Defence Technology 13 (2017) 263e268

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Defence Technology
journal homepage: www.elsevier.com/locate/dt

Electrostaticspray preparation and properties of RDX/DOS composites

Jian Yao*, Jian Liu, Yong-xu Wang, Bin Li, Li-feng Xie
School of Chemical Engineering, Nanjing University of Science and Technology, Jiangsu, Nanjing 210000, PR China

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

Article history: A composite explosive based on 1, 3, 5-trinitro-1, 3, 5-triazinane (RDX) was prepared by electro-
Received 13 January 2017 staticspray method with dioctyl sebacate (DOS) as desensitizer. After preparation, the particle size and
Received in revised form crystal structure were characterized and chemical features, such as chemical bonds, functional groups,
31 March 2017
thermal decomposition parameters and mechanical sensitivity were investigated as well. In terms of the
Accepted 10 May 2017
morphologies of the composites, the particle sizes were in the range of 1e3 mm. Compared with RDX, the
Available online 10 May 2017
crystal types, chemical bonds and functional groups of the RDX/DOS composites were unchanged. The
activation energy of the composites was lower than that of raw RDX, and the 3wt % DOS composites had
Keywords:
RDX
the lowest activation energy. The impact sensitivity and friction sensitivity of the RDX/DOS composites
DOS were lower than those of raw RDX, and the 10wt% DOS composites had the highest H50 (125.9 cm) and
Electrostaticspray the lowest friction sensitivity (8%).
Composites © 2017 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://
Insensitive creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction energetic materials. In this work, RDX-based composites with DOS

The improvement in the energy of one explosive always brings
the increase in its sensitivity, which results to the development of
compound explosives. RDX is one of the common explosives with
great power and high mechanical sensitivity. How to reduce
sensitivity of RDX as well as maintain a high energy is a challenging
question [1e7]. DOS, an oily substance, can be used to coat RDX and
the excellent sensitivity of the RDX/DOS composites has been
proved [8,9]. In the production of RDX-based composite explosives,
it is common to combine RDX and DOS together with traditional
mixing method (mixing and stirring) [10e14], but the uniformity of
mixture cannot be maintained well and fundamental changes on
the characteristics of mixture components were never found. It is
meaningful to develop a new method to update the mixing process.
In this paper, we demonstrated the preparation of the RDX/DOS
composites by electrostaticspray method, which was used to break
molten liquid or solution into tiny droplets by the electrostatic field
force, had successfully been used to produce uniform nanometer-
sized particles [15e21]. However, insufficient researches had
been conducted into electrostaticspray method in the field of
* Corresponding author.
E-mail addresses: yaojian216@163.com (J. Yao), 1121270251@qq.com (J. Liu),
876002529@qq.com (Y.-x. Wang), wrilber@sina.com (B. Li), xielifeng319@sina.
com (L.-f. Xie).
Peer review under responsibility of China Ordnance Society.
were prepared by electrostaticspray. Furthermore, the properties of
the composites were characterized and analyzed in detail.
2. Materials and methods
2.1. Materials
Raw RDX (99.9%) was provided by Jiangsu Yongfeng Machinery
Co. Ltd.; DOS (AR, 97%) was provided by Aladdin Reagent
(Shanghai) Co. Ltd; acetone (AR, 99.5%) was provided by Shanghai
Lingfeng Chemical Reagent Co. Ltd.
2.2. Preparation of the RDX/DOS composites
RDX and DOS (1000 mg in total, and the mass ratios of F2604 to
RDX were 1:99, 3:97, 5:95 and 10:90, respectively) were dissolved
in acetone (25 ml) to form a solution. As shown in Fig. 1, the RDX/
DOS composites were prepared by electrostaticspray method. The
solution was sprayed in four injection syringes by the TYD01-02
Syringe Pump (Lead Fluid Ltd., China). The voltage was 19 kV,
which was provided by the high voltage direct-current power
supply (Dongwen High Voltage Power Supply (Tianjin) Ltd., China),
the flow rate of solution in the injection syringe was 1 ml h-1, and
the receiving distance was 10 cm. The composite particles were
collected on aluminum foils.

http://dx.doi.org/10.1016/j.dt.2017.05.002
2214-9147/© 2017 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
264 J. Yao et al. / Defence Technology 13 (2017) 263e268

(SEM) (FEI Ltd., America) with an electron beam spot of 2.0 and a
generator voltage of 15 kV.
The chemical bonds and functional groups were studied by
VERTEX70 fourier infrared spectrometer (FT-IR) (Bruker Ltd. Ger-
many) with the spectral area of 500e4000 cm
1.
The crystal structure was studied by the D8 advance X-ray
diffractometer (XRD) (Bruker Ltd. Germany) with Cu-Ka radiation
at a generator voltage of 40 kV and a generator current of 200 mA.
The scan range in 2q was from 10 to 60 .
The thermal decomposition properties of the composites were
studied by DSC1 differential scanning calorimeter (DSC) (Mettler
Toledo Ltd. Switzerland) with closed stainless steel crucibles and
about 0.7 mg of samples. The analysis was performed under a pure
nitrogen atmosphere (50 ml min-1) at the heating rates of 1, 2, 4, 10
K$min-1 and the temperature was tested from 160  C to 280  C.
Fig. 1. The experimental set up.

2.4. Tests of mechanical sensitivity

2.3. Characterization
The morphologies and sizes of the RDX/DOS composite particles
were studied by QUANTA 250 FEG scanning electron microscope
The impact sensitivity of the RDX/DOS composites was tested
with a sample mass of 30 ± 1 mg and a drop weight of 2 kg. Two
groups of each sample and 25 same samples from each group were
tested. The results were shown in terms of the critical drop-height

Fig. 2. The SEM images of raw RDX and the RDX/DOS composites.
 J. Yao et al. / Defence Technology 13 (2017) 263e268 265

Table 1
The relative mass ratios of the elements in the samples.

Samples The relative mass ratios/wt%

C N O

raw RDX 21.60 35.21 43.19

1wt%DOS þ RDX 25.72 33.00 41.28
3wt%DOS þ RDX 25.91 32.13 41.96
5wt%DOS þ RDX 28.97 31.39 39.65
10wt%DOS þ RDX 36.51 26.72 36.78

of 50 per cent explosion probability (H50).

The friction sensitivity of the RDX/DOS composites was tested
with a sample mass of 20 ± 1 mg, a pendulum weight of 1.5 kg, a
swing angle of 90 , and a pressure of 3.92 MPa. Two groups of each
sample and 25 same samples from each group were tested. The
results were shown in terms of the explosion probability.
Fig. 4. The XRD patterns.

3. Results and discussion

3.1. SEM characterization
Fig. 2 showed the SEM images of the RDX/DOS composites and
raw RDX. In Fig. 2(aed), the RDX/DOS composite sizes were in the
range of 1e3 mm, while the size of raw RDX was in the range of
15e30 mm. The distributions of the Carbon, Nitrogen and Oxygen
elements in the composites’ surface were tested by energy
dispersive spectrometer (EDS) connected with the SEM, and the
relative mass ratios of the elements were listed in Table 1. The
relative mass ratio of Carbon increased as the increase of DOS
quantity, while the relative mass ratio of Nitrogen decreased, which
indicated the existence of DOS in the composites.
3.3. XRD characterization
Fig. 4 showed that the positions and shapes of the diffraction
angles of the RDX/DOS composites were similar to those of raw
RDX, which were in accordance with the referenced data of RDX in
the PDF2-2004 card, and the crystal structure parameters of the
samples were calculated by MDI Jade 6 software and were listed in
Table 2. DOS had some small influences on the crystal structure of
the RDX/DOS composites. The diffraction peaks of the composites
were weaker (diffraction peak intensity below 1500 a. u.) than
those of raw RDX (diffraction peak intensity below 40000 a. u.). It
was because that the sizes of the composites were smaller than that
of raw RDX.

3.2. FT-IR characterization 3.4. DSC characterization

As shown in Fig. 3, compared with raw RDX and DOS, the RDX/
DOS composites had similar FT-IR spectra, which indicated that the
chemical bonds and functional groups of composites were in
accordance with those of raw RDX and DOS. The infrared absorp-
tion peaks near 2900 cm
1 (the symmetrical stretching vibration
and anti-symmetric stretching vibration of eCH3 in DOS) and
1750 cm
1 (the stretching vibration of C¼O in DOS) were gradually
getting stronger with the increase in DOS quantity. The results
indicated the purity of the composites and the uniform distribution
of DOS and RDX in the composites.
Fig. 5(aee) showed the DSC curves of raw RDX and the RDX/DOS
composites at 1, 2, 4, 10 K min
1 heating rates respectively. The
exothermic peak temperatures of the RDX/DOS composites were
close to each other and higher than that of raw RDX.
The thermal decomposition kinetics parameters of raw RDX and
the RDX/DOS composites could be calculated by the Kissinger
method (Equation (1)) [22].

. 
ln b TP2 ¼ lnðAR=EÞ
E=ðRTP Þ (1)

in which b, the heating rate, K$min
1; Tp, the temperature of the

exothermic peak at heating rate b, K; E, the activation energy,
J$mol
1; A, the pre-exponential factor; R, the gas constant,
8.314 J mol
1 K
1.
As shown from Fig. 5(fej), the activation energy and the pre-
exponential factor of the RDX/DOS composites were obtained.
The activation energy of the RDX/DOS composites were close to
each other and lower than that of raw RDX, which was

Table 2
The crystal structure parameters of the samples.

Samples a b c a b g
RDX(46e1606) 13.202 11.601 10.717 90 90 90
raw RDX 13.2312 12.4294 10.5082 90 90 90
1wt%DOS þ RDX 13.1738 11.5935 10.7076 90 90 90
3wt%DOS þ RDX 13.1986 11.6376 10.6977 90 90 90
5wt%DOS þ RDX 13.1926 11.5487 10.7151 90 90 90
10wt%DOS þ RDX 13.1642 11.5804 10.6717 90 90 90
Fig. 3. The FT-IR absorption spectra.
266 J. Yao et al. / Defence Technology 13 (2017) 263e268

Fig. 5. The DSC curves at different heating rates and Kissinger plots of the samples.
 J. Yao et al. / Defence Technology 13 (2017) 263e268
Fig. 5. (continued).
194.614 kJ mol
1. Fig. 6 showed that the 3wt% composites had the
lowest activation energy, which was 152.186 kJ mol
1.
On the one hand, the scales of the composites were smaller than
that of raw RDX. On the other hand, the addition of DOS led to
solvent effect [23] and insensitive effect. DOS was a polar plasti-
cizer, which could decrease the stability of the crystal lattice of RDX
by dissolving the surface layers of the nitramine crystal. When DOS
mass ratio was less than 3wt%, the solvent effect made more dif-
ference in the stability of the composites than the insensitive effect.
Conversely, when DOS mass ratio was more than 3%, the insensitive
effect made more difference. When the ratio was from 1wt% to 3wt
%, the DOS dissolved the crystal surface layers of RDX gradually, the
thermal stability as well as the activation energy decreased. When
Fig. 6. The changing curve of the activation energy.
267
the DOS mass ratio reached 3wt%, DOS almost completely coated
the crystal surface layers. However, when the DOS mass ratio went
on increase, the lubrication of DOS began to affect the properties of
the nitramine crystals, and the insensitive effect played a major role
in the stability of the composites, which resulted to the increase on
the activation energy.
3.5. Mechanical sensitivity
As shown in Fig. 7(a), the H50s of the RDX/DOS composites were
higher than that of raw RDX, which was 40.5 cm. The 3wt% DOS
composites had the lowest H50, which was consist with the lowest
activation energy. In Fig. 7(b), the friction sensitivity of the RDX/
DOS composites decreased with the increase of DOS quantity, and
lower than that of raw RDX, which was 100%. The results proved
that DOS made a great difference in reducing the mechanical
sensitivity of raw RDX.
4. Conclusions
The composites, which contained RDX and DOS, were prepared
successfully by the electrostaticspray method. The particle sizes
were in the range of 1e3 mm in size. The crystal structure and FT-IR
spectra of the RDX/DOS composites were similar to those of raw
RDX. The activation energy of the RDX/DOS composites was lower
than that of raw RDX. The 3wt% composites had the lowest acti-
vation energy and H50. The impact sensitivity and friction sensi-
tivity of the RDX/DOS composites were lower than those of raw
RDX. These results suggested that the RDX/DOS composite was an
insensitive explosive with excellent properties.
268 J. Yao et al. / Defence Technology 13 (2017) 263e268

Fig. 7. The mechanical sensitivity trends of the samples.

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