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Graphene-Iron Oxide Nano Composite (GINC): An Efficient Catalyst

for Ammonium Perchlorate (AP) Decomposition and Burn Rate
Enhancer For AP based Composite Propellant
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RSC Advances Accepted Manuscript

5 Abhijit Deya*, Javaid Athara, Pankaj Varmaa, Hima Prasanta, Arun K.Sikder a*, Santanu Chattopadhyayb*

Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x

A facile and ecofriendly method for synthesis of nano size iron oxide (Fe2O3) decorated graphene (GINC) hybrid by the use of
ultrasonication via microwave irradiation has been developed. During this process, nano size Fe2O3 particles with a size of approximately
10 20-30 nm were decorated uniformly over graphene sheet. The nano hybrid was characterized by XRD, HRTEM and Raman spectroscopy
and mapping. To study the enhancement of catalytic activity of iron oxide by making 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
catalyst with 1-5 weight % concentrations were also prepared and evaluated. Experimental results showed that GINC with 5 weight %
concentration was much more effective as compared to other compositions. To extend this application further as a burn rate enhancer in
15 composite propellant, several formulations of composite propellant containing 1 part of different burn rate enhancers like Fe2O3, nano
size Fe2O3 and GINC were made and evaluated by means of 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 burn rate of propellant increases from micron size Fe2O3 (30%
increases) to nano Fe2O3 (37% increase). In the presence of GINC, a significant increase (52%) in burn rate is achieved. In GINC,
20 effective iron content is about 50% as compared to nano and micron size Fe2O3. Hence GINC was found to be excellent burn rate
modifier for advance AP based propellant system.

1. Introduction Due to the excellent properties with large surface area,

Graphene is a special type of carbon having a flat sheet graphene nanosheets (GNs) with a 2D geometry have been
25 with just one atom thick. It catches the great attention in recent considered as a new class of promising materials for prospective
time due to the unique feature like electrical, optical, catalytic and applications in solar cells, actuators, sensors, field-effect
mechanical properties. The nanosheet of graphene shows very 50 transistors, field-emission devices, batteries and super capacitors
1-9
high electrical conductivity at room temperature due to high . Besides this, the production cost of graphene is much lower
mobility of electrons. Graphene was discovered in 2004 by Andre than that of CNT10-11. Hence large scale production is feasible. Li
30 Geim and Konstatin Novoselov. They obtain graphene sheet by et al. 12 has mentioned a facile approach to synthesize graphene
splitting graphite crystals into increasingly thinner particle until materials. It opens up tremendous opportunity for various
individual atomic planes were reached. This remarkable 55 technological applications. Graphene is composed of sp2
contribution was felicitated by Noble prize in physics in 2010 and hybridized carbon atoms and has a honeycomb structure13-16. A
led to a sudden increase of research interest in graphene1-2. thorough review by Noorden17 on different carbon nanostructure
35 Graphene is the mother form of all the graphitic forms. concluded that research interests on fullerene and carbon
It is a building unit for carbon nano structures of all other nanotube become saturated but the increased research interest
dimensionalities. For example 0D Bucky balls, 1D nanotubes and 60 may be expected for graphene in the next decade.
3D graphite. It has a lot of similarities to carbon nanotube (CNT) Recently, Graphene sheets have been successfully used
like structure, properties with high aspect ratio (i.e. Lateral as a substrate which helps to stabilize and dispersed nano particle
40 size/thickness), large surface area, good mechanical properties (CdS, CdSe, Fe3O4,TiO2, SnO2, Co3O4 etc.)18-24 . This dispersion
and rich electronic state. It has lots of scope in different areas along with stabilization of nano particle helps to enhance
where CNTs have been already exploited. Graphene is a better 65 catalytic activity. Hence, it is required to be synthesized by facile
electrode material compared to CNTs. The 2D planar geometry of and environmentally benign techniques.
graphene sheet assists electron transport. Table S1 (see ESI) The metal/metal oxide particles have got much
45 depicts some properties of graphene as compared with CNTs. attention due to their distinctive optical, electronic and catalytic
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properties25-26. Transition metal particles (Fe, Co and Ni) and Then, GINC was prepared by ultrasonication through microwave
metal oxides (Fe3O4, TiO2, SnO2, Co3O4 etc.) have distinctive irradiation and characterized. The comparative study of GINC’s
catalytic nature. These have been widely used to make a new 60 catalytic effect within the AP decomposition reaction was
class of nanocomposite by decorating CNT. These investigated. Along with this, catalytic performance with a
5 nanocomposites show enhancement of catalytic behavior. On the variety of concentrations were also evaluated and optimized.
other hand, relatively less attention has been given to Several propellant compositions with different burn rate modifier
metal/metal oxide nanoparticles supported on graphene sheet.27-29 (1 part) i.e. normal Fe2O3, nano Fe2O3, GINC and a blank sample
Iron oxide is a very good magnetic material that has been 65 were processed and evaluated by strand burn rate data,
broadly used in magnetic storage, microwave absorbing simultaneous thermal analysis (STA), differential scanning
10 materials, catalyst and new devices. Raw iron oxide is a good calorimetry (DSC) and activation energy calculation.
burn rate enhancer in ammonium perchlorate based composite 2. Experimental Section
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propellant. When nano size iron oxide was used in the 2.1 Synthesis procedures

RSC Advances Accepted Manuscript

composition, catalytic activity increases as per the reported 70 All the chemicals used were analytical grade and used
journal30. We hope that Fe2O3/graphene nanocomposite(GINC) without further purification. Graphite flakes used in this work
15 can make a possible synergistic effect or a combination of the were purchased from Reinste nano ventures, India. The graphene
properties of the two components (graphene sheet and Fe2O3) in was prepared in three steps reported in the literature36. In the first
the new composite materials that imparts unique feature for step, graphite oxide was prepared from graphitic flakes by
catalysis and nanotechnology. 75 Hummers method37 In the second step, thermally expanded
To evaluate the effect of GINC in AP based composite graphene oxide (TEGO) was prepared by thermal
20 propellants, several compositions were processed. Composite expansion/exfoliation at 1050 ºC (Ar, 30s). Finally, graphene
propellant mainly consists of two parts i. e. HTPB based binder nanosheet (GNS) was obtained by hydrogen reduction of TEGO
and oxidizer. AP is generally used as workhorse oxidizer. The at 400 ºC for 2 hours.
burn rate is one of the vital property for composite propellant. For 80 Synthesis of nano iron oxide consists of two steps viz.
strategic reason, propellant with different burn rate were required preparation of polymeric gel citrate followed by gel calcination.
25 to be processed for different missiles. From ultra low burn rate (r Gel preparation was carried out in gel preparation unit and
≤ 3 mm/s at 70 ksc) to very high burn rate propellant (r ≥ 50mm/s calcination carried out in calcination unit i.e. muffle furnace. A
at 70 ksc) were processed and used in different missile systems. typical batch operation was as follows: solid citric acid and ferric
As shown in the many studies, the reaction rate, activation energy 85 nitrate nonahydrate were dissolved in ethylene glycol, in the
and temperature of the thermal decomposition of propellant are dissolution vessel to get a brown color solution. The solution was
30 closely related to the burn rate of the composite propellants. The slowly heated to 90°C by circulating hot thermic fluid (silicone
lower the decomposition temperature, the higher will be the oil) in the reactor jacket. An initial exothermicity was observed at
burning rate of propellant31-33. The burn rate enhancing effect of reaction temperature ~100°C with evaluation of NOx fumes
some transition metal oxides in different composite propellant 90 which was controlled by stopping the circulation of hot thermic
have been widely used. The outcome shows that the final fluid in the reactor jacket. However exothermicity subsidies
35 decomposition temperature of composite propellant directly during the rest of the reaction period. Then the hot oil circulation
depends on added amount of burn rate catalyst as well as the was started with the reactor jacket and temperature of reaction
particle size of the burn rate enhancer are all important factors mass was increased from 100°C to 140°C. Water molecule
which affect the decomposition temperature of the propellant. It 95 evolved during the reaction was condensed by condenser using
is well proven that nano size catalyst is more effective as chilling water circulation in the tubes. Uncondensed gases were
40 compared to the micron size catalyst34, 35. It is also known that scrubbed by venturi scrubber. After collection of ~3.5L
nanoparticles are able to agglomerate due to their small size, large condensate, the polymeric gel was prepared. Then, it kept in the
surface area, and high surface activity. It affects greatly to the muffle furnace. The gel was first dried at 300°C for 2 hrs. under
catalytic behavior. However, the agglomeration makes 100 oxigen rich atmosphere by purging compressed air. Evolve gas
inhomogeneous dispersion of nano catalyst. Hence, reduced were exhausted through a chimney by ID fan. Then dried gel was
45 catalytic efficiency was observed, which leads to increase the calcined at 600°C for 6 hours to get pure nano α Fe2O3.
practical cost of the catalyst. Graphene has a very large surface For making GINC, 50 mg graphene was first
area of nanoparticle to disperse and distribute on. It has many dispersed in absolute ethanol by ultrasonication for 40 min. After
more important properties like low mass density, good thermal 105 ultrasonication, nano iron oxide was added into the graphene
stability, chemical inertness and high electrical and thermal dispersion and further ultrasonication was continued for 120 min.
50 conductivity (see Table S1). After ultrasonication, the dispersed composite solution kept in
Herein, we have highlighted (see scheme 1) a simple, ambient condition for drying. After evaporation of ethanol,
facile method of decoration of iron oxide nano particle over the material was deposited on the petri dish. The deposited material
graphene substrate. Presently, the catalytic behavior of transition 110 placed into the microwave reactor for 2 min for better exfoliation.
metal oxide decorated graphene nanocomposite in the propellant After cooling, the sample was collected in the sample vial (see
55 burning rate as well as thermal decomposition of AP has rarely scheme1).
been reported. In this connection, In this work, graphene and
nano iron oxide were prepared and characterized separately.

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Scheme 1: Synthesis, processing and application of GINC as burn rate modifier in missile system

5 To study the efficiency of catalytic behavior of GINC mixed in 10 kg batches using a vertical planetary mixer of 15 L
for AP decomposition, four different compositions with different capacity. During mixing, vacuum (2-3 tor) was applied at 55 °C,
catalyst like graphene, iron oxide (micron size and nano size) and in order to remove air bubbles from the formulation prior to
GINC with 1 wt. % concentration was made and characterized. casting. The propellant mixture was cast under vacuum by slurry
Composite Propellant processing 40 cast techniques38. The propellant was cured at 60 °C for 10-12
10 To evaluate the burn rate enhancing capability of GINC days in a water-jacketed oven. The base composition, without
with respect to other burn rate enhancer for composite propellant, burning rate enhancer, was also processed in the same manner.
several formulations (4 nos) were processed. Composite The propellant formulations were subjected to various
propellant consists of two parts, i.e. binder and solid ingredient. performance tests. The detail process flow chart was given in Fig.
The binder, consisting of hydroxy terminated polybutadiene, 45 1.
15 (HTPB: OH value 40-50 mg/g, moisture 0.15%, from Orion
Chemicals), was cured with toluene di-isocyanate (TDI: purity
99%, RI 1.565-1.567 at 30 °C; from Bayers). Dioctyl adipate
(DOA: saponification value 303 ±3, moisture 0.5%, from Subhas
Chemicals) was used as a plasticizer to increase the
20 processibility. Indigenously made GINC, nano iron oxide,
graphene and micron size iron oxide (from S. D. fine chemicals)
were used as a burning rate enhancer. The mixture (1:2) of
trimethylolpropane (OH value 1220, moisture 0.5%, :purchased
from Celenese) and butane-1,4-diol (OH value 1220, RI 1.444
25 ±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 formulations.
The first consisted of pure, research grade ammonium perchlorate
(purity 99%, density 1.95, from Tamilnadu chlorates) with an
30 average particle size of 300 µm. The other size of ammonium
perchlorate was made by grinding ammonium perchlorate (> 99%
pure) in a fluid energy mill to an average particle size of 60 µm. Fig. 1: Flow chat for the processing of composite propellant
Aluminum metal powder (from MEPCO) of average particle size 50
15 µm, was used as a metal fuel. The propellant formulation was 2.2. Characterizations
35 given in Table S3 (see ESI). The propellant formulations were 2.2.1 GINC characterizations
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Sonication was conducted by using ultrasonication bath drop weight) using the Bruceton Staircase method41 and the
(35 kHz, Kudos). Microwave irradiation was carried out by a results were given in terms of the statically obtained 50%
microwave reactor (make: Raga). Environmental scanning 60 probability of explosion (H50). The friction sensitivity was
electron microscopy (ESEM) was carried out with Quanta 200, measured with a Julius Peter apparatus by incrementally
5 FEI. High resolution transmission microscopy (HRTEM images, increasing the load from 0.2 to 36 kg, until there was an
SAED pattern) characterization was carried out by TACHNAI F- ignition/explosion in five consecutive test samples.
30, FEI with 300 kV field emission gun (FEG). Nano Fe2O3, The ignition temperature was measured by Julius Peters
graphene and graphene-iron oxide nanocomposite was dispersed 65 apparatus. The sample was heated uniformly at a constant rate (5
in methanol with ultrasonication. The dispersion was placed on °C/min) in a Woods metal bath, until it exploded or ignited at the
10 TEM grid. The Solvent was evaporated by oven drying. Fourier ignition temperature.
Transform Infrared Spectroscopy (FTIR) were collected by Thermo physical properties were also evaluated by
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Nicolet 5700, Thermoscientific. Raman traces and mapping were Flash line-3000, Anter corporation) Thermal analysis of the

RSC Advances Accepted Manuscript

measured by Invia reflex micro Raman, Renishaw. X-Ray 70 propellants was carried out by STA (Q-600,USA), Perkin Elmer
Diffraction traces were collected by X- Ray Diffractometer D8 Pyris Diamond DSC apparatus at a heating rate of 20 °C/min
15 advance, Bruker with Cu Kα source in the measurement angle under an N2 atmosphere (sample mass ~10 mg). The activation
range 2θ=2-90º with a scan rate 2º/ min. energy for propellant combustion was also determined with the
To evaluate the catalytic effect of GINC on AP help of DSC at different heating rate by following Kissinger
decomposition reaction thermo gravimetric analysis (TGA) and 75 Ozowa equation.
differential thermal analysis (DTA) were carried out by Mettler The mechanical properties were obtained with an Instron
20 Toledo, Model-TGA/SDTA851 with a heating rate 20ºC min-1 in device (Model TIC-1185, UK). The operating instrumental
a static nitrogen atmosphere with alumina reference material. parameters were always maintained constant; gauge length 25
Comparison with different burn rate enhancers like iron oxide mm, crosshead speed 50 mm/min. The stress and strain properties
(micron size), nano iron oxide and graphene with concentration 80 were determined using a dumbbell-shaped specimen as per
variation were also carried out. specification ASTM-D-638.
25 3. Results and discussion
2.2.2 Propellant characterization High resolution transmission electron microscopy
Before making actual composition, some important (HRTEM) and an selected area electron defraction (SAED)
ballistic properties like characteristic velocity (C*), Flame 85 pattern were carried out to inspect the quality of nano iron oxide
temperature (Tf) and Specific impulse (Isp) were calculated by decoration in the graphene layer. Fig. 2 shows, HRTEM
30 NASA CEC-71 software. micrographs with an SAED pattern of graphene, nano iron oxide
To study the effect of GINC in AP based composite and GINC. The results are confirmed that the size of nano iron
propellant, several important properties have been evaluated oxide and graphene are in the nano range. Graphene sheets were
during the course of propellant processing. During processing, 90 clearly visible. Both nano iron oxide and graphene were found to
viscosity is one of the important parameters. Viscosity of the be crystalline in nature as confirmed by SAED pattern. According
35 propellant mix. was characterized by Brookfield viscometer at a to Fig.2c, iron oxides nano particles were placed over the
40ºC. These measurements were carried out at one hour interval graphene sheet and forming nano composite. It shows nicely
up to 4-5 hrs. arranged lattice fringes in GINC
After completion of curing reaction, the strand burning 95 (I) (II) (III) (IV)
rate of the propellants was determined in the pressure range 5-9 (a)
40 MPa by employing an acoustic emission technique39, 40. The
methodology involved combustion of the strand (ignited by
means of a Nichrome wire) of dimensions 100×6×6 mm in the
nitrogen pressurized steel bomb. The acoustic signal generated
and the perturbations caused by the propellant deflagration were (b)
45 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%. (c)
50 Cal-val (make-) was carried out by bomb calorimeter
(make: Parr, Germany). The densities of propellant compositions
were determined by a Mettler density kit (density 1.432 g/cc, heat
of formation -565.8 kJ/mol). Toluene was used as a liquid.
Density = (weight of the sample/weight of the sample in
55 solvent) ×specific gravity of the solvent (toluene). Fig.2: HR-TEM image (I,II, III) and SAED pattern (IV) of (a)
The sensitivity to impact stimuli of the propellant nano iron oxide, (b) graphene, (c) graphene-iron oxide
compositions was determined with a fall hammer apparatus (2 kg nanocomposite (GINC).

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Fig.3 (a) shows FTIR spectrum, it confirms absence of calculated crystallite size of graphene nano sheet (GNS), nano
functional group and presence of low defect on graphene surface. 35 Fe2O3 were 28 nm, 38nm, respectively.
Along with this, the Raman traces of Fe2O3 were observed.
Raman Spectroscopy was used to examine the quality of
5 graphene sheet before and after nanocomposite formation by Fe2O3
above mentioned techniques. The most pronounced Raman traces
were D band at 1310 cm-1 corresponding to defect and G band
1575 cm-1 which corresponds to in plane vibration of sp2 carbon. Graphene
2D band at 2627cm-1, which is generated due to a two phonon
10 double resonance process, has also been observed. According to 40
the Fig. 3b, D band of graphite was weak, while graphene shows
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small D band. The lower intensity D band indicates the presence GINC

RSC Advances Accepted Manuscript

of a lower defect on graphene flakes. Coleman and Co worker
suggested42 that the defects are mainly present at the edges of the
15 flakes, the basal plane is found to be defect free. The I(D)/I(G) of Fig. 4: XRD traces of (a) iron oxide, (b) graphene (c) graphene
the GINC is increased by 2 times (0.993) with repect to pure 45 iron oxide nanocopmposite (GINC)
graphene (0.497). Several defects with sp2 domain were formed Table S2 (See ESI) depicts the thermal analysis results of AP and
during nanocomposite formation.. Fig. 3 (b) shows characteristic AP with 1 wt.% of different burn rate enhancers i.e. graphene,
raman signature. The decoration of nano iron oxide over GINC, nano Fe2O3, micron size Fe2O3 etc. The results shows that
20 graphene substrate was confirmed by Raman mapping (See Fig AP decomposes at lower temperature and gives higher ∆H value
3b). 50 in the presence of 1 weight % GINC as compared to other burn
Iron oxide Wed Oc t 09 11:24:1 5 2013 ( GMT+05:30)
80
(a) Fe2O3
60
rate enhancers. Hence, GINC was found to be a more efficient
40 catalyst for AP decomposition reaction. This was also supported
%T

20
by thermo gravimetric analysis data where 73.81% weight loss
43 0.7

0
51 5.0

-20 was observed in a temperature range of 224.7-384.5ºC. These

Graphene Iron o xide nano co mpos ite We d Oct 09 11:13:05 2013 (GMT+05:30)

90
GINC 55 temperature regions were relatively low when compared to other
%T 80 compositions. Further, the catalytic efficiency of GINC,
%T

70
graphene, nano iron oxide and normal iron oxide with
49 5.7
43 7

60
concentration variation (from 1, 3, 5 wt.%) were also studied. The
50 Pure Gr aphene W ed Sep 11 1 6:16:54 201 3 (GMT+05:3 0)

Graphene catalytic efficiency of all the burn rate enhancer were found to be
40 60 increased with concentration (see Fig. 5a to 5l).
%T

30 (a)

3500 3000 2500 2000 1500 1000 500

-1
Wavenumbers
Wavenumbers (cm-1) (cm )

(b)

I
(a.u) Graphene traces

(b)
-1
Raman shift(cm )
Fig.3(a) shows FTIR traces, it confirm the presence of low defect
25 content in graphene. Fig. 3(b) shows characteristic raman
signature. The decoration of nano iron oxide over graphene
substrate is confirmed by raman mapping. Fig.4 a, b, c depicts
the typical XRD pattern of nano iron oxide, graphene and GINC
from angle 0-100 degree. All the peaks were assigned to
30 crystallographic phases. XRD pattern of GINC (Fig.3c) showed
graphene peaks as well as nano Fe2O3 peaks. It was revealed that
during processing, the crystallographic phases of graphene and
iron oxide remains intact. According to the Scherrer equation, the

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(c) (h)
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RSC Advances Accepted Manuscript

(d) (i)

(e) (j)

(k)
(f)

(l)
(g)

5 10

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Fig 5: DTA traces of (a) AP, (b) AP with 1, 3, 5 % Graphene, (c) (a)
AP with 1, 3, 5 % Iron Oxide , (d) AP with 1, 3, 5 % nano iron
oxide, (e) AP with 1, 3, 5 % Graphene iron oxide nanocomposite
(GINC), TGA traces of (f) AP with 1, 3, 5 % Graphene (g) AP
5 with 1, 3, 5 % Iron Oxide, (h) AP with 1, 3, 5 % Nano iron
Oxide, (i) AP with 1, 3, 5 % Graphene iron oxide nanocomposite
(GINC). Comparative bar diagram of (j) HTD with different
compositions in DSC analysis, (k) ∆H, (l) Final temperature of
different compositions in DTA analysis.
10 DTA results also support DSC result. The final temperature i.e. Tf
was found to be lowest in case of GINC (see Fig 5l)
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To evaluated the efficiency of different burn rate enhancers (iron

RSC Advances Accepted Manuscript

oxide, nano iron oxide and GINC etc.), four different propellant
compositions based on AP/HTPB/Al, were processed (see Table- (b)
15 4 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 iron oxide and GINC was computed using
NASA CEC-71(see Table S4 in ESI). From Table 4 (see ESI), it
20 was observed that the flame temperature (Tf), C*, and specific
impulse (Isp) were decreased due to incorporation of burn rate
enhancers. The overall percentage of inert material get
increased, which was reflected by the predicted theoretical data.
During processing, marginal increase in mix. viscosity
25 of CP-2 propellant composition (containing 1wt.% GINC over
the batch) was observed with respect to base composition. For (c)
Fe2O3 and nano Fe2O3, the viscosity of propellant mix increases
significantly which creates processing problem (see Fig.6a).
The strand burning rate experiments were conducted in the
30 pressure range of 5-10 MPa, and the base composition exhibited a
burning rate of 6.7-9.5 mm/s (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 enhancer like micron
size Fe2O3 and nano Fe2O3 also increase the burning rate. But the
35 rate of increase with GINC was found to be maximum (52%
increase) compare to other compositions. Though the burning rate
of GINC containing composition was much higher than other
(d)
compositions, but the pressure exponent was found to be
relatively low which is the most desirable43 condition for
40 composite propellants (see Fig. 6d). Indeed for missiles,
composite propellant burns at pressure ranges of 5-10 MPa. At
this pressure range, shifting of n value was not observed. Beyond
these pressure range i.e. at 60-70MPa, marginal variation in
pressure exponent can be observed. Along with this, a propellant
45 composition containing soot based iron oxide has been processed
and the burn rate was measured at a pressure of 70 MPa. In this
experimentation, we have maintained moisture level less than
0.01%. Further enhancement of burn rate was not observed due to
presence of soot. The results are also support by one of the works 60
50 reported in contemporary literature44.
All of the propellant formulations containing different CP-1: Binder (15%)+Al(17%)+AP(68%)+Burn rate enhancer
burn rate modifier were marginally more sensitive to impact and (Fe2O3)- Nil, CP-2: Binder (15%)+Al(17%)+AP(68%)+ Burn
friction as compared to the base composition (see Table 4 in ESI). rate enhancer( GINC)- 1wt.% over the batch, CP-3: Binder
65 (15%)+Al(17%)+AP(68%)+Burn rate enhancer(nano Fe2O3)- 1
The sensitiveness may be attributed to the presence of the burning
wt. % over the batch, CP-4: Binder (15%)+Al(17%) +AP(68%)
55 rate enhancer in contrast to the AP. +Burn rate enhancer(Micron size Fe2O3)- 1 wt. % over the batch

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Fig. 6: Comparative bar diagram of (a) viscosity (b) UTS (c) (3) The exothermic high temperature decomposition
Peak temperature in DTA (d) burn rate of propellant. process(HTD) of AP would take place (450-480ºC). The
Table S5 (see ESI) shows the DSC, STA results of four heterogeneous decomposition of deprotonized HClO4 gas on the
compositions containing burn rate enhancer. In presence of solid surface is occured in the third step.
5 GINC, peak temperature decreases upto 44ºC, which mainly 65 According to the above experimental finding, it can be assumed
govern the catalytic efficiency. For Fe2O3 and nano Fe2O3, peak
that GINC accelerate both LTD and HTD. A probhable
temperature decreases upto 34 ºC. Graphene as a substrate
increase the electron transfer process. Hence, catalytically mechanism has been given in the scheme 2
enhance heat release by two fold. In presence of graphene, For LTD, gas and solid phase reaction, occur simultaneously.
10 catalytic activity of nano sized Fe2O3 increases tremendously. During this process, dissociation and sublimation take place 52,53
This results also supported by the activation energy 70 as highlighted in the second step. For LTD, the transfer of
calculation through Kissenger Ozowa equation. DTA results also electron from ClO4- to NH4+ should be the controlling step, while
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agree with the above finding. TGA results showed that GINC for HTD, the controlling step is the transformation from Oxygen

RSC Advances Accepted Manuscript

based composition (CP-2), weight loss started at 230ºC, which (O2) to superoxide (O2-). It is well known that graphene exhibits
15 was approximately 20 ºC lower than other compositions (see Fig. several unique properties like good conductivity, distinct electric
6c). TGA data were measured between 50°C to 400°C. At this 75 field effect with a charge concentration as high as 1013 cm-13 and
temperature range, 25% residual materials were present. With the mobility54 as high as 1.5 ×104 cm2V-1s-1. The movement of
increases of temperature i.e. beyond 400°C, residual material also elentron in graphene is much faster than in metal atoms and can
gets burnt and form gaseous product reach an effective speed 300 times less than the speed of light in
20 Thermophysical properties were also highlighted in a vacuum and travel large distance with out deflection 1. Hence,
Table 5 (see ESI). CP-2 showed lowest thermal expansion 80 the synthesized GINC used here, help to accelerate the electrons
coefficient (81.4×10-6/C at 30ºC) indicating better structural to speed up above mentioned controlling steps. In other ward, due
integrity of propellant grain with temperature. Thermal to accelerated electron flow provided by graphene, NH4+ and
conductivity of CP-2 was found to be higher in comparison to ClO4- are transforming to NH3 and HClO4. After that, HClO4
25 other compositions. Due to presence of GINC, thermal generates O2 which subsequently form superoxide (O2-) more
conductivity was increased with decrease in curing time. 85 rapidly with the help of graphene as perfect bed for accelerated
The mechanical properties (see Table 4 in ESI) were evaluated electron flow. These superoxide ion help to decompose NH3 with
for all the four compositions. Only marginal changes in the other side products generated from HClO4 and finishes the
properties (TS, %E and E modulus) were observed between base decomposition of AP totally.
30 comnposition (TS: 10.5 ksc, % E: 43%, E modulus: 45 ksc) and
In case of bare nano iron oxide, no supporting substrate is
CP-2(TS: 10.0 ksc, %E: 36.1%, E modulus: 52 ksc). In case of
GINC formulation (CP-2), elongation is reduced by 17% with 90 available, hence it is more likely tto form aggregate and rendering
respect to CP-4. If we look at other two mechanical parameters less active sites to adsorb gas molecule (NH3, HClO4) to
i.e. tensile strength and modulus, it is found that GINC accelerate the reaction. However, when decorated on graphene,
35 formulation (CP-2) having higher TS and modulus compare to which is the best catalyst substrate with the theoretical surface
CP-4. By two ways, elongation can be maintained in CP-2 with area10 of 2600 m2g-1, The decorated particles can able to unfold
respect to CP-4. These are: By tailoring NCO/OH ratio- with 95 on the graphene substrate to genertate the more active sites and
decrease of NCO/OH ratio or by increasing of quantity of chain
react with NH3 of HClO4, hence accelerates the catalysis process.
extender (n-butane diol).
40 For other two compositions (CP-3 and CP-4) However, the marginal difference was observed for the catalytic
mechanical properties (TS and modulus) degraded significantly. performance of 3% and 5% GINC.
This was due to the addition of non reinforcing filler like Fe2O3 Like AP decomposition reaction, GINC also enhances the burn
which reduced the mechanical properties (see Fig. 6b). 100 rate of propellant. The enhancement was found to be much
Mechanism of thermal decomposition of AP higher when compared to the other burn rate enhancer like
45 A number of studies were carried out to realize the decomposition graphene, Fe2O3(micron size), Fe2O3(nano size) etc. During
mechanism of AP45-50 those provide good accounts of the
combustion of propellant, AP dcomposes following the above
probable decomposition mechanism of AP. Numerous
mechanisms are proposed, but still it is a debated matter. Two mentioned mechanism. Along with this, the combustion of
probable mechanisms have been highlighted here. 105 propellant binder(HTPB based) also occur at a faster rate due to
50 Electron transfer mechanism rapid electron flow to the combustion step from graphene
In this mechanism, AP decomposition follows three stepped substrate. Hence, higher burn rate of propellant was observed.
mechanism as proposed by the Song and Zhang51
(1) In the first step, the endothermic transformation happens
from orthorhombic phase (low temperature) to cubic phase (high
55 temperature)
(2) In the second step, exothermic low temperature
decomposition process(LTD) of AP (300-330ºC) was take place
as follows
NH4ClO4 NH4+ + ClO4- NH3(g)+ HClO4(g)
60 NH3(s)+ HClO4(s) 110

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Scheme 2: Decomposition mechanism of AP in presence of 65 significantly. The presence of nano Fe2O3, reduces the activation
GINC energy of propellant combustion and graphene help to improve
Proton transfer mechanism the flow of electrons which can further increases heterogeneous
Jackobs et al. have proposed scheme for thermal decomposition decomposition rate of deprotonized HClO4 gas on the outer
5 of AP by proton transfer mechanism (Boldyrev55; Jacobs and surface of catalyst particle. Lower catalyst concentratin favours
Russel-Jones56, 57):
70 further decomposition of AP. When GINC catalyst was used in
NH4ClO4 NH4+ (a) + ClO4- (a) NH3(g)+ HClO4(g)
lower concentration (1 weight %), the catalysis effect arrive to
This mechanism also consists of three stepped mechanism. Step I
involves pair of ions in perchlorate ammonium lattice. In Step II, cheaper. These process is covinient for further scale up. The way
10 the decomposition step starts with proton transfer from the cation of preparation for GINC highlightd in this paper can be extended
NH4+ to the anion ClO4- via molecular complex . This molecular to other metal/graphene nanocomposites used for AP and AP
complex decomposes into ammonia and perchloric acid in step 75 based composite propellant. It can be foreseen that graphene
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III. based metal/metal oxide will be potential catalysts for AP based

RSC Advances Accepted Manuscript

composite propellants.
15 In this mechanism, NH3 and HClO4 molecule either react in the
absorbed layer over the surface of perchlorate or desorbed and
sublime interact in the gas phase. Several reactions occur quickly Notes and references
in the gas phase between NH3 and HClO4, forming O2, N2O, a
High Energy Materials Research Laboratory, Sutarwadi, Pashan, Pune-
Cl2, NO, and H2O as side products at low temperature (˂ 350ºC). 80 411021, India. Fax: (+91)-20-25869316; Tel: (020) 25912225; E-mail:
20 A crucial feature of AP decomposition mechanism is that it abhidey_bkn@yahoo.com (Abhijit Dey)
occurs in pores beneath the surface at a distance of few microns. ak_sikder@yahoo.com (Arun K. Sikder)
b
This is the basic difference between sublimation and Rubber technology centre, Indian Institute of Technology, Kharagpur
decomposition of AP. India.. Fax; (+91)-03222-255303; Tel: 91-9932790504; E-mail:
During this mechanism, perchloric acid is desorbed more quickly 85 santanu@rtc.iitkgp.ernet.in.
25 compared to ammonia56, 57. Hence causes incomplete oxidation of † Electronic Supplementary Information (ESI) available: [Table S1:
ammonia, creating a saturated atmosphere56, 57 of NH3. As a Comparison of important properties of graphene with CNT, Table S2:
Thermal analysis results with different burn rate enhancer with AP , Table
result, HTD decelerates and undergoes incomplete
S3:Approximate propellant compositions, Table S4: Physico-chemical
transformation. During HTD, NO, O2, Cl2 and H2O products are
90 properties with different burn rate suppressant in propellant composition,
produced in gas phase reaction. Table S5: Thermal analysis results with different burn rate suppressant in
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from NH4+ to ClO4- anion. The difference between LTD and different burn rate suppressant in propellant composition]. See
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10

5 Table of content:

15
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RSC Advances Accepted Manuscript

Development of a facile and ecofriendly route for synthesis of GINC, followed by characterization
20 and evaluation in propellants for missiles.

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