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Defence Technology xx (2015) 1e8
www.elsevier.com/locate/dt

Tuning the particle size and morphology of high energetic material

nanocrystals
Raj KUMAR a, Prem Felix SIRIL a,*, Pramod SONI b
a
School of Basic Sciences and Advanced Materials Research Centre, Indian Institute of Technology Mandi, Mandi, 175005, Himachal Pradesh, India
b
Terminal Ballistics Research Laboratory, Sector-30, Chandigarh, 160030, India
Received 21 March 2015; revised 28 July 2015; accepted 30 July 2015
Available online ▪ ▪ ▪

Abstract

Morphology controlled synthesis of nanoparticles of powerful high energetic compounds (HECs) such as 1,3,5-trinitro-1,3,5-triazinane
(RDX) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) were achieved by a simple solventeantisolvent interaction (SAI) method at 70
C.
The effects of different solvents on particle size and morphology of the prepared nano-HECs were studied systematically. Particle size and
morphology of the nano-HECs was characterized using field emission scanning electron microscopy (FE-SEM) imaging. X-ray diffraction
(XRD) and Fourier transform infrared (FTIR) spectroscopy studies revealed that RDX and HMX were precipitated in their most stable poly-
morphic forms, i.e. a and b, respectively. Thermogravimetric analysis coupled with differential scanning calorimetry (TGA-DSC) studies
showed that the thermal response of the nanoparticles was similar to the respective raw-HECs. HEC nanoparticles with spherical and rod shaped
morphology were observed under different solvent conditions. The mean particle size also varied considerably with the use of different solvents.
Copyright © 2015, China Ordnance Society. Production and hosting by Elsevier B.V. All rights reserved.

Keywords: Nano-RDX; Nano-HMX; High energetic materials; Spherical nanoparticles; Nanorods; Morphology control

1. Introduction release can be controlled. They have found extensive use in

High energetic materials (HEMs) are rich sources of en-
ergy stored in the form of chemical bonds [1]. They are
thermodynamically unstable, but the kinetics of energy
Abbreviations: RDX, 1,3,5-trinitro-1,3,5-triazinane; HMX, 1,3,5,7-
tetranitro-1,3,5,7-tetrazocane; CL, 20-2, 4, 6, 8, 10, 12-hexanitro-2, 4, 6, 8,
10, 12-hexazaisowurtzitane; TATB, 1, 3, 5-triamino-2, 4, 6-trinitrobenzene;
ICDD, The International Centre for Diffraction Data; HMXb, Bulk-HMX;
HMXn, nano-HMX; Tm.p, melting point; Texo, exothermic peak temperature;
Tendo, endothermic peak temperature; DH, enthalpy change; Tid, initial
decomposition temperature; Tfd, final decomposition temperature; Dmass,
mass loss; TBRL, Terminal Ballistics Research Laboratory; AC, acetone; EA,
ethyl acetate; EN, ethanol; MN, methanol; DMSO, dimethyl sulfoxide; DMF,
dimethylformamide; NMP, N-methylpyrrolidone.
* Corresponding author. Tel.: þ91 1905 207040; fax: þ91 1905 237942.
E-mail address: prem@iitmandi.ac.in (P.F. SIRIL).
Peer review under responsibility of China Ordnance Society.
explosives, rocket propellants and gas generators for auto-
mobile air bags [1,2]. Focus of research on HEMs has
recently been to synthesize novel molecules with high energy
density combined with insensitivity to hazardous stimuli
[1,2]. Unfortunately, the research and development of new
HECs has been very slow. RDX and HMX, which were
developed many decades ago, are still being used as the main
explosives due to their technological-economical character-
istics such as their ready availability in large scale [2].
Powerful explosives such as CL-20 and octanitrocubane have
much higher energetic performance than RDX and HMX
[2,3]. But, their sensitivity to accidental stimuli is a matter of
concern. Sensitivity of explosives is related to their chemical
as well as physical characteristics [4]. The physical properties
such as crystal size, shape, morphology, purity, inclusions and
crystal defects can be altered to improve the performance of
existing explosives [5,6]. Previous studies reported that the

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(2015), http://dx.doi.org/10.1016/j.dt.2015.07.002
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2 R. KUMAR et al. / Defence Technology xx (2015) 1e8
novel behaviour in deflagration to detonation transition was
observed with submicron particles [7]. A few studies have
indicated that the particle size of explosives influences the
impact sensitivity and maximum energy output from a deto-
nation [8]. Thus, the preparation of micrometer or sub-
micrometer sized solid particles is of great interest in
explosives.
However, the limited production strategies are only
available for making organic nanoparticles in general
compared to the large array of methods that are available for
the preparation of inorganic nanoparticles. Some of the
methods for the preparation of sub-micron sized HEMs in-
cludes rapid crystallisation from solvent by the addition of
antisolvent [9,10], solegel method [11,12], rapid expansion
of supercritical solution (RESS) [13,14], mechanical milling
[15e17] and aero-sol method [18]. An excellent review on
the various methods for the preparation of nanoenergetic
materials was published recently [19]. Unfortunately, many
of these techniques proved to be less attractive in large scale
production of organic nano-sized materials. Among various
techniques for the reduction of particle size, the antisolvent
precipitation process is a simple and effective technique to
produce the nanosized particles by introducing the organic
solution containing an active substance to the antisolvent
(e.g. water) that is solvent-miscible under rapid mixing,
which generates high supersaturation leading to fast nucle-
ation rates [20e25]. Instantaneous precipitation occurs by a
rapid desolvation of the hydrophobic active ingredient in the
antisolvent medium [26e29]. The antisolvent may contain
hydrophilic stabilizers such as polymers or surfactants. The
hydrophilic stabilizer in the antisolvent gets adsorbed on the
particle surface to inhibit particle growth [20e25]. We have
recently prepared nano-HECs by a simple evaporation
assisted solvent-antisolvent interaction (EASAI) method
using acetone as solvent at 70
C [26,27]. The same method
was also used to prepare nanodrugs [28,29]. It has been
shown that the particle size can be controlled by varying a
number of experimental parameters such as the concentra-
tion, ratio of solvent to antisolvent, temperature of the
antisolvent during injection, stirring speed etc. Infact, a lot
more experimental parameters such as ultrasonication,
nozzle geometry, mixing rate, nature of solvent and nature of
antisolvent also are known to affect the particle properties
[30]. Although there has been some studies on the effect of
many of these experimental parameters, only very few re-
ports are there in the literature about the effects of different
solvents on particle size and morphology of HECs. Here we
demonstrate that particle size and even morphology of nano-
HECs can be tuned by changing the solvent using the SAI
method.
2. Materials and methods
2.1. Materials
RDX (98.2%) and HMX (99.1%) were prepared in an in-
house facility using Bachmann process [31]. Solvents,
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dimethylsulfoxide (DMSO), dimethyl formamide (DMF),
ethyl acetate (EA), N-methyl-2-pyrrolidone (NMP), methanol
(MN) and ethanol (EN) were purchased from Sigma Aldrich
and used as received. Ultra-pure water (18.2 MU-cm) from
double stage water purifier (ELGA PURELAB Option-R7)
was used throughout the process of preparation. HPLC
micro syringe was purchased from Hamilton, USA. Syringe
filter with pore size of 0.22 mm was purchased from Millipore,
USA. Whatman Anodisc® 25 filter with pore size of 0.02 mm
was purchased from Sigma Aldrich, India.
2.2. Preparation of RDX and HMX nanoparticles
Solution of HECs (5 mM) in different solvents was pre-
pared by adding accurately weighted amount of HECs. The
solution (100 ml, 5 mM) was quickly injected into water
(25 ml) as antisolvent at 70
C under magnetic stirring using
an HPLC micro-syringe to precipitate nanoparticles. The so-
lution of HECs was always filtered using a syringe filter with
pore size of 0.22 mm before injection to ensure that no particle
was present in it. The nanoparticles were collected by filtration
using Whatman Anodisc® 25 filter membrane
(diameter ¼ 25 mm and pore size ¼ 20 nm). The membrane
was dried in an oven at 40
C for 24 h to collect the sample for
further characterization.
2.3. Particle size and morphology
Accurate particle size and morphology of the prepared
nanoparticles were observed using an FESEM (Zeiss FEI
Quanta FEG 450 and Supra 55 VP model). The suspension of
RDX and HMX nanoparticles in water was drop-coated on an
1 cm2 glass slide and dried. The dried sample containing the
glass slide was kept on a clean aluminum stub that was
covered with carbon tape. The sample was subsequently
sputter-coated with gold at 20 mA for 180 s before the FESEM
observation. Particle size of more than 300 nanoparticles from
different FESEM images that were taken from different re-
gions of the sample was calculated in each experimental
condition using Image J software.
2.4. FTIR spectroscopy
FTIR spectroscopy was performed using the Perkin Elmer
FTIR emission spectrometer (Spectrum Two). The FTIR
spectra of raw and nanoparticles of RDX and HMX were
recorded in the frequency range from 4000 to 600 cm1 with a
resolution of 4 cm1. The samples were properly grounded
with KBr powder and then pressed to obtain a suitably sized
pellet for FTIR spectrum measurement. Pure KBr pellet was
used for background correction.
2.5. Powder X-ray diffraction (XRD)
XRD patterns were recorded on a smart lab X-ray
diffractometer (Rigaku, Japan) using Cu Ka radiation as X-ray
source (l ¼ 0.15418 nm) at room temperature. The voltage
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R. KUMAR et al. / Defence Technology xx (2015) 1e8 3

and current applied were 45 kV and 100 mA, respectively.
The samples were placed on a scorch tape and scanned at 2q
from 10
to 70
at a scan rate of 2
/min1 with a step size
of 0.02
.
2.6. TGA-DSC
TGA-DSC analyses were carried out by using Netzsch STA
449 F1 Jupiter instrument. Small amount of the sample
(2e3 mg) was taken in a standard alumina pan with an
alumina lid with a pin hole at the middle. An empty crucible
was used as reference. The samples were heated from room
temperature to 500
C at a heating rate of 5
C/min1 under
nitrogen atmosphere with the flow rates of 60 ml/min1 pro-
tective gas and 40 ml/min1 purge gas.
3. Results and discussion
The nanoparticles of RDX and HMX were precipitated
immediately on the injection of their respective solution into
antisolvent (water). Stirring was continued up to a few mi-
nutes after the injection to complete the mixing to precipitate
smaller particles with narrow size distribution [30].
Precipitation of the HECs did not produce any turbidity due
to the tiny size as well as the very low concentration of the
particles. However, the particles could be detected using
DLS. Precipitation was performed from a number of different
solvents in order to study the effects of solvents on the size
and shape of nanoparticles. While varying the solvents, the
previously optimized experimental conditions for obtaining
small particles of RDX from acetone were used [26]. The
experimental conditions were: temperature (70
C), solvent
to antisolvent ratio (1:250) and concentration (5 mM) [26].
The particle sizes and morphologies of the prepared nano-
RDX and nano-HMX were studied using FESEM imaging.
The representative FESEM images of nano-RDX and nano-
HMX are given in Figs. 1 and 2, respectively. Average par-
ticle sizes were calculated from the FESEM images using
Image J software. The average particle sizes that were
calculated from FESEM images of solvents are listed in
Table 1.
3.1. Particle size and morphology
It is evident from Figs. 1 and 2 that the spherical nano-
particles with almost uniform particle sizes were formed in

Fig. 1. FESEM images of nano-RDX in different solvent conditions.

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Fig. 2. FESEM images of nano-HMX in different solvent conditions.

most of the conditions. However, the cubical and rod shaped are not listed in Table 1 as they were non-spherical. EA was
nanoparticles were formed when EA was used as the solvent. the least polar among all the solvents used in the present
This is a significant observation as the control of particle study. The miscibility of EA is the least with the antisolvent
morphology is usually difficult to achieve without any addi- (water), which may have resulted in significant reduction in
tives such as surfactants or polymers. The particle sizes of nucleation and growth of particles. Slow nucleation and
RDX and HMX nanoparticles prepared from EA as solvent growth led to the growth of particles into relatively larger
size.
From Table 1, it is clearly evident that the particle size
Table 1
depends on the nature of the solvent. Size of RDX nano-
Particle size measured from FESEM images of nano-HECs that were
precipitated from different solvents. Some physical properties of the solvents particles varied in the range from 38 ± 15 nm to
are also given. 331 ± 145 nm whereas size of HMX nanoparticles were in
Properties of solvents Particle size/(d$nm1) the range from 30 ± 7 nm to 385 ± 46 nm when they were
a precipitated from different solvents. Chung et al. [32] studied
Solvent Boiling P.I Miscibility with Nano-RDX Nano-HMX
point/
C water/(g$100 g1) the effects of solvents on the particle size of low molecular
weight organic compounds at 298 K. They concluded that
EA 76 4.4 8.7 e e
MN 65 5.1 100 208 ± 35 58 ± 18 both the solubility of compound and the polarity of solvent
EN 78 5.2 100 229 ± 18 78 ± 27 are the key factors determining particle size [32,33]. The
DMF 153 6.4 100 331 ± 145 385 ± 46 boiling point and miscibility of solvent with the antisolvent
DMSO 189 7.2 25.3 54 ± 23 368 ± 93 seems to be the deciding factors in controlling the particle
NMP 202 7.1 10.0 183 ± 68 68 ± 36
size of HMX nanoparticles with the exception of NMP.
ACb 56 5.1 100 38 ± 15 30 ± 7
a
Among the solvents having high miscibility (100%) with
P.I: polarity index; AC: Acetone.
b water, the particle size decreases with decrease in boiling
Data from Refs. [26,27].

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point. Reduction in particle size, when the precipitation is

evaporation assisted using SAI method, has been consistently
reported in Refs. [26e29]. Lower boiling point of the sol-
vents results in evaporation-assisted precipitation that leads to
the formation of large number of nuclei. Further growth of the
nuclei into large particles is not possible, as substantial
depletion of the HEC molecules in the solution takes place
during nucleation.
Unfortunately, any such generalization was not possible for
the observed variation in particle size with the change in
solvents for nano-RDX. There was no clear trend in the data
given in Table 1 to correlate the properties of the solvent with
the particle size of nano-RDX. This is because the nucleation
and growth at 70
C are expected to be an intricate interplay of
a number of dynamic factors, such as miscibility of the solvent
with the antisolvent, diffusivity, viscosity and solubility of
HECs, in the mixture of solvent and antisolvent [33]. Unfor-
tunately, many of these factors are not precisely known for the
studied system to make any meaningful correlation.
Fig. 3. FTIR spectra of prepared nano-HECs and raw-HECs.

3.2. FTIR
nanoparticles prepared by SAI method were also crystalline.
The crystal structure of RDX is well known to have at least 5
FTIR spectroscopy was used to determine the chemical
different polymorphs: a, b, g, d and ε. The a-form is the most
compositions of RDX and HMX before and after the anti-
stable one at room temperature (orthorhombic, a ¼ 1.3182,
solvent precipitation. The FTIR spectra of raw-HECs are
b ¼ 1.1574 and c ¼ 1.0709 nm) [39,40]. HMX crystals can
shown in Fig. 3 along with the spectra of the prepared nano-
exist in one of the four different polymorphs: a (ortho-
HECs. It is clearly evident from Fig. 3 that nano-RDX sam-
rhombic), b (monoclinic), g (monoclinic) and d (hexagonal)
ples have similar IR bands as bulk-RDX. The major bands for
phases. Among these, b-HMX is highly dense and is the most
the RDX samples were as follows: 1592 cm1 (ns NO2),
stable at room temperature (monoclinic, a ¼ 0.65370,
1270 cm1 (ns NO2 þ n NeN), 1039 cm1 (ring stretching
b ¼ 1.10540 and c ¼ 0.87018 nm) [41e43]. The XRD patterns
bands), 945 and 783 cm1 (d NO2 and gNO2) and 604 cm1
of all the RDX and HMX samples showed similar patterns
(t þ g NO2). Two peaks were observed for all the RDX
corresponding to a-RDX and b-HMX, respectively
samples at 736 and 754 cm1, as highlighted in Fig. 3. Peaks
[8,39,44,45]. The diffraction peaks of all the RDX samples at
in the range of 700e760 cm1 are characteristic of a-poly-
2q ¼ 13.1
, 13.4
, 15.4
, 17.4
, 17.8
, 20.4
, 22.0
, 25.4
and
morph form of RDX, and there are no peaks in this range for
29.3
confirmed that the RDX samples were in a-polymorphic
b-RDX [34]. Similarly, the major IR bands that were observed
form [JCPDS PDF#44e1618] [46]. The diffraction peaks of
for the nano-HMX samples matched well with the raw-HMX
all the HMX samples at 2q ¼ 14.7
, 16.0
, 23.0
, 26.1
, 29.6

[35,36]. The major IR bands for HMX samples were assigned
as follows: 1564 cm1 (ns NO2), 1145 cm1 (ns NO2, n ring),
964 cm1 and 946 cm1 (ring stretching bands), 830 and
761 cm1 of (d and g NO2), 625 and 600 cm1 (t þ g NO2).
No peak was observed in the FTIR spectrum of HMX in the
range of 700e750 cm1 as marked in Fig. 3. This indicates
that all the HMX samples were in the b-polymorph form
[37,38]. Additionally, it can be concluded that SAI method
does not lead to any change in chemical structure or crystalline
nature of RDX and HMX.

3.3. Powder X-ray diffraction (XRD)

XRD was performed to ascertain the crystalline state of the

nano-HECs. XRD patterns of the nano-HECs are shown in
Fig. 4 along with the diffraction pattern of raw-HECs. The
XRD patterns of the nano-HECs show the presence of
numerous distinct peaks showing the crystalline nature of the
samples. The XRD patterns of raw-HECs matched well with
the nano-HECs. This clearly indicates that the HMX Fig. 4. XRD of prepared nano-HECs and raw-HECs.

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and 31.9
confirmed that the HMX samples were in b-poly- Table 2
morphic form [JCPDS PDF#44e1620] [47]. Phenomenological TGA-DSC data of nano-HECs along with raw-HECs.
Solvent used Nano-RDX Nano-HMX



3.4. TGA-DSC Tonset/ C Td/ C Tspt/
C Td/
C
EA 202.0 229.7 190.9 274.3
The thermal properties of energetic compounds are MN 201.7 229.8 191.2 277.7
important characteristics as the initiation of HECs is intrinsi- EN 201.5 230.2 181.9 272.2
cally related to the thermal properties. TGA-DSC thermal DMF 201.6 230.5 189.4 277.1
DMSO 201.7 229.0 180.2 277.3
curves of raw and nano-HECs are shown in Fig. 5. The pho- NMP 201.0 230.3 184.3 273.8
nomenological data of raw-HECs along with the prepared AC# 202.8 230.0 188.0 279.0
nano-HECs are summarized in Table 2. The overall thermal Raw 201.0 230.5 186.0 277.0
response of the nano-HECs was very much similar to that of # Data from refs. [26,27].
the raw-HECs. RDX melts initially and then decomposes to
give gaseous products. Melting of RDX was registered as an from b to d phase [49e52]. Exothermic thermal decomposi-
endothermic event at around 202
C in the DSC thermal tion leading to almost complete mass loss was observed for all
curves. Rapid mass loss follows after melting. Almost 100% the HMX samples after 270
C. This result is also similar to
mass loss was observed in TGA thermal curves with a the characteristic thermal response of HMX which is reported
simultaneous exotherm in DSC thermal curves. These thermal in Refs. [52,53].
events are typical of raw-RDX that was recorded under similar
experimental conditions [48]. The DSC thermal curves of raw- 4. Conclusions
HMX and the nano-HMX samples showed an endotherm at
around 190
C. This corresponds to solid state phase transition The particle sizes and shapes of nano-RDX and nano-
HMX can be controlled using SAI method by changing the
solvent without affecting the chemical structure and crystal
morphology. Particle morphology was spherical when RDX
and HMX were precipitated from all the solvents studied
using SAI method; except from EA. Poor miscibility of EA
with water led to the formation of rod-shaped nanoparticles.
Any meaningful correlation of solvent properties with the
particle size of RDX was difficult to achieve. Overall thermal
response of nano-RDX and nano-HMX was more or less
similar to those of the raw-RDX and raw-HMX from which
they were prepared. However, the boiling points and mis-
cibilities of solvents with water emerged as the key factors
controlling the particle size of HMX nanoparticles using SAI
method.

Acknowledgements

Thanks are due to IIT Mandi for providing laboratory fa-

cilities. Financial assistance from ARMREB (DRDO) under
grant No. ARMREB/CDSW/2012/149 and research fellowship
to Mr. Raj Kumar from UGC are gratefully acknowledged. Mr.
Sudhir Scarlch, NIT Hamirpur and Dr. Kenny Pandey, (So-
phisticated Instrument Centre) IIT Indore are also thanked for
FESEM imaging.

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Please cite this article in press as: KUMAR R, et al., Tuning the particle size and morphology of high energetic material nanocrystals, Defence Technology
(2015), http://dx.doi.org/10.1016/j.dt.2015.07.002