and 2–3 drops of potassium chromate solu-
in the burette was noted down. The procedure was repeated three tion was added to it. Then, the water sample (Fig. 4.2) was titrated
times to get the average strength of the AgNO3 solution. with silver nitrate solution by adding drop wise the silver nitrate
Strength of the Silver Nitrate solution is determined by using solution from the burette. The end of titration was determined by
the formula; the appearance of orangish red precipitate (Fig. 4.3) and the vol-
V ol ume o f NaCl ∗Mol arity o f NaCl ume level of silver nitrate solution in the burette was noted down.
Strength o f AgN O3 = (14)
V ol ume l evel o f AgN O3 in burette The procedure was repeated three times to get the average value.
 U. Vellaisamy and S. Biswas / Combustion and Flame 221 (2020) 326–337 331

temperature to 1273 K under nitrogen flow at the flow rate of

60 mL/min. The amount of the sample used for study was about
2–3 mg for each runs studied at the given 5 Kmin−1 ramp rate.

3. Results and discussions

3.1. Theoretical performance parameters evaluation

Theoretical results indicate that the addition of metal additives

such as Al, Mg (15%) increase the performance characteristics of
AP/HTPB propellant system as compared to the base AP/HTPB sam-
ple with oxidizer loading of 65% AP as well as from the test for-
mulation used AP/HTPB sample with oxidizer loading of 80% AP.
The increment could be because of the rise in the adiabatic flame
temperature with the addition of metal additives to AP/HTBP pro-
pellant samples. For the Li added samples there is an increase in
the Isp as compared to the base sample having 65% oxidizer load-
ing but its lower than that obtained for 80% oxidizer loading. This
is again attributed to the lower values of adiabatic flame tempera-
ture obtained from the Li added samples, as Li have lower melting
Fig. 4.2. Mid-point of titration. (For interpretation of the references to color in this point of 454 K and boiling point of 1600 K, which is mentioned
figure, the reader is referred to the web version of this article.)
in the studies of Blackman and Kuehl [24]. From the theoretical
calculation for the bimetallic additives it is observed that the per-
formance parameters are almost same as that of the test formula-
tion which used 80% oxidizer loading sample (Table 2). In general
the metalized propellant samples showed a rise in adiabatic flame
temperature because of its high melting and boiling point [28]. In-
crease in the percentage of metal loading affect the performance of
the propellant by producing the products of high molecular weight
(Mw) and by increasing the adiabatic flame temperature (Tad ).
Tad and Mw is an important parameter as it is directly in-
fluences the specific impulse of the propulsion system. Though
addition of metals produces products of high molecular weight
which decreases the Isp, this reduction is compensated by produc-
ing products of high adiabatic flame temperature. Metal affinity to
oxidizer and halogens affected the performance of the propellants
with bimetal additives as at the same time the two metals would
be reacting with the oxygen and halogen ions present in the oxi-
dizer. Increasing Li percentage in the binary metal additives (Al–Li,
Mg–Li) showed the decrement in the Isp because of the formation
of LiCl as also observed in the studies done by other researchers
[29]. C∗ is a measure of the energy available from the combustion
process. It depends on the heat capacity of the exhaust gas and is
Fig. 4.3. End point of titration. (For interpretation of the references to color in this inversely related to the molecular weight of the exhaust gas. Addi-
figure, the reader is referred to the web version of this article.)
tion of metal additives affect the C∗ and there is an increment in
its value this could be due the high heat capacity of the exhaust
Chloride concentration in the water sample is determined by product gas due to the presence of metals. Binary metal additive
using the formula; (Al–Mg) based propellant results in decrement of C∗ which could
be due to higher molecular weight of the exhaust gaseous prod-
Chloride content ucts obtained during combustion. As the metal oxides and metal
volume o f AgNO3 in burette∗NAgNo3 ∗Mw(Cl )∗ 10 0 0 chlorides in the exhaust gas would increase the molecular weight
= (15) of the exhaust gas and as C∗ is inversely proportional to the molec-
volume o f water sample
ular weight of the exhaust gas the C∗ value decreases though the
The above mentioned procedure is repeated for all water sam-
heat capacity of the exhaust gas increases.
ples with dissolved propellant exhaust gases to obtain the chloride
content for each propellant sample. The titration was carried out
three times for each sample and the chloride content determined 3.1.1. Effect of metal additives on the neutralization of HCl
for each titration done to get the average value. The effect of metal additives in neutralizing the HCl in the
combustion exhausts products of AP/HTPB propellant system has
2.9. Thermal degradation studies also been studied. HCl reduction percentage is obtained by cal-
culating chloride ion concentration using Molarity Relationship.
A simultaneous thermal analyzer (STA Model 409 PG luxx) Table 2 shows the theoretical mole fraction of exhaust HCl concen-
of NETZSCH, Germany was used to carry out the TGA analysis tration of all propellant samples and metalized propellants used
of the samples under non-isothermal conditions. Heating rates in this study. The results show that the effect of metal additives
of 5 Kmin−1 was considered for the study under nitrogen at- in neutralizing the HCl in the combustion exhausts products of
mosphere. The temperature range studied was from an ambient AP/HTPB propellant system.
332 U. Vellaisamy and S. Biswas / Combustion and Flame 221 (2020) 326–337

Table 2
Theoretical performance parameters for all propellant samples at 10 0 0 psi.

Sample no. Samples Isp (s) C∗ (m/s) Tad (K) HCl Mole fraction

1. AP/HTPB (65:35) 221.78 1426.2 1877.08 0.2

8. AP/HTPB (80:20) 263.27 1675.8 2980.79 0.2
2. AP/HTPB/Al (5%) 244.07 1576.1 2379.35 0.2
3. AP/HTPB/Al (10%) 257.16 1656.8 2780.79 0.2
4. AP/HTPB/Al (15%) 267.09 1711.8 3422.15 0.19
5. AP/HTPB/Mg (5%) 240.67 1550.2 2363.00 0.1
6. AP/HTPB/Mg (10%) 260.46 1665.2 2976.23 0.95
7. AP/HTPB/Mg (15%) 263.93 1691.4 3187.92 0.94
AP/HTPB/Li (5%)a 246.07 1573.7 2300.14 0.01
AP/HTPB/Li (10%)a 255.71 1615.5 2496.87 0.01
AP/HTPB/Li (15%)a 258.44 1627.3 2572.73 0.0
9. AP/HTPB/Al–Mg (5−5%) 258.44 1647.3 2670.72 0.10
10. AP/HTPB/Al–Mg (5−10%) 262.65 1673.2 3216.66 0.10
AP/HTPB/Al–Li (5−5%)a 266.41 1708.4 2953.08 0.2
AP/HTPB/Al–Li (5−10%)a 263.24 1692.0 3018.83 0.16
AP/HTPB/Mg–Li (5−5%)a 260.42 1678.3 2789.50 0.003
AP/HTPB/Mg–Li (5−10%)a 259.74 1657.3 2814.36 0.0004
a
Lithium samples were included in the experimental studies.

Mg and Li as metal additives resulted in better neutralization of

HCl by forming reactive base Magnesium hydroxide (Mg(OH)2 ) and
Lithium Hydroxide LiOH respectively.
It is observed that at high-temperature HCl molecules tend to
react with metal particles. When particles of Mg metal are incor-
porated into AP solid propellants, magnesium chloride is formed in
the exhaust. Mg atoms react with HCl by the following reactions
[30]:
2Mg + O2 → 2MgO
In the presence of humidity:
MgO + H2 O → Mg(OH )2
The hydroxide formed reacts with hydrogen chloride to give
magnesium chloride and water
Mg(OH )2 + 2HCl → MgCl2 + H2 O
In the aluminium added AP solid propellants, the Al metal re-
acts to the oxygen of AP to form aluminium oxide along with the
formation of aluminium chloride and water vapour [23]. Fig. 5. SEM image of AP/HTPB/Mg (15%) (X200).

Al + NH4 ClO4 → Al2 O3 + AlCl3 + H2 O + N2

Lithium reacts with ammonium perchlorate to give the follow-
ing products [24]: matrix. Actual density of bimetal based solid propellant is higher
NH4 CIO4 + Li → N2 + H2 + Li2 0(s ) + LiCl(l ) due to the compact packing of bimetals with HTPB binder as com-
pared to base composition and test formulation propellant. Even
Al–Mg combination showed lesser effect in reduction of HCl be- the theoretical density of bimetal based solid propellant is higher
cause of the negative neutralizing effect of Magnesium Aluminate due to the low atomic mass of added metals which would lead
(MgAl2 O4 ) as per the combustion mechanism mentioned in the to better packing of the metals in the binder matrix. AP/HTPB/Al
Doll and Lund [25]. Al–Li and Mg–Li resulted as better HCl scav- (5%) results in slight rubbery nature of the propellant as observed
engers than Al–Mg combination. Despite lithium based propellant physically. Rubbery nature of solid propellant may be due to the
samples shows better results among all, it cannot be considered as presence of 35% HTPB binder and plasticizer in the propellant
the green propellant because it releases lithium chloride as one of formulation.
its exhaust product, which is toxic and also handling of high reac-
tive lithium based propellant is difficult.
Theoretical density values of magnesium based solid propel-
lants are higher as compared to the actual density the propellant. 3.2. Surface morphology
Magnesium is not compatible with the cross linking agent glycerol
which results in porous propellant with blow holes in the trans- The image is taken with 200X magnification to check the sur-
verse surface of the propellant due to the evolution of gas. The face texture of the propellant samples. The surface shows the
gas evolution occurs when the magnesium metal reacts with glyc- proper blending of binder and oxidizer. The white particles on the
erol and also presence of moisture during curing process which surface represent the fine oxidizer particles. Slight brittle nature is
has also been observed by Mills et al. [31]. The evolution of gas observed on the surface by the observance of cracks in the pro-
is reduced by the addition of aluminum powder. Al–Mg combi- pellant surface which could be attributed to the higher loading of
nation also reduces the porous nature of the propellant by com- crystalline AP as shown in SEM image. Fig. 5 presents the interface
pact binding of the spherical Al and flakes of Mg in the binder SEM image for AP/HTPB/Mg with 15% metal loading.
 U. Vellaisamy and S. Biswas / Combustion and Flame 221 (2020) 326–337 333

Fig. 7. SEM image of AP/HTPB/Al–Mg (15%) (X200).

Fig. 6a. SEM image of AP/HTPB/Al (5%) (X200).

3.3. Burn rate studies and density studies

The burn rate studies for the AP/HTPB propellant was carried
out in the Crawford strand burner setup as shown in Fig. 2. The
following plots show the effect of pressure on the burning behav-
ior of AP/HTPB based propellant system. The temperature sensitiv-
ity coefficient (a) and combustion index (n) of each propellant is
estimated form the log r vs. log P plot. The burning rate of the pro-
pellant vs the pressure for the understanding the effect of pressure
in presented in Fig. 8.
From the Table 3 it is interpreted that the sample AP/HTPB/Al–
Mg shows highest burn rate of 20.2 mm/s and higher combustion
index of n = 0.599 at 4.136 MPa than the base propellant. AP based
solid propellant with pure metal additives (Al) shows lesser burn
Fig. 6b. SEM image of AP/HTPB/Al(15%) (X200). rate with respect to the base AP/HTPB (80:20) sample. Addition of
metals to the base propellant makes it more fuel rich, thereby the
reactivity of metals with oxidizer is decreased which leads to lower
Porous nature is observed with high percentage of magnesium burn rates. The same findings have been observed by the studies
this could be due to the reaction of magnesium with glycerol or conducted by other researchers [28]. Another reason for the lower
the presence of traces of H2 O in propellant slurry during curing burning rates could be slower metal/oxidizer reactions compared
process which leads to gas evolution, the same result is observed with the AP/binder reactions.
in the studies by other researchers [31]. Addition of Mg in the propellant samples increases the burn
Figure 6a and shows the interface SEM image of AP/HTPB/Al rates drastically which could be attributed to the low density and
5% and 15% Al loading at 200X magnification respectively. The sur- highly porous nature of the propellant sample. Another reason
face shows the proper blending of binder, oxidizer and aluminium for high burning rate could be due to low melting point of Mg
metal (Fig. 6a). Increase in the percentage of Al results in hard (650 °C), low ignition temperature and high reactivity of magne-
solid propellant, this shows the compact packing of metal parti- sium during combustion reaction.
cles in HTPB binder matrix of the propellant surface. Figure 6b Table 4 shows the values of theoretical and actual density, ‘a’
shows less interfacial voids and holes as a result of dewetting phe- and ‘n’ for AP based propellants with and without metal addi-
nomenon as observed for the 15% Al loaded samples. This could be tives. Theoretical density (ρ th ) of composite solid propellant sam-
because the binder is a viscoelastic material; the oxidizer is an or- ples is determined by using density ratio. Actual density (ρ a) of
ganic crystal and the metallic fuel being elastoplastic, there is on- the propellant is calculated using water displacement method (As
set of decohesion at the particle binder interfaces which induces discussed in Section 2.7). Theoretical density values of solid pro-
interfacial micro cracks or holes [32]. pellants were higher as compared to the actual density the propel-
The porous nature of AP/HTPB/Mg (15%) is reduced by the addi- lant. Compact packing of the bimetal in the binder matrix of the
tion of aluminum. Addition of aluminum to the magnesium based solid propellant lead to higher density as compared to the base
propellant reduces porous nature of the propellant by forming propellant and the test formulation samples studied. This could be
compact binding with the binder and a consistent structure of the due to the different structure of the metal particles, aluminum be-
Al–Mg propellant is observed as shown in the SEM image. ing spherical and the magnesium having a flake structure.
A consistent structure of the propellant surface is observed in The value ‘a’ represents the sensitivity of burn rate of propel-
Fig. 7 for AP/HTPB/Al–Mg (15%) which could be because of met- lants to temperature (Table 4). The value ‘n’ represents the sensi-
als of different structural nature, i.e. aluminium being spherical tivity of burn rate to pressure. The values of ‘a’ and ‘n’ are empir-
and flake type magnesium being incorporated into the elastomeric ical constants which are determined from burn rate experiments.
binder matrix. The value of n is an important parameter which tells the operating
334 U. Vellaisamy and S. Biswas / Combustion and Flame 221 (2020) 326–337

80

70

60
Buring rate r (mm/s)
50

40

30

20

10

0
0 100 200 300 400 500 600 700 800
Pressure (Psi)
1, AP/HTPB (65:35) 8, AP/HTPB (80:20) 4, AP/HTPB/Al (15%)
7, AP/HTPB/Mg (15%) 9, AP/HTPB/Al-Mg (10%) 10, AP/HTPB/Al-Mg (15%)

Fig. 8. Burn rate vs pressure for the propellant samples.

Table 3
Effect of metal additives and pressure on burn rate of AP based solid propellant.

Samples no. Samples Burn rate (mm/s) at different pressures (MPa)

0.7MPa 1.4MPa 2.7MPa 4.1MPa

1 AP/HTPB (65:35) 4.1 4.6 5.8 7.5

8 AP/HTPB (80:20) 9.6 10.7 11.7 13.1
2 AP/HTPB/Al (5%) 6 7.7 9.6 10
3 AP/HTPB/Al (10%) 6.2 7.9 9.9 11.9
4 AP/HTPB/Al (15%) 6.3 9.1 10.9 12.8
5 AP/HTPB/Mg (5%) 8.9 10.1 11 13.9
6 AP/HTPB/Mg (10%) 15.4 21.1 23.4 33.8
7 AP/HTPB/Mg (15%) 12.9 22.4 43.7 75.5
9 AP/HTPB/Al–Mg (10%) 5.1 7.7 10.9 13.1
10 AP/HTPB/Al–Mg (15%) 6.9 10.6 15.7 20.2

Table 4
Density of the propellant samples with a and n values.

Sample no. Samples Theoretical density (ρ th ) (g/cc) Actual density ρ a (g/cc) a (mm/s) n

1 AP/HTPB (65:35) 1.62 1.54 1.82 0.32

8 AP/HTPB (80:20) 1.78 1.70 2.66 0.23
2 AP/HTPB/Al (5%) 1.62 1.54 2.20 0.41
3 AP/HTPB/Al (10%) 1.69 1.62 2.22 0.43
4 AP/HTPB/Al (15%) 2.01 1.93 2.22 0.45
5 AP/HTPB/Mg (5%) 1.61 1.47 2.58 0.22
6 AP/HTPB/Mg (10%) 1.53 1.35 3.32 0.39
7 AP/HTPB/Mg (15%) 1.59 1.29 3.16 0.97
9 AP/HTPB/Al–Mg (10%) 1.69 1.61 2.01 0.53
10 AP/HTPB/Al–Mg (15%) 2.10 1.99 2.34 0.59

pressure regime of solid motor. As per the studies previous studies, This could be because of its incompatible nature with cross link-
the n value for steady operating condition ranges from n = 0.3– ing agent (Glycerol). The porous nature of magnesium based solid
0.7. In this present work Al–Mg combination results in results in propellant is reduced by the infusion of aluminum particles. Thus
higher burn rate with higher pressure index value of 0.59. The ‘n’ it can be concluded from the observed results that, combination
value for Al added sample is also increased by the addition of Mg. of Al–Mg (15%) to the propellant sample, the burn rate increases
Thus, it can be concluded from the study that the reactivity of alu- by 54% as compared to that of AP/HTPB (80:20) solid propellant
minum is increased by the addition of magnesium. AP/HTPB/Mg and enhances the burn rate of AP/HTPB (65:35) solid propellant by
(15%) solid propellant has low density and on visual inspection 170%. Addition of Al–Mg (15%) in the AP/HTPB (65:35) solid pro-
the propellant appears to be a porous propellant with low density. pellant results in higher pressure index of 0.599 when compared to
 U. Vellaisamy and S. Biswas / Combustion and Flame 221 (2020) 326–337 335

Table 5 Table 6
Effect of metal additives on the Heat of Combustion of AP based composite solid Theoretical and experimental ppm values of chloride ion in the tested samples.
propellant.
Samples Theoretical chloride Experimental chloride
Samples Weight (g) Heat of Combustion (cal/g) content (ppm) content (ppm)

AP/HTPB (65:35) 0.96±0.02 912±2.6 AP/HTPB (65:35) 5289.13 680.42±1.3

AP/HTPB/Al (5%) 0.97±0.00 966.05±4.8 AP/HTPB (80:20) 7092 703±3.8
AP/HTPB/Al (10%) 0.96±0.00 1019.64±7.5 AP/HTPB/Al (15%) 5213.7 664.397±0.9
AP/HTPB/Al (15%) 0.96±0.00 1073.22±6.3 AP/HTPB/Mg (15%) 2916 360.09±2.6
AP/HTPB/Mg (5%) 0.96±0.02 993.37±1.5 AP/HTPB/Al–Mg (10%) 3900 527.14±1.2
AP/HTPB/Mg (10%) 0.97±0.01 1162.95±2.4 AP/HTPB/Al–Mg (15%) 3058.99 422.36±1.4
AP/HTPB/Mg (15%) 0.97±0.01 1336.13±1.9
AP/HTPB /Al–Mg (10%) 0.97±0.01 1143.09±1.2
AP/HTPB /Al–Mg (15%) 0.96±0.00 1354.95±2.9
AP/HTPB (80:20) 0.961±0.05 1238.51±0.5
Table 7
Reduction % of Cl- ion by metal additives as compared to the base composition
65:35 and 80:20 solid loading.

Propellant sample Percentage reduction of HCl as compared to base

the AP/HTPB(80:20) solid propellant due to the increment of burn propellant sample
rate with pressure rise. Thus, it can be established that bimetal
65:35 80:20
addition makes eutectic composition at the time of combustion
which results in the formation of its metal oxides at one sharp AP/HTPB/Al (15%) 2 5
AP/HTPB/Mg (15%) 47 48
temperature which raises its enthalpy. Therefore, Al–Mg results in
AP/HTPB/Al–Mg (10%) 22 25
higher burn rate because reactivity of Al is increased by the addi- AP/HTPB/Al–Mg (15%) 37 40
tion of Mg which leads to lower ignition temperature. The density
of the bimetallic propellant is also higher than the base propellant
which could be attributed to the compact packing of Al–Mg in the
binder matrix.
From the Table 7 it is observed that AP/HTPB/Mg (15%) shows
3.4. Heat of combustion of the metallized propellants higher reduction in Cl− by 48% with respect to the base propel-
lant sample with 80% solid loading of AP. In case of Mg addition
The heat content of propellant samples is determined by using as additives, the neutralization of HCl is achieved by neutralization
Parr 6200 bomb calorimeter in nitrogen atmosphere and the re- reaction of magnesium oxide (reactive base) and HCl (acid) which
sults are presented in Table 5 and it is observed that addition of gives magnesium chloride and H2 O. Binary metal additives resulted
metal additives increases the heat of combustion. in reduction of Cl ion by 40% with respect to the base propellant
It is observed that the calorific value of the metalized propel- sample with 80% solid loading. Although the addition of Mg as ad-
lant have increased substantially in comparison with the base pro- ditives results in better reduction of HCl% in comparison to Al–Mg
pellant. The higher the percentage of metal addition, the higher is but the propellant obtained has lower density and high porosity
the calorific value. It was observed that the heat of combustion is in its structure which makes it unsuitable to be used as practical
lower for the Al-based propellants than the Mg-based propellants; solid propellant.
however the heat of combustion of aluminium (16.44 MJ/kg) was
higher than magnesium (14.92 MJ/kg). This lower heat of combus-
tion for Al based propellants than Mg based propellant samples
have also been reported by other researchers [30]. The bimetal- 3.6. Thermal degradation studies
lic sample Al–Mg (15%) based propellant has a high calorific value
then the pure metal addition samples, because of the formation of The burn rate of a conventional solid propellant largely depends
two metal oxides (Al2 O3 and MgO) is highly exothermic in nature on the decomposition of AP since a substantial part of the weight
which contributes to high heat of combustion values. Also the ig- of the propellant formulation is AP. Pure AP decomposes in five
nition of the samples is easier due to lower ignition temperature stages. From Fig. 9 it is interpreted that there is no significant
of Mg. change in the onset temperature on addition of metals to the AP
based solid propellant samples. It implies that the metal addition
3.5. Reduction in HCl concentration does not affect the decomposition of AP, because metals require
more heat energy for breakdown. Addition of metals affect the end
The combustion exhaust gases of AP base composite solid pro- temperature of decomposition of AP based a propellant which im-
pellant with and without metal additives were collected by gas plies that the decomposition of HTPB is affected by metals.
bubbling method. The water samples was titrated by Mohr’s titra- It is observed from Fig. 9 that the number of steps in the de-
tion method to determine the chloride content of propellant water composition of the base AP/HTPB propellant sample is reduced
sample and the experimental results are compared with the theo- with the addition of metals. The first peak is largely unaffected
retical results. Table 6 shows the chloride ion content (ppm) of the which corresponds to AP decomposition whereas the second peak
propellant. is shifted to lower temperature. The peak corresponding to HTPB
The results of Cl− ion reduction in the exhaust of the metallized decomposition at 440 °C is shifted to 420 °C and also the inten-
propellant samples as compared to the 65:35 AP:HTPB base pro- sity of the peak is reduced. It can be interpreted that addition of
pellant sample and 80:20 AP: HTPB propellant sample is presented bimetals (Al–Mg) reduces the steps of decomposition because of
in Table 7. It is observed from the table that AP/HTPB/Al (15%) formation eutectic composition at the time of combustion itself. It
reduces Cl- ion content by 5% as compared to the AP/HTPB (80% is concluded from the study that metal addition affects the pyrol-
AP oxidizer loading) sample. In case of Al addition, HCl is removed ysis of HTPB and it reduces the complexity of combustion of AP
by neutralization reaction of aluminum oxide (reactive base) and based solid propellant by reducing the number of steps of the re-
HCl (acid) which gives aluminum chloride and H2 O as products. action as observed from the TG and DTG curves.
336 U. Vellaisamy and S. Biswas / Combustion and Flame 221 (2020) 326–337

Fig. 9. TGA and DTG of the propellant samples with and without metal additives.

4. Conclusions pellant AP/HTPB (65:35) and compared to the AP/HTPB(80:20)

it results in 48% of HCl reduction.
In the present study, an attempt has been made to study the 7. Al–Mg (15%) combination as metal additives in the AP/HTPB
effect of metal addition on the burn rate and the HCl reduction (65:35) solid propellant results in 37% of HCl reduction and it
of the AP based composite propellants. Based on the results ob- results in 40% reduction of toxic HCl when compare to the test
tained from experimental and theoretical calculation the following formulation solid propellant (AP/HTPB (80:20)).
conclusions are derived: 8. Thermal degradation studies reveal the reduction in the num-
ber steps of the decomposition reaction with the addition of
bimetals to AP/HTPB propellant.
1. Metal additions to the AP based solid propellant increased the
Therefore, it can be concluded that the addition of bimetallic
theoretical performance and decreased the HCl concentration in
additives [Al–Mg (15%)] to the AP based solid propellant can pro-
the exhaust. Especially additions of Al–Mg (15%) increase the
vide a desirable propellant for practical application to meet the
theoretical Isp of AP/HTPB (65:35) solid propellant by 18.5% and
performance criteria with reduction of toxic HCl exhaust.
also decreased the HCl concentration in the exhaust by 51%.
2. Burn rate of solid propellant is enhanced by 14.02% using
Declaration of Competing Interest
Al 15% as metal additives as compared to the base sample
AP/HTPB (80:20).
The authors declare that they have no known competing finan-
3. AP/HTPB/Mg 15% shows high burn rate of 75 mm/s at
cial interests or personal relationships that could have appeared to
4.136 MPa though the prepared propellant sample is porous in
influence the work reported in this paper.
nature.
4. Density of AP /HTPB solid propellant is enhanced by 16.74% us-
Acknowledgment
ing Al–Mg (15%) as metal additive due to the compact packing
of Al and Mg particles of different atomic structure as also ob-
Authors are thankful to the Central Instrumentation Facility
served from the surface morphology studies. The heat content
(CIF), BIT Mesra, for carrying out the SEM surface morphology
of the propellants is also increased by the addition of the metal
studies of the prepared propellant samples used in the present
additives.
work.
5. The porous nature of magnesium based solid propellant is re-
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