International Journal of Aerospace Sciences 2014, 3(2): 31-36

DOI: 10.5923/j.aerospace.20140302.01

Combustion Study of Composite Solid Propellants

Containing Metal Phthalocyanines
Lalith V. Kakumanu1, Narendra Yadav1,*, Srinibas Karmakar2

1
Department of Space Engineering and Rocketry, Birla Institute of Technology, Mesra, Ranchi, India
2
Department of Aerospace Engineering, Indian Institute of Technology, Kharagpur, India

Abstract Transition metal Phthalocyanines have been used as burn rate modifiers for AP-HTPB composite solid
propellants. An effort has been made to investigate the effect of Cu-Co-and Fe Phthalocyanines on the burn rate of composite
propellants, as also on the combustion characteristics of such propellants. The burn rate has been determined in Crawford
Strand Burner at 56 kg/cm2 pressure as also in low pressure burner setup at vacuum of 0.5 kg/cm2. Thermal analysis was
performed using Thermo Gravimetric Analyzer (TGA), Differential Scanning Calorimeter (DSC) and heat of reaction has
been measured by conventional Bomb Calorimeter. Scanning Electron Microscope (SEM) and Elemental Analyzer have
been used for material characterization and possible composition of composite solid propellants. Metal Phthalocyanines have
been found to influence the decomposition and to enhance the burn rate of the composite solid propellants.
Keywords Composite Solid Propellant, Burn Rate, Combustion Characteristics, Metal Catalysts, Fuel-Binder

applications like molecular electronics, liquid crystal

1. Introduction displays, gas sensors and organic laser materials. Their
useful properties are attributed to their efficient electron
The design and operation of a rocket motor depends upon transfer abilities. The central cavity of MPc is known to be
the burn rate of the propellant and the grain geometry of the capable of accommodating 63 different elemental ions. The
propellant grain. The knowledge of burn rate thus becomes functions of MPc are almost universally based on electron
an important condition for a successful design of a solid transfer reactions because of the 18 π electron conjugated
rocket motor. The combustion chamber pressure has been ring system found in their molecular structure [1]. They have
found to be one of the most important design parameter, as excellent stability against heat, light and air- moisture, and
the burn rate is exponentially dependent on the pressure. All found to be effective in many especially designed catalytic
the same, at a selected combustion chamber pressure, the reactions [2]. Bill, et al. [3] have suggested their uses as
designed burn rate of the propellant is feasible with the radiation absorbers. Henry [4] has reported their activeness
selected propellant not always available. The right selection for catalyzing oxidation reactions. According to Hronec, et al.
of oxidizer particle size and oxidizer percentage does modify [5] metal Phthalocyanines act towards electrode reduction of
the burn rate; however the designed mechanical strength and oxygen. Wheatley et al. [6] reported improvement of thermal
other characteristics also get affected by these. Embedding stability and enhancement of burn rate with decreased
metal wires or staples in the propellant also allows pressure exponent by adding copper Phthalocyanines (CuPc).
modification of burn rate; however the logistics and other Lundstrom et al. [7] used CuPc as a low pressure combustion
complexities have desisted selection of this method as an chamber. Fong, et al. [8] studied the effect of CuPc in
attractive method of modification. The burn rate of a AP-HTPB based propellant and reported increase of the
composite propellant can also be modified by incorporating pressure range of combustion and enhancement of burn rate
burn rate modifier catalysts. In fact, this method has been of DDI cured HTPB. Bain and Rudy [9] reported the
found to be the best and most effective method. Extensive tendency towards combustion instability by addition of
research has been advanced in search of an effective catalyst, CuPC. Kandaz, et al. [10] as well as Bolker and Salker [11]
and metal Phthalocyanines happen to be one of such conducted studies with Cobalt Phthalocyanine (CoPc).
catalysts. Zheng and Zhang [12] found that Iron Phthalocyanine (FePc)
The MPcs are candidate materials in high technology has large ionization potential and better di-oxygen binding
capability making them a worthy catalyst. Eileen, et al. [13]
* Corresponding author:
[email protected] (Narendra Yadav)
showed high oxygen reduction activity by using FePc. In the
Published online at http://journal.sapub.org/aerospace light of this, the background investigation has been carried
Copyright © 2014 Scientific & Academic Publishing. All Rights Reserved out using CuPc, CoPc and FePc as catalysts in AP-HTPB
32 Lalith V. Kakumanu et al.: Combustion Study of Composite Solid Propellants Containing Metal Phthalocyanines

composite solid propellants. Combustion study of solid carried out with the help of Shimadzu DTG-60 Thermo
propellants containing various contents of MPcs have been Gravimetric Analyzer (TGA) and differential thermal
investigated and an effort has been made to obtain detailed analysis (DTA) techniques whereas, TA Instrument
experimental data on the burning characteristics of USA-Q10 differential scanning calorimeter (DSC) was used
AP-HTPB based solid propellants to understand the role of to characterize the propellant samples at heating rate of
MPcs as burn rate modifier. 10°C/min, in the temperature range between 30 to 300°C.
The surface examination of propellant samples were
performed with the help of scanning electron microscopy
2. Experimental (SEM) (Model: Jeol-JSM 6390 LV, Japan) with the
following specification; accelerating voltage (10 KeV),
2.1. Materials secondary electron image mode, and with 20 mm working
Cobalt (II) Phthalocyanines (CoPc), 97%, Iron (II) distance. The test samples were mounted on aluminum stub
Phthalocyanines (FePc), 90% and Copper (II) and coated with gold metal to avoid electrical charging
Phthalocyanines (CuPc), 95% were purchased from Alfa during analysis. Heat of reactions of prepared propellant
Aesar India Ltd. HTPB of R45M grade was supplied by kind samples was determined with the help of Digital Bomb
request from Vikram Sarabhai Space Center (VSSC), India. Calorimeter (ARICO, India) at atmospheric pressure and
Ammonium Perchlorate (AP) was purchased from inert atmosphere. Linear burn rates of solid propellants were
Tamilnadu Chlorate, India Ltd. Bis(2-ethylhexyl) adipate measured by using standard Crawford Strand Burner and
(BEHA) of 99%, and Tolylene-2,4-diisocyanate (TDI) of Low Vacuum combustion setup respectively.
95% pure were procured from Sigma-Aldrich. Glycerol of
analytical grade from CDH India Ltd. was used for
propellant formulation.
3. Results and Discussion
3.1. Thermal Properties
2.2. Processing of Solid Propellants
Thermal decomposition characteristics of solid
The composite solid propellants (CSPs) were formulated propellants (as shown Figure 1) with and without catalysts
by using HTPB fuel binder and AP as a solid oxidizer. AP (MPcs) are investigated by thermo gravimetric analysis
composition was taking uniform, 70 percent, in all such (TGA). The percentage weight loss and residual mass
propellants samples. The average particle sizes of AP were percent of each sample between 30 to 500°C have been
44µ and 250µ in the ratio of 3:1 in the propellant samples. evaluated and properly presented in Table 2. The
BEHA was used as a plasticizer. The products made with it decomposition of Virgin AP-HTPB sample was found to be
have good softness and excellent viscoelastic property. It three staged, but on addition of 2% of CuPc, CoPc and FePc.
was dehumidified before the usage. Toluene Di-Isocyanate The thermal decomposition has become a two staged
(TDI) was used as a curing agent because it reacts with decomposition with a sudden mass loss, thus increasing the
hydroxyl groups in HTPB to form poly urethane linkages. decomposition rate. The decomposition patterns indicated
Besides this, Glycerol was used as a cross-linking agent to that primarily depolymerization and partial decomposition of
provide necessary branching for the fuel binder. The CuPc, crosslinked HTPB matrixes. Certain products made by
CoPc and FePc have been used as burn rate modifier self-cyclization at given temperature which may decompose
catalysts. The composition is given below (Table 1) in comparatively at higher temperature range.
weight percentages, catalysts are added extra. The requisite
quantity of ingredients was weighed properly, thoroughly
100
mixed, casted and cured for 6 days at 60 ±1°C in a hot air
oven and cut into strands for the experimentation.
80
Table 1. Composition of solid Propellant samples by weight percents
Weight (%)

AP 70 70 70 70 60

HTPB 21.60 21.60 21.60 21.60

DOA 6.60 6.60 6.60 6.60 40
(2% CuPc)
TDI 1.68 1.68 1.68 1.68 (Virgin AP-HTPB)
(2% CoPc)
Gly 0.12 0.12 0.12 0.12 20

CuPc - 2.00 - - (2% FePc)

CoPc - - 2.00 - 0

FePc - - - 2.00
0 100 200 300 400 500
0
2.3. Instrumentals Temperature ( C)

Thermal decomposition process of the propellants was Figure 1. TGA curves for propellant samples
 International Journal of Aerospace Sciences 2014, 3(2): 31-36 33

Table 2. Thermal decomposition (TGA) data of propellant samples shows partial loss in mass with the function of temperature.
Start End Weight Residual The first endothermic peak in DSC analysis as presented in
Sample
T (°C) T (°C) Loss (%) Mass (%) Table 4 corresponds to the transition from orthorhombic to
30 260 11.72 cubic phase as there is no significance mass loss observed.
Virgin 260 400 75.17
Just after the endothermic peak, an exothermic peak has also
AP-HTPB 1.47 been observed, which refers to decomposition of AP
400 500 11.64 relatively at temperature. This finding is in accordance with
30 260 6.45 the reports of Rajic and Suceska [16].
260 400 84.30 Table 3. Differential thermal analysis (DTA) data
CuPc 0
400 500 9.25
Sample Sample (mg) Endo Peak (0C) Exo Peak (0C)
30 260 11.58
Virgin
260 400 86.12 3.46 249 428
CoPc 0 AP-HTPB
400 500 2.30 CuPc 3.60 248 336
30 260 10.20 CoPc 3.62 246 346
260 400 83.76 FePc 3.76 244 334
FePc 0
400 500 6.04
The decomposition mechanism of AP-HTPB based
propellants can be illustrated through following steps;
The dissociation-sublimation of AP takes place in low
temperature (300°C) region,
NH4ClO4 NH3(g) + HClO4(l) (1) (1)
DTA (micro Volts)

In the second step, HTPB reacts with HClO4 and extracts

(2% FePc) the hydrogen content and forms HCl and H2O. Then the
carbonaceous residue reacts with O2 to form CO and CO2.
(2% CoPc)
The addition of MPc increases the rate of extraction of O2
from HClO4 due to the metal Phthalocyanine redox couple,
(2% CuPc) thus increasing the overall rate of reaction [17].
(Virgin AP-HTPB) MPcII + O2 MPcIIIO2 (2)(2)

MPcIIIO2 + e H Product + MPcIII (3)(3)

0 100 200 300 400 500
0
Temperature ( C) MPcIII + e MPcII (4) (4)

Figure 2. DTA thermograms of propellant samples

Measurement of heat of reaction experiments were
performed in a digital bomb calorimeter under a closed hood.
The DTA thermograms (as shown in Figure 2) of solid The experiments were carried out in the presence of 2L of
propellant sample with and without catalysts (MPcs) showed distilled water at ambient condition. Approximately 1g
that the AP molecules are subjected to phase transformation samples were placed on a stainless steel crucible, and
nearly 250°C in all such propellants. There is no remarkable combustion was initiated with an ignition unit via electrical
difference between first endothermic peaks, however, the discharge through a Ni-Cr alloy fuse wire (length of 10 cm)
variation in exothermic peak due to oxidation of AP in contact with the sample. Temperature increases were
molecule within the fuel-binder matrix was observed by the determined from PT-sensor embedded in the system. The
incorporation of MPcs catalysts. FePc was found to accuracy of the system was determined by measuring the
influence larger compared to other MPcs as clearly presented standard energy of combustion of benzoic acid, having a
in Table 3. Based on the literature, it has been found that the quoted energy of combustion of 6318 cal/g. Using the
thermal decomposition of AP under isothermal conditions is standard calibration method, total 3 calibrations were done,
started even at 150°C. The complex decomposition the experimental heat capacity for the unit was 2476cal/°C.
mechanisms of AP facilitate several unusual characteristics As shown in Table 5 it can be observed that the calorific
in wide temperature range. value of the catalyzed AP-HTPB propellants have increased
The observation made in this study is suggested that the substantially in comparison with the non-catalyzed
AP molecule undergoes autocatalytic reaction at 245°C, AP-HTPB propellants. The higher the percentage of catalyst,
which stops after the decomposition of approximately 30%, the higher is the calorific value. It can be inferred that sample
leaving ammonium perchlorate as the residual itself as also with Iron Phthalocyanine as catalyst has highest heat of
investigated [14, 15]. At temperatures above 250°C, the reaction followed by Cobalt Phthalocyanine and then Copper
decomposition of AP occurs which is not autocatalytic but it Phthalocyanine. This inferred that the MPcs certainly
34 Lalith V. Kakumanu et al.: Combustion Study of Composite Solid Propellants Containing Metal Phthalocyanines

enhanced the enthalpies on the incorporation in solid irregular but dispersion of MPcs molecules was found to
propellants. uniform throughout the surfaces. AP particles were also seen
encapsulating with HTPB which leads to development of
Table 4. Differential scanning calorimeter data
cubic crystal rather than spherical shape. SEM images
Sample Onset T Endo Peak T End set T evidence the morphology of the material and the absence of
Sample
Mass (mg) (°C) (°C) (°C) micro-voids and dewetting phenomena. We notice that on
Virgin the addition of 2% CoPc, the mixture is not homogeneous as
3.35 245 245 253
AP-HTPB compared to the virgin AP-HTPB mixture but the
CuPc 3.47 244 246 252 consistency is better than the sample of 2% CuPc. Small
CoPc 3.44 245 247 255 amounts of AP-HTPB chunks coated with CoPc can be seen
FePc 3.30 244 246 253 in SEM image.

Table 5. Results of heat of reaction 3.3. Elemental Analysis

Heat of reaction at ambient

In this analysis, each sample was combusted at high
Sample temperatures in oxygen rich environment and all the
condition (cal/gm)
Virgin AP-HTPB 1094.74
combustion products were swept out of the combustion
chamber by an inert carrier gas (helium). These products
CuPc 1165.55 were passed over a heated high purity copper which removes
CoPc 1239.41 unconsumed oxygen and converts nitrogen oxides into
nitrogen gas. These gases were passed through a thermal
FePc 1266.10
conductivity detector which detects the amount of Carbon,
Hydrogen, Nitrogen and Sulfur present in the compound.
3.2. Surface Characterization
Table 6 gives the results of the CHNS Analysis. It can be
SEM image of virgin-AP HTPB propellant (Figure 3) observed that the C/N Ratio has increased on the addition of
showed that AP and HTPB have blended well with each Metal Phthalocyanines. This phenomenon has to be studied
other and have formed a uniform composite matrix. On the further to get an insight into the actual combustion process
addition of 2% CuPc, the texture of propellants become that is taking place.

AP-HTPB 2% CuPc

2%CoPc 2% FePc

Figure 3. Surface morphologies of solid propellant samples

 International Journal of Aerospace Sciences 2014, 3(2): 31-36 35

Table 6. Results of CHNS elemental analysis as catalyst have the highest burn rate in comparison with
Sample
others at low vacuum conditions.
C/N As the pressure increases, the speed of the elementary
Sample Weight N% C% H%
Ratio
(mg) reactions in the decomposition of AP-HTPB rises which may
Virgin lead to the flame being closer to the material. This could be
5.52 2.97 8.40 24.96 6.28 the reason for the increase in burn rate with pressure.
AP-HTPB
CuPc 5.50 3.25 8.56 27.80 6.10 The burn rate studies at high pressure were carried out in a
CoPc 5.56 3.25 8.40 27.32 6.51 Crawford Burner and the burning rate was obtained by
FePc 6.54 3.00 8.74 26.15 6.44
sequential breaking of two fused wires, which were
embedded in the propellant strands. For few cases, there was
3.4. Burning Characteristics difficulty to get burning signal and sometime even there was
no signal. The experiments on those cases had been repeated
The burn rate studies at high operating pressures were by several times until the burn rate data was reproducible in
investigated using a Crawford Strand Burner. The propellant an average sense. While performing the experiments, it has
strands were electrically ignited and the time taken for 4 cm been observed that the propellant strands of CoPc are getting
length of the strand to combust was recorded and then burn damp by absorbing moisture. Thus, the special care for
rate was calculated. The firing vessel was filled with nitrogen storing the propellant strands is necessary.
gas at 56 kg/cm2 to simulate the operating chamber pressure
conditions. From Figure 4 we notice that there is an increase
in the burn rate of the propellants on the addition of metal
phthalocyanines. Of all the propellant samples, with FePc as
catalyst have the highest burning rate in comparison with
others at high pressure. Similar effect with FePc was also
observed by Fong et al. [8]. This increase in burn rate could
be because of the MPc addition. The addition of MPc
increases the O2 reduction activity which is controlled by the
MPcII/MPcIII redox couple as quoted in the mechanism in the
earlier section.

Figure 5. Plot of burn rate of propellants at low pressure

4. Conclusions
The following conclusions can be drawn from the present
investigations on the combustion characteristics of
AP-HTPB composite solid rocket propellants with and
without metal Phthalocyanines as burn rate modifiers.
All the samples except the one with 2% CuPc blendedwell
with the AP-HTPB slurry. This is because CuPc coats the
Figure 4. Plot of burn rate of propellants at high Pressure
slurry as soon as it comes in contact with the slurry and does
not mix thoroughly to get a consistent mixture as compared
The burn rate studies at low vacuum operating pressures to the other metal phthalocyanines used.
were investigated using a Low Vacuum Strand Burner. The On addition of 2% of CuPc, CoPc and FePc, the thermal
propellant strands were electrically ignited and the time decomposition of virgin AP-HTPB which was found to be a
taken for 3 cm length of the strand to combust was recorded three staged decomposition has become a two staged
and then burn rate was calculated. The firing vessel was decomposition with a sudden mass loss, thus increasing the
filled with vacuum up to 0.5 kg/cm2 in order to simulate the decomposition rate.
operating chamber pressure conditions. From the Figure 5, Addition of metal phthalocyanines does not show
we notice that there is an increase in the burn rate of the appreciable reduction in onset, endset and endothermic peak
propellants on the addition of metal Phthalocyanines. Of all temperatures; however, a significant reduction in the
the propellant samples, samples with Iron Phthalocyanines exothermic peak temperature has been observed.
36 Lalith V. Kakumanu et al.: Combustion Study of Composite Solid Propellants Containing Metal Phthalocyanines

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