RSC Advances

PAPER

Graphene-iron oxide nanocomposite (GINC): an

efficient catalyst for ammonium perchlorate (AP)
Cite this: RSC Adv., 2015, 5, 1950
decomposition and burn rate enhancer for AP
based composite propellant†
Abhijit Dey,*a Javaid Athar,a Pankaj Varma,a Hima Prasant,a Arun K. Sikder*a
and Santanu Chattopadhyay*b

Received 19th September 2014
Accepted 14th November 2014
DOI: 10.1039/c4ra10812d
www.rsc.org/advances
A facile and ecofriendly method for the synthesis of nano-sized iron oxide (Fe2O3) decorated graphene
(GINC) hybrid by ultrasonication via microwave irradiation has been developed. During this process,
nano-sized Fe2O3 particles with a size of approximately 20–30 nm were uniformly decorated over a
graphene sheet. The nanohybrid was characterized by XRD, HRTEM, Raman spectroscopy and Raman
mapping. To study the enhancement of catalytic activity of iron oxide by preparing GINC, several AP
based compositions containing 1–5 weight% GINC were made and characterized through simultaneous
thermal analysis (STA). Along with this, formulations with other catalysts with 1–5 weight%
concentrations were also prepared and evaluated. Experimental results showed that GINC with 5
weight% concentration was considerably more effective as compared to other compositions. To further
extend this application as a burn rate enhancer in composite propellants, several formulations of
composite propellants containing 1 part of different burn rate enhancers, such as Fe2O3, nano-sized
Fe2O3 and GINC, were prepared and evaluated using theoretical prediction, viscosity, ballistic properties,
sensitivity parameter and thermophysical properties. To quantify the burn rate enhancement in the
presence of GINC, burn rate measurement, STA, DSC and activation energy calculation were performed.
The results show that the burn rate of propellant increases from micron-sized Fe2O3 (30% increases) to
nano-sized Fe2O3 (37% increase). In the presence of GINC, a significant increase (52%) in burn rate is
achieved. In GINC, effective iron content is about 50% as compared to nano- and micron-sized Fe2O3.
Hence, GINC was found to be an excellent burn rate modifier for an advanced AP based propellant system.

2004 by Andre Geim and Konstantin Novoselov. They obtained a

1. Introduction
Graphene is a special type of carbon having a at sheet, which is
just one atom thick. It has attracted great attention in recent
years due to its unique features such as electrical, optical,
catalytic and mechanical properties. Graphene nanosheet
shows very high electrical conductivity at room temperature due
to the high mobility of electrons. Graphene was discovered in
a
High Energy Materials Research Laboratory, Sutarwadi, Pashan, Pune-411021, India.
E-mail: abhidey_bkn@yahoo.com; ak_sikder@yahoo.com; Fax: +91-20-25869316;
Tel: +91-20-25912225
b
Rubber Technology Centre, Indian Institute of Technology, Kharagpur, India. E-mail:
santanu@rtc.iitkgp.ernet.in; Fax: +91-3222-255303; Tel: +91-9932790504
† Electronic supplementary information (ESI) available: Table S1: comparison of
important properties of graphene with CNT, Table S2: thermal analysis results
with different burn rate enhancer with AP, Table S3: approximate propellant
compositions, Table S4: physico-chemical properties with different burn rate
suppressant in propellant composition, Table S5: thermal analysis results with
different burn rate suppressant in propellant composition, Table S6:
physico-chemical properties with different burn rate suppressant in propellant
composition. See DOI: 10.1039/c4ra10812d
graphene sheet by splitting graphite crystals into increasingly
thinner particles until individual atomic planes were obtained.
This remarkable contribution was felicitated by the Nobel Prize
in Physics in 2010 and led to a sudden increase in research
interest on graphene.1,2
Graphene is the mother form of all the graphitic forms. It is a
building unit for carbon nanostructures of all other dimen-
sionalities such as 0D Bucky balls, 1D nanotubes and 3D
graphite. It has a lot of similarities to carbon nanotube (CNT)
such as structure, properties with high aspect ratio (i.e. lateral
size/thickness), a large surface area, good mechanical properties
and rich electronic states. It has lots of scope in different areas
where CNTs have already been exploited. Graphene is a better
electrode material compared to CNTs. The 2D planar geometry
of graphene sheet assists electron transport. Table S1 (see ESI†)
depicts some properties of graphene as compared with CNTs.
Due to excellent properties with large surface area, graphene
nanosheets (GNSs) with a 2D geometry have been considered to
be a new class of promising materials for prospective

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Paper
applications in solar cells, actuators, sensors, eld-effect tran-
sistors, eld-emission devices, batteries and super capacitors.1–9
In addition to this, the production cost of graphene is consid-
erably lower compared to CNTs10,11 and hence large scale
production of graphene is feasible. Li et al.12 have mentioned a
facile approach to synthesize graphene materials. It opens up
tremendous opportunities for various technological applica-
tions. Graphene is composed of sp2 hybridized carbon atoms
and has a honeycomb structure.13–16 A thorough review by
Noorden17 on different carbon nanostructures concluded that
research interests on fullerenes and carbon nanotubes become
saturated but increased research interest may be expected for
graphene in the next decade.
Recently, graphene sheets have been successfully used as a
substrate that helps to stabilize and disperse nanoparticles
(CdS, CdSe, Fe3O4, TiO2, SnO2, Co3O4).18–24 This dispersion
along with the stabilization of nanoparticles helps to enhance
catalytic activity; hence, it needs to be synthesized by facile and
environmentally benign techniques.
Metal/metal oxide particles have received considerable
attention due to their distinctive optical, electronic and catalytic
properties.25,26 Transition metal particles (Fe, Co and Ni) and
metal oxides (such as Fe3O4, TiO2, SnO2, and Co3O4) have a
distinctive catalytic nature. They have been widely used to form
a new class of nanocomposites by decorating CNTs. Note that
these nanocomposites show enhancement in catalytic behavior.
On the other hand, relatively less attention has been given to
metal/metal oxide nanoparticles supported on graphene
sheets.27–29 Iron oxide is a very good magnetic material that has
been broadly used in magnetic storage, microwave absorbing
materials, catalysts and new devices. Raw iron oxide is a good
burn rate enhancer in ammonium perchlorate based composite
propellant. When nano-sized iron oxide was used in the
composition, catalytic activity increased as per a previously
reported study.30 We hope that Fe2O3/graphene nanocomposite
(GINC) can have a possible synergistic effect or a combination of
the properties of the two components (graphene sheet and
Scheme 1 Synthesis, processing and application of GINC as burn rate modifier in missile system.
This journal is © The Royal Society of Chemistry 2015
RSC Advances
Fe2O3) in new composite materials that impart unique features
for catalysis and nanotechnology.
To evaluate the effect of GINC in AP based composite
propellants, several compositions were processed. Composite
propellant mainly consists of two parts, i.e. HTPB based binder
and oxidizer. AP is generally used as a potential oxidizer. Burn
rate is one of the vital properties for a composite propellant. For
strategic reasons, propellants with different burn rates were
required to be processed for different missiles. From ultra low
burn rate (r # 3 mm s
1 at 70 ksc) to very high burn rate,
propellants (r $ 50 mm s
1 at 70 ksc) were processed and used
in different missile systems. As shown in many studies, the
reaction rate, activation energy and temperature of the thermal
decomposition of propellant are closely related to the burn rate
of the composite propellants. The lower the decomposition
temperature, the higher will be the burning rate of the propel-
lant.31–33 The burn rate enhancement effects of some transition
metal oxides in different composite propellants have been
widely used. The result shows that the nal decomposition
temperature of composite propellant directly depends on the
amount of burn rate catalyst added, as well as the particle size of
the burn rate enhancer, both of which are important factors
that affect the decomposition temperature of the propellant. It
is well proven that a nano-sized catalyst is more effective as
compared to a micron-sized catalyst.34,35 It is also known that
nanoparticles are able to agglomerate due to their small size,
large surface area, and high surface activity, which greatly
affects their catalytic behavior. However, agglomeration causes
an inhomogeneous dispersion of the nanocatalyst; hence,
reduced catalytic efficiency was observed, which leads to an
increase in the practical cost of the catalyst. Graphene has a very
large surface area of nanoparticle to disperse and distribute on;
moreover, it has many more important properties such as low
mass density, good thermal stability, chemical inertness and
high electrical and thermal conductivity (see Table S1†).
Herein, we have highlighted (see Scheme 1) a simple, facile
method for the decoration of iron oxide nanoparticle over a
RSC Adv., 2015, 5, 1950–1960 | 1951
RSC Advances
graphene substrate. Presently, the catalytic behavior of transi-
tion metal oxide decorated graphene nanocomposite in the
propellant burning rate, as well as thermal decomposition of
AP, have rarely been reported. Therefore, in this work, graphene
and nano-sized iron oxide were separately prepared and char-
acterized. GINC was prepared by ultrasonication through
microwave irradiation and characterized. The comparative
study of GINC's catalytic effect within the AP decomposition
reaction was investigated. Along with this, catalytic perfor-
mance with a variety of concentrations were also evaluated and
optimized. Several propellant compositions with different burn
rate modiers (1 part), i.e. normal Fe2O3, nano-sized Fe2O3,
GINC and a blank sample were processed and evaluated by
strand burn rate data, simultaneous thermal analysis (STA),
differential scanning calorimetry (DSC) and activation energy
calculation.
2. Experimental section
2.1 Synthesis procedures
All the chemicals used were of analytical grade and used
without further purication. Graphite akes used in this work
were purchased from Reinste nano ventures, India. Graphene
was prepared in three steps as reported in the literature.36 In the
rst step, graphite oxide was prepared from graphitic akes by
the Hummers method.37 In the second step, thermally
expanded graphene oxide (TEGO) was prepared by thermal
expansion/exfoliation at 1050  C (Ar, 30 s). Finally, the graphene
nanosheet (GNS) was obtained by hydrogen reduction of TEGO
at 400  C for 2 hours.
The synthesis of nano-sized iron oxide consists of two steps:
the preparation of polymeric gel citrate, followed by gel calci-
nation. Gel preparation was carried out in a gel preparation unit
and calcination was carried out in a calcination unit, i.e. muffle
furnace. A typical batch operation was as follows: solid citric
acid and ferric nitrate nonahydrate were dissolved in ethylene
glycol in the dissolution vessel to get a brown color solution.
The solution was slowly heated to 90  C by circulating hot
thermic uid (silicone oil) in the reactor jacket. Initial
exothermicity was observed at a reaction temperature of
100  C with evolution of NOx fumes, which was controlled by
stopping the circulation of hot thermic uid in the reactor
jacket. Exothermicity of the reaction subsides during the rest of
the reaction period. Then, the hot oil circulation was started in
the reactor jacket and temperature of reaction mass was
increased from 100  C to 140  C. Water molecules evolved
during the reaction were condensed by a condenser using
chilling water circulation in the tubes, and uncondensed gases
were scrubbed by venturi scrubber. Aer the collection of 3.5 L
condensate, the polymeric gel was prepared, and then, it was
placed in the muffle furnace. The gel was rst dried at 300  C for
2 h under oxygen rich atmosphere by purging compressed air.
Evolved gas was exhausted through a chimney by an ID fan.
Then, the dried gel was calcined at 600  C for 6 hours to obtain a
pure nano-sized a-Fe2O3.
For preparing GINC, rst, 50 mg graphene was dispersed in
absolute ethanol by ultrasonication for 40 min. Aer
1952 | RSC Adv., 2015, 5, 1950–1960
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ultrasonication, nano-sized iron oxide was added into the gra-
phene dispersion and further ultrasonicated for 120 min. Aer
ultrasonication, the dispersed composite solution was placed in
ambient condition for drying. Aer the evaporation of ethanol,
the material was deposited on a Petri dish. The deposited
material was placed into the microwave reactor for 2 min for
better exfoliation. Aer cooling, the sample was collected in a
sample vial (see Scheme 1).
To study the efficiency of catalytic behavior of GINC for AP
decomposition, four different compositions with different
catalysts such as graphene, iron oxide (micron-sized and nano-
sized) and GINC with 1 wt% concentration were prepared and
characterized.
2.1.1 Composite propellant processing. To evaluate the
burn rate enhancing capability of GINC with respect to other
burn rate enhancers for the composite propellant, several
formulations (4 nos) were processed. Composite propellant
consists of two parts, i.e. binder and solid ingredient. The
binder, which consist of hydroxy terminated polybutadiene
(HTPB: OH value 40–50 mg g
1, moisture 0.15%, from Orion
Chemicals), was cured with toluene di-isocyanate (TDI: purity
99%, RI 1.565-1.567 at 30  C; from Bayer). Dioctyl adipate (DOA:
saponication value 303  3, moisture 0.5%, from Subhash
Chemicals) was used as a plasticizer to increase the process-
ability. Indigenously prepared GINC, nano-sized iron oxide,
graphene and micron-sized iron oxide (from S. D. Fine Chem-
icals) were used as a burning rate enhancer. The mixture (1 : 2)
of trimethylolpropane (OH value 1220, moisture 0.5%,
purchased from Celanese) and butane-1,4-diol (OH value 1220,
RI 1.444  0.002 at 30  C, moisture 0.5%, purchased from Biaf)
was used as an adduct in the composition. Two different sizes of
ammonium perchlorate were used in the propellant formula-
tions. The rst consisted of pure, research grade ammonium
perchlorate (purity 99%, density 1.95, from Tamil Nadu Chlo-
rates) with an average particle size of 300 mm. The other size of
ammonium perchlorate was prepared by grinding ammonium
perchlorate (>99% pure) in a uid energy mill to an average
particle size of 60 mm. Aluminum metal powder (from MEPCO)
of an average particle size of 15 mm was used as a metal fuel. The
propellant formulation is given in Table S3 (see ESI†). The
propellant formulations were mixed in 10 kg batches using a
vertical planetary mixer of 15 L capacity. During mixing,
vacuum (2–3 Torr) was applied at 55  C, in order to remove air
bubbles from the formulation prior to casting. The propellant
mixture was cast under vacuum by slurry cast techniques.38 The
propellant was cured at 60  C for 10–12 days in a water-jacketed
oven. The base composition, without burning rate enhancer,
was also processed in the same manner. The propellant
formulations were subjected to various performance tests. The
detailed process ow chart is given in Fig. 1.
2.2 Characterizations
2.2.1 GINC characterizations. Sonication was conducted
using an ultrasonication bath (35 kHz, Kudos). Microwave
irradiation was carried out by a microwave reactor (make: Raga).
Environmental scanning electron microscopy (ESEM) was
This journal is © The Royal Society of Chemistry 2015
Paper
Fig. 1 Flow chart for the processing of composite propellant.
carried out with a Quanta 200, FEI. High resolution trans-
mission microscopy (HRTEM images, SAED pattern) charac-
terization was carried out by Tecnai F-30, FEI with a 300 kV eld
emission gun (FEG). Nano-sized Fe2O3, graphene and graphene-
iron oxide nanocomposite were dispersed in methanol with
ultrasonication. The dispersion was placed on a TEM grid, and
the solvent was evaporated by oven drying. Fourier transform
infrared spectroscopy (FTIR) was performed using a Nicolet
5700, Thermoscientic. Raman traces and mapping were
measured by inVia reex micro Raman, Renishaw. X-ray
diffraction traces were collected by X-ray diffractometer D8
Avance, Bruker, with Cu Ka source in the measurement angle
range of 2q ¼ 2–90 with a scan rate of 2 min
1.
To evaluate the catalytic effect of GINC on AP decomposition
reaction, thermogravimetric analysis (TGA) and differential
thermal analysis (DTA) were carried out by Mettler Toledo,
Model-TGA/SDTA851 at a heating rate of 20  C min
1 in a static
nitrogen atmosphere with alumina reference material.
Comparison with different burn rate enhancers, such as
micron-sized iron oxide, nano-sized iron oxide and graphene
with concentration variation were also carried out.
2.2.2 Propellant characterization. Before making an actual
composition, some important ballistic properties, such as
characteristic velocity (C*), ame temperature (Tf) and specic
impulse (Isp), were calculated by NASA CEC-71 soware.
To study the effect of GINC in AP based composite propel-
lant, several important properties have been evaluated during
the course of propellant processing. During processing,
viscosity is one of the important parameter, and viscosity of the
propellant mixture was characterized by Brookeld viscometer
at 40  C. These measurements were carried out for 4–5 h at an
interval of one hour.
Aer the completion of curing reaction, the strand burning
rate of the propellants was determined in the pressure range of
5–9 MPa by employing an acoustic emission technique.39,40 The
methodology involved the combustion of the strand (ignited
using a Nichrome wire) of dimensions 100  6  6 mm in the
nitrogen pressurized steel bomb. The acoustic signal generated
This journal is © The Royal Society of Chemistry 2015
RSC Advances
and the perturbations caused by the propellant deagration
were transmitted through the water medium to a piezoelectric
transducer (200 kHz) connected to an oscilloscope. The burning
rates were computed from the time that was recorded in the
trial conducted at each pressure for each sample. The standard
deviation was of the order of 0.2%.
Calorimetric values were obtained using a bomb calorimeter
(make: Parr instruments, Germany). The densities of propellant
compositions were determined by a Mettler density kit (density
1.432 g cm
3, heat of formation
565.8 kJ mol
1). Note that
toluene was used as a liquid.
Density ¼ (weight of the sample/weight of the sample in solvent)
 specific gravity of the solvent (toluene).
The sensitivity to impact stimuli of the propellant composi-
tions was determined with a fall hammer apparatus (2 kg drop
weight) using the Bruceton Staircase method41 and the results
are given in terms of the statically obtained 50% probability of
explosion (H50). The friction sensitivity was measured with a
Julius Peter apparatus by incrementally increasing the load
from 0.2 to 36 kg, until there was an ignition/explosion in ve
consecutive test samples.
The ignition temperature was measured by a Julius Peters
apparatus. The sample was uniformly heated at a constant rate
(5  C min
1) in a Wood's metal bath until it exploded or ignited
at the ignition temperature.
Thermophysical properties were also evaluated by Flashline-
3000, Anter Corporation. Thermal analysis of the propellants
was carried out using STA (Q-600, USA), Perkin Elmer Pyris
Diamond DSC apparatus at a heating rate of 20  C min
1 under
a N2 atmosphere (sample mass 10 mg). The activation energy
for propellant combustion was also determined with the help of
DSC at different heating rates by following the Kissinger Ozawa
equation.
The mechanical properties were obtained with an Instron
device (Model TIC-1185, UK). The operating instrumental
parameters were always maintained constant: gauge length, 25
mm; crosshead speed, 50 mm min
1. The stress and strain
properties were determined using a dumbbell-shaped specimen
as per the ASTM-D-638 specication.
3. Results and discussion
High resolution transmission electron microscopy (HRTEM)
and a selected area electron diffraction (SAED) were carried out
to inspect the quality of nano-sized iron oxide decoration on the
graphene layer. Fig. 2 shows the HRTEM micrographs with an
SAED pattern of graphene, nano-sized iron oxide and GINC. The
results conrmed that the size of nano-sized iron oxide and
graphene are in the nano range. In fact, graphene sheets were
clearly visible, and both nano-sized iron oxide and graphene
were found to be crystalline in nature as conrmed by the SAED
pattern. According to Fig. 2c, iron oxide nanoparticles were
placed over the graphene sheet to form a nanocomposite;
moreover, it nicely shows arranged lattice fringes in GINC.
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RSC Advances Paper

Fig. 2 HR-TEM image (I, II and III) and SAED pattern (IV) of (a) nano-
sized iron oxide, (b) graphene, (c) graphene-iron oxide nanocomposite
(GINC).

Fig. 3(a) shows the FTIR spectrum, which conrms the

absence of a functional group and presence of low defect on
the graphene surface. Along with this, the Raman traces of
Fe2O3 were observed. Raman spectroscopy was used to
Fig. 3 (a) shows FTIR traces, confirming the presence of low defect
examine the quality of the graphene sheet before and aer content in graphene. (b) shows a characteristic Raman signature. The
the formation of nanocomposite using the abovementioned decoration of nano-sized iron oxide over graphene substrate is
techniques. The most pronounced Raman traces were a D confirmed by Raman mapping.
band at 1310 cm
1, corresponding to defects, and a G band at
1575 cm
1, which corresponds to the in-plane vibration of
sp2 carbon. A 2D band at 2627 cm
1, which is generated due compositions. Furthermore, the catalytic efficiencies of GINC,
to a two phonon double resonance process, has also been graphene, nano-sized iron oxide and normal iron oxide with
observed. According to Fig. 3b, the D band of graphite was concentration variation (from 1, 3, 5 wt%) were also studied.
weak, whereas graphene shows a small D band. The Fig. 4a–c depicts the typical XRD pattern of nano-sized iron
lower intensity D band indicates the presence of a lower oxide, graphene and GINC from 0 to 100 . All the peaks were
defect on graphene akes. Coleman and coworkers sug- assigned to crystallographic phases. The XRD pattern of GINC
gested42 that the defects are mainly present at the edges of (Fig. 4c) showed graphene peaks, as well as nano-sized Fe2O3
the akes, and the basal plane is found to be defect free. The peaks. It was revealed that during processing, the crystallo-
I(D)/I(G) of the GINC is increased by 2 times (0.993) with graphic phases of graphene and iron oxide remains intact.
respect to pure graphene (0.497). Several defects with sp2 According to the Scherrer equation, the calculated crystallite
domain were formed during the formation of nano- sizes of graphene nanosheet (GNS) and nano-sized Fe2O3 were
composite. Fig. 3(b) shows a characteristic Raman signature; 28 nm and 38 nm, respectively. The catalytic efficiencies of all
moreover, the decoration of nano-sized iron oxide over gra-
phene substrate was conrmed by Raman mapping (see
Fig. 3(b)).
Table S2 (see ESI†) depicts the thermal analysis results of
AP and AP with 1 wt% of different burn rate enhancers, i.e.
graphene, GINC, nano-sized Fe2O3, and micron-sized Fe2O3.
The results show that AP decomposes at lower temperature
and gives higher DH value in the presence of 1 weight% GINC
as compared to other burn rate enhancers. Hence, GINC was
found to be a more efficient catalyst for AP decomposition
reaction. This was also supported by thermogravimetric
analysis data in which 73.81% weight loss was observed in a
temperature range of 224.7–384.5  C. These temperature Fig. 4 XRD traces of (a) iron oxide, (b) graphene (c) graphene iron
regions were relatively low when compared to other oxide nanocomposite (GINC).

1954 | RSC Adv., 2015, 5, 1950–1960 This journal is © The Royal Society of Chemistry 2015
Paper RSC Advances

Fig. 5 DTA traces of (a) AP; (b) AP with 1%, 3%, 5% graphene; (c) AP with 1%, 3%, 5% iron oxide; (d) AP with 1%, 3%, 5% nano-sized iron oxide; and
(e) AP with 1%, 3%, 5% graphene iron oxide nanocomposite (GINC). TGA traces of (f) AP with 1%, 3%, 5% graphene; (g) AP with 1%, 3%, 5% iron
oxide; (h) AP with 1%, 3%, 5% nano-sized iron oxide, and (i) AP with 1%, 3%, 5% graphene iron oxide nanocomposite (GINC). Comparative bar
diagrams of (j) HTD with different compositions in DSC analysis; (k) DH; and (l) final temperature of different compositions in DTA analysis.

This journal is © The Royal Society of Chemistry 2015 RSC Adv., 2015, 5, 1950–1960 | 1955
RSC Advances Paper

the burn rate enhancers were found to increase with increase in

concentration (see Fig. 5a–l).
The DTA results also support the DSC result. The nal
temperature, i.e. Tf, was found to be lowest in case of GINC (see
Fig. 5l).
To evaluate the efficiency of different burn rate enhancers
(iron oxide, nano-sized iron oxide, GINC), four different
propellant compositions based on AP/HTPB/Al were processed
(see Table S4 in ESI†). Burn rate enhancers were added at a
concentration level at 1 weight% over the batch in three
formulations. The theoretical performance of the formulations
containing graphene, iron oxide, nano-sized iron oxide and
GINC was computed using NASA CEC-71 (see Table S4 in ESI†).
From Table S4 (see ESI†), it was observed that the ame
temperature (Tf), C*, and specic impulse (Isp) were decreased
due to the incorporation of burn rate enhancers. The overall
percentage of inert material increased, which was reected by
the predicted theoretical data.
During processing, marginal increase in mixture viscosity of
CP-2 propellant composition (containing 1 wt% GINC over the
batch) was observed with respect to base composition. For
Fe2O3 and nano-sized Fe2O3, the viscosity of propellant mix
signicantly increases, which creates a processing problem (see
Fig. 6a).
The strand burning rate experiments were conducted in a
pressure range of 5–10 MPa, and the base composition
exhibited a burning rate of 6.7–9.5 mm s
1 (see Table S6 in
ESI†). The addition of GINC leads to a 30–40% enhancement
in the burning rate of the propellant composition. Other
burn rate enhancers, such as micron size Fe2O3 and nano-
sized Fe2O3, also increased the burning rate. However, the
rate of increase with GINC was found to be maximum (52%
increase) compared to other compositions. Though the
burning rate of GINC containing composition was consider-
ably higher compared to other compositions, the pressure
exponent was found to be relatively low, which is the most
desirable43 condition for composite propellants (see Fig. 6d).
Indeed, for missiles, composite propellant burns at pressure
ranges of 5–10 MPa. At this pressure range, shiing of n value
was not observed. Beyond these pressure ranges, i.e. at 60–70
MPa, marginal variation in the pressure exponent can be
observed. Along with this, a propellant composition con-
taining soot-based iron oxide has been processed, and the
burn rate was measured at a pressure of 70 MPa. In this
experiment, we have maintained the moisture level less than
0.01%, and further enhancement of burn rate was not
observed due to the presence of soot. The results are also
supported by one of the works reported in contemporary
literature.44
All of the propellant formulations containing different burn
rate modiers were marginally more sensitive to impact and Fig. 6 Comparative bar diagram of (a) viscosity, (b) UTS, (c) peak
temperature in DTA, and (d) burn rate of propellant.
friction as compared to the base composition (see Table S4 in
ESI†). The sensitiveness may be attributed to the presence of the
burning rate enhancer in contrast to AP. 3: binder (15%) + Al (17%) + AP (68%) + burn rate enhancer
CP-1: binder (15%) + Al (17%) + AP (68%) + burn rate (nano-sized Fe2O3)
1 wt% over the batch; and CP-4: binder
enhancer (Fe2O3)
Nil; CP-2: binder (15%) + Al (17%) + AP (15%) + Al (17%) + AP (68%) + burn rate enhancer (micron-sized
(68%) + burn rate enhancer (GINC)
1 wt% over the batch; CP- Fe2O3)
1 wt% over the batch.

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Paper
Table S5 (see ESI†) shows the DSC, STA results of four
compositions containing burn rate enhancer. In the presence of
GINC, peak temperature decreases up to 44  C, which mainly
governs the catalytic efficiency. For Fe2O3 and nano-sized Fe2O3,
peak temperature decreases up to 34  C. Note that graphene as a
substrate increases the electron transfer process; hence, cata-
lytically enhanced heat is released by two fold. In the presence
of graphene, catalytic activity of nano-sized Fe2O3 increases
tremendously.
These results are also supported by the activation energy
calculation through Kissinger Ozawa equation. DTA results also
agree with the above nding. TGA results showed that with the
GINC based composition (CP-2), weight loss started at 230  C,
which was approximately 20  C lower compared to other
compositions (see Fig. 6c). TGA data were measured between
50  C and 400  C. At this temperature range, 25% residual
materials were present. With increases in temperature, i.e.
beyond 400  C, residual material also gets burnt and forms a
gaseous product.
Thermophysical properties were also highlighted in Table
S5 (see ESI†). CP-2 showed the lowest thermal
expansion coefficient (81.4  10
6/C at 30  C), indicating
better structural integrity of propellant grain with tempera-
ture. Thermal conductivity of CP-2 was found to be higher in
comparison to other compositions. Due to the presence of
GINC, thermal conductivity was increased with decrease in
curing time.
The mechanical properties (see Table S4 in ESI†) were eval-
uated for all the four compositions. Only marginal changes in
the properties (TS, %E and E modulus) were observed between
base composition (TS: 10.5 ksc, %E: 43%, E modulus: 45 ksc)
and CP-2 (TS: 10.0 ksc, %E: 36.1%, E modulus: 52 ksc). In the
case of GINC formulation (CP-2), elongation is reduced by 17%
with respect to CP-4. If we look at two other mechanical
parameters, i.e. tensile strength and modulus, it is found that
GINC formulation (CP-2) has higher TS and modulus compared
to CP-4. Elongation can be maintained in CP-2 with respect to
CP-4 by two ways: either by tailoring NCO/OH ratio with
decrease in NCO/OH ratio or by increasing the quantity of chain
extender (n-butane diol).
For other two compositions (CP-3 and CP-4), mechanical
properties (TS and modulus) signicantly degraded. This was
due to the addition of non-reinforcing ller, such as Fe2O3,
which reduced the mechanical properties (see Fig. 6b).
3.1 Mechanism of thermal decomposition of AP
A number of studies were carried out to realize the decom-
position mechanism of AP45–50 and they provide
good accounts of the probable decomposition mechanism of
AP; moreover, numerous mechanisms have been proposed,
but the decomposition mechanism of AP is still a debated
matter. Two probable mechanisms have been highlighted
here.
3.1.1 Electron transfer mechanism. In this mechanism, AP
decomposition follows a three step mechanism as proposed by
Song and Zhang:51
This journal is © The Royal Society of Chemistry 2015
RSC Advances
(1) In the rst step, the endothermic transformation
happens from the orthorhombic phase (low temperature) to the
cubic phase (high temperature).
(2) In the second step, the exothermic low temperature
decomposition process (LTD) of AP (300–330  C) takes place as
follows:
NH4ClO4 4 NH4+ + ClO4
4 NH3 (g) + HClO4 (g)
4 NH3 (s) + HClO4 (s)
(3) In the third step, the exothermic high temperature
decomposition process (HTD) of AP would take place (450–480

C), and the heterogeneous decomposition of deprotonized
HClO4 gas on the solid surface occurs.
According to the above experimental ndings, it can be
assumed that GINC accelerates both LTD and HTD. A probable
mechanism has been shown in Scheme 2.
For LTD, the gas and solid phase reactions occur simulta-
neously. During this process, dissociation and sublimation take
place52,53 as highlighted in the second step. For LTD, the
transfer of an electron from ClO4
to NH4+ should be the
controlling step, while for HTD, the controlling step is the
transformation from oxygen (O2) to superoxide (O2
). It is well
known that graphene exhibits several unique properties, such
as good conductivity, distinct electric eld effect with a charge
concentration as high as 1013 cm
3 and mobility54 as high as 1.5
 104 cm2 V
1 s
1. The movement of an electron in graphene is
considerably faster than in metal atoms and can reach an
effective speed of 300 times less than the speed of light in
vacuum and travel a large distance without deection.1 Hence,
the synthesized GINC used here helps to accelerate the elec-
trons to speed up the abovementioned controlling steps. In
other words, due to the accelerated electron ow provided by
graphene, NH4+ and ClO4
are transformed to NH3 and HClO4.
Next, HClO4 generates O2, which subsequently forms super-
oxide (O2
) more rapidly with the help of graphene as a perfect
bed for accelerated electron ow. These superoxide ions help to
decompose NH3 with other side products generated from HClO4
and ensure complete decomposition of AP.
In case of bare nano-sized iron oxide, no supporting
substrate is available; hence, it is more likely to form an
aggregate and render less active sites to adsorb a gas molecule
(NH3, HClO4) to accelerate the reaction. However, when
decorated on graphene, which is the best catalyst substrate
with the theoretical surface area10 of 2600 m2 g
1, the deco-
rated particles are able to unfold on the graphene substrate to
Scheme 2 Decomposition mechanism of AP in the presence of GINC.
RSC Adv., 2015, 5, 1950–1960 | 1957
RSC Advances
generate more active sites and react with NH3 of HClO4, and
hence accelerate the catalysis process. However, a marginal
difference was observed for the catalytic performance of 3%
and 5% GINC.
Similar to AP decomposition reaction, GINC also
enhances the burn rate of propellant. The enhancement was
found to be considerably higher when compared to the other
burn rate enhancers such as graphene, Fe2O3 (micron-sized),
and Fe2O3 (nano-sized). During the combustion of propel-
lant, AP decomposes as per the abovementioned mechanism.
Along with this, the combustion of propellant binder (HTPB
based) also occurs at a faster rate due to rapid electron ow to
the combustion step from the graphene substrate. Hence, a
higher burn rate of propellant was observed.
3.1.2 Proton transfer mechanism. Jackobs et al. have
proposed a scheme for the thermal decomposition of AP by
proton transfer mechanism (Boldyrev;55 Jacobs and Russell-
Jones56,57):
NH4ClO44NH4+ (a) + ClO4
(a) 4NH3 (g) + HClO4 (g)
This mechanism also consists of a three step mechanism.
Step I involves pairs of ions in a perchlorate ammonium lattice.
In Step II, the decomposition step starts with proton transfer
from the cation NH4+ to the anion ClO4
via a molecular
complex. This molecular complex decomposes into ammonia
and perchloric acid in Step III.
In this mechanism, NH3 and HClO4 molecules either react in
the absorbed layer over the surface of perchlorate or interact in
gas phase by desorption and sublimation. Several reactions
quickly occur in the gas phase between NH3 and HClO4, form-
ing O2, N2O, Cl2, NO, and H2O as side products at a low
temperature (<350  C).
A crucial feature of the AP decomposition mechanism is that
it occurs in pores beneath the surface at a distance of a few
microns. This is the basic difference between sublimation and
decomposition of AP.
In this mechanism, perchloric acid is desorbed more quickly
compared to ammonia;56,57 hence, it causes incomplete oxida-
tion of ammonia, creating a saturated atmosphere56,57 of NH3.
As a result, HTD decelerates and undergoes incomplete trans-
formation; moreover, during HTD, NO, O2, Cl2 and H2O prod-
ucts are produced in the gas phase reaction.
Both HTD and LTD have a common start, i.e. transfer of
proton from NH4+ to ClO4
anion. The difference between LTD
and HTD is only in the fact that a low temperature stage occurs
on crystal defects (topochemistry), whereas a high temperature
slow reaction proceeds in the lattice of the remaining normal
crystal. During LTD, orthorhombic modication proceeds in
the pores below the surface in the sites where secondary
dissociated product gets accumulated, and the sites where
active centre regeneration exists. This occurs due to the gener-
ation of pressure caused by gases formed in the pores or due to
perchloric acid decomposition and interaction of decomposi-
tion product with ammonia. This accumulation of reaction
product and the formation of new active centres are the main
1958 | RSC Adv., 2015, 5, 1950–1960
Paper
reasons for the decomposition of the orthorhombic
modication.
The scenario changes when high temperature is employed.
At this stage, the process takes place at the surface of the crystal.
Adsorption and desorption of ammonia and chloric acid take
place. Thus, the role of the primary process is connected with
proton transfer. By addition of dopant, changes the concen-
tration of the protons in the lattice during decomposition of the
cubic modication and stronger effect on ammonia. The
assumption formulated by Kaidymov and Gavazova58,59 is quite
relevant to mention.
It refers to the catalytic activity of the orthorhombic modi-
cation with respect to perchloric acid decomposition, which is
an important stage through which thermal decomposition
proceeds. Note that thermal decomposition is quite high
compared to the cubic modication. Hence, despite the
improvement in investigating the mechanism of AP decompo-
sition, the primary mechanism is still uncertain.
4. Conclusions
Graphene and nano-sized iron oxide were separately
prepared and characterized. GINC was successfully synthe-
sized by a one-pot, green synthesis method by using gra-
phene and nano-sized iron oxide as raw materials. It showed
excellent catalytic activity on the thermal decomposition of
AP and signicantly increased the burn rate of propellant.
The presence of nano-sized Fe2O3 reduces the
activation energy of propellant combustion, and graphene
helps to improve the ow of electrons, which can further
increase heterogeneous decomposition rate of deprotonized
HClO4 gas on the outer surface of the catalyst particle.
Lower catalyst concentration favours further decomposition
of AP. When GINC catalyst was used in lower concentration (1
weight%), the catalysis effect became cheaper.
These processes are convenient for further scale up. The
method of preparation of GINC highlighted in this paper can
be extended to other metal/graphene nanocomposites
used for AP and AP based composite propellant. Moreover, it
can be foreseen that graphene based metal/metal oxides
will be potential catalysts for AP based composite
propellants.
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1960 | RSC Adv., 2015, 5, 1950–1960 This journal is © The Royal Society of Chemistry 2015