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Advanced plastic explosive based on BCHMX compared with Composition C4

and Semtex 10

Article · April 2011

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New Trends in Research of Energetic Materials, Czech Republic, 2011 [Content]

Advanced plastic explosive based on BCHMX

compared with Composition C4 and Semtex 10
Ahmed Elbeih*, Jiri Pachman*, Svatopluk Zeman*, Waldemar Trzciński**
and Zbyněk Akštein***
* Institute of Energetic Materials, Faculty of Chemical Technology, University of Pardubice,
53210 Pardubice, Czech Republic
** Institute of Chemistry, Military University of Technology, PL-00-908 Warsaw, Poland
*** Research Institute of Industrial Chemistry, Explosia, CZ-531 17 Pardubice

elbeih.czech@gmail.com

Abstract:
BCHMX was studied as a plastic explosive bonded by Silicone matrix. For comparison the
original plastic explosives, Composition C4 based on RDX as explosive filler and Semtex
10 based on PETN as explosive filler, were studied. Pure explosives used as active mate-
rial in the plastic compositions were included as well. Sensitivity to impact and friction
were measured. The thermal stability was studied using differential thermal analysis
(DTA) and the outputs were evaluated by Kissinger method. The detonation velocity was
measured experimentally and the detonation characteristics were calculated by means of
CHEETAH code. On the basis of mutual comparison of all the obtained results, it was
concluded that the new formulation has lower sensitivity to impact and friction than Com-
position C4 and Semtex 10; also it has higher thermal stability. Detonation pressure and
detonation energy of the new formulation were higher than the original plastic explosives
used while its measured detonation velocity were at the same level of Composition C4.
Keywords: plastic explosives; BCHMX; composition C4; Semtex 10; silicone

1 Introduction
BCHMX (cis-1,3,4,6- tetranitrooctahydroimidazo-[4,5-d]imidazole or Bicyclo-HMX) [1]
is an attractive compound with TMD = 1.86 g.cm-3, theoretically it has detonation velocity =
9050 m s-1, detonation pressure = 37 GPa and explosion heat = 6.518 MJ kg-1 [2]. It has friction
sensitivity in the same range as HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane) and impact sensi-
tivity about the same as PETN (Pentaerythritol tetranitrate) [2]. BCHMX was studied as plastic
explosive bonded by the C-4 matrix where the results showed that its detonation characteris-
tics are higher than the original composition C4 but unfortunately more sensitive [3,4,5]. Also
the replacement of PETN by BCHMX in Semtex 10 showed enhancement of the detonation
characteristics and remaining the same sensitivity level as Semtex 10 but its detonation charac-
teristics are still lower than Composition C4 [6].
The goal of this work is to prepare a plastic explosive based on BCHMX with higher deto-
nation characteristics and lower sensitivity than Composition C4, in the mean time has higher
detonation energy than Semtex 10 and can be easily prepared. Silicone matrix was selected to
prepare plastic explosive based on BCHMX. Sensitivity, thermal stability and the detonation
characteristics of the prepared samples were determined and compared with the original plastic
explosives, Composition C4 and Semtex 10, in addition to the individual explosives [7, 2].
CHEETAH code was used to calculate the detonation characteristics of all the studied samples
[8].

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New Trends in Research of Energetic Materials, Czech Republic, 2011 [Content]

2 Experimental

2.1 Preparation of Plastic explosives

The plastic explosives were prepared in the Explosia Company (Research institute of in-
dustrial chemistry). BCHMX was prepared at the institute of energetic materials (IEM) in 2
stages method for its synthesis (unpublished). Silicone matrix with the desired average molecu-
lar mass and viscosity (unpublished) was obtained from polydimethyl-siloxane. BCHMX 88%
wt. was mixed with the polymeric matrix 12% wt. at 25 oC for 90 min. using computerizing
mixer Plastograph. Composition C4 and Semtex 10 were prepared as reported in references
[5, 6]. The prepared samples were extruded to obtain cylinders of plastic explosives with
length 200 mm and diameter 16 mm. compositions of all the prepared plastic explosives are
reported in Table 1.
Table 1: Compositions of the prepared samples.
Explosive filler Polymeric matrix
Composition
substance content compound content
BCHMX-silicone BCHMX 88% Polydimethy-siloxane 12%
C4 matrix; Polyisobutylene + dioctyl-
Composition C4 [5] RDX 91% 9%
sebacate + oily material
semtex matrix; rubber + non-energetic
Semtex 10 [6] PETN 85% 15%
plasticizer

2.2 Elemental Analysis

Fisons - EA-1108 CHNS-O elemental analyzer was used to detect the % of C, H and N in
the prepared samples which were needed for the theoretical calculation of the detonation pa-
rameters for all the prepared samples. The results of the elemental analysis were recalculated to
match the nitrogen content to the individual explosive and reported in Table 2. The summary
formula calculated in this way was used as if it was individual explosive and it was used in the
different methods for calculation of the detonation parameters

2.3 Heat of combustion

Automatic combustion calorimeter MS10A was used for measuring the heat of combustion
of the samples. The samples were prepared and placed in bomb filled by excess of oxygen [9].
The data obtained from the measurements are reported in Table 2. These data are used for cal-
culation of the heat of formation of the samples which were needed for the calculation of the
detonation parameters.
Table 2: Data obtained for calculation of detonation parameters.
Mol. Heat of Heat of
No. Sample Code Formula Weight combustion formation
(g mol-1) (J g-1) (kJ mol-1)
1 BCHMX cryst. C4 H6 N8 O8 294.17 9124 236.5
2 BCHMX-silicone C5.02 H9.18 N8 O8.47 Si0.54 332.33 11328 -27.16
3 pure RDX C3 H6 N6 O6 222.14 9522 66.2
4 Composition C4 C4.66 H8.04 N6 O5.99 243.7 12356 22.0
5 PETN C5 H8 N4 O12 316.15 8182 -538.7
6 Semtex 10 C8.05 H12.64 N4 O12.37 363.38 11942 -646.8

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New Trends in Research of Energetic Materials, Czech Republic, 2011 [Content]

2.4 Thermal stability

DTA 550 Ex apparatus was used for thermal analysis of explosives [9]. The measurements
were carried out at the atmospheric pressure, the tested sample being in a direct contact with
the air. The tested sample (0.05 g) was placed in a test tube made of Simax glass, 5 mm in di-
ameter and 50 mm long. The reference standard was 0.05 g aluminum oxide. Linear heating
rate of 5, 10 and 15 oC min-1 were measured. Peak temperatures of exothermic thermal decom-
position at linear heating rate of 5 °C min-1 for all samples are reported in Table 3. The exo-
thermic effects of the thermal decomposition and the endothermic peaks of the prepared sam-
ples at heating rate 5 oC min-1 are presented in Fig. 1. Outputs obtained from the measurements
at the different heating rates were processed by the Kissinger method [10] and presented in
Fig 2. The slopes of Kissinger relationship (EaR-1), which were taken as the characteristics of
thermal reactivity [11, 12] are reported in Table 3.

Figure 1: The typical DTA curves for the studied samples (at heating rate 5 °C min-1)

-5
y = -32127x + 55.375
2 y = -26735x + 47.753
-6 R = 0.9596 2
R = 0.9997
RDX
-7 PETN

-8 y = -30408x + 57.081
BCHMX-Silicone 2
R = 0.9502
-9 y = -29355x + 48.09
ln ( T-2)

2 Semtex10
R = 0.9978
-10

-11

-12
composition
-13 C4
BCHMX
y = -19274x + 28.997
-14 y = -33743x + 56.794 2
2 R = 0.9195
R = 0.9731
-15
0.0018 0.0019 0.002 0.0021 0.0022 0.0023
-1 -1
T /K

Figure 2: Evaluation of DTA outputs by Kissinger method

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New Trends in Research of Energetic Materials, Czech Republic, 2011 [Content]

2.5 Impact sensitivity measurements

The standard impact tester (Julius Peter [13]) was used with exchangeable anvil, the
amount of tested substance being 40 mm3. 2 and 5 kg weight drop hammers were used. The
probit analysis [14] was used to determine the probability levels of the initiation. The obtained
sensitivity was expressed as the drop energy (Ed) versus percentage of initiation. Only the 50%
probability of initiation is used in this article and is reported in Table 3.

2.6 Friction sensitivity measurements

BAM friction test apparatus was used to determine the sensitivity to friction by applying
the standard test conditions [13]. Sensitivity to friction was determined by spreading about
0.01g of the dry explosive on the surface of the porcelain plate in the form of a thin layer. Dif-
ferent loads were used to change the normal force between the porcelain pin and the plate. The
sample initiation was observed through sound, smoke appearance, or by the characteristic
smell of the decomposition products. Using the probit analysis [14], only the normal force at
which 50% of initiation occurs is reported as the friction sensitivity as in Table 3.

Table 3: Sensitivity and thermal stability measurements.

Impact Friction Kissinger slope
DTA peak
No. Sample Code sensitivity sensitivity Ea R-1
(N) (5oC min-1) (K)
(J)
1 BCHMX cryst. 3.2 88 225.4 -33743
2 BCHMX-silicone 24.3 232 226.3 -29355
3 pure RDX 5.6 120 213.1 -32127
4 Composition C4 21.1 214 212.9 -19274
5 PETN 2.9 44 184.7 -26735
6 Semtex 10 15.7 206 176.6 -30408

2.7 Detonation velocity measurements

The detonation velocity of all the prepared plastic explosives were measured by the ioni-
zation copper probe method [13] where the data were reported on the oscilloscope (Tektronix
TDS 3012). The samples were prepared in the form of cylinder with a 16 mm diameter and 200
mm length. The copper probes were inserted in the charge. The first probe was inserted at dis-
tance of 50 mm from the booster and the second probe was inserted at 100 mm distance from
the first probe. Charges were set off using a booster charge (Semtex 1A which had mass = 6 g
and diameter = 16 mm) initiated by standard industrial electric detonator no. 8. The tests were
done in triplicate with variation between readings being lower than 62 m s-1 and reported in
Table 4.

2.8 Calculation of the detonation characteristics

The theoretical detonation characteristics (detonation velocity, D, detonation energy, Ed,
detonation pressure, P) of the prepared samples as well as the pure explosives were calculated
by using CHEETAH code [8]. The BKWS set of parameters for the BKW EOS was applied,
these parameters are: α = 0.5, β = 0.298, κ = 10.50, Θ = 6620. Formic acid was first included
in the detonation gaseous products [5] but it doesn't seem to be possible, so we recalculated the

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New Trends in Research of Energetic Materials, Czech Republic, 2011 [Content]

detonation parameters after removing the formic acid from the gaseous products and reported
the recalculated detonation characteristics of all the tested explosives in Table 4.

3 Results and discussion

From the method of preparation, it was observed that the average molecular mass and the
viscosity of the silicone matrix have a great effect on both the time needed to complete the
mixing process and the characteristics of the prepared samples. Also the particle sizes of the
explosive filler affect the elasticity of the prepared composition.
According to the sensitivity tests, it is obvious from Table 2 that the impact energy
needed to initiate BCHMX crystals which were coated by silicone binder is approximately 7-8
times higher than that needed to initiate the pure BCHMX. The impact sensitivity of the plastic
BCHMX-silicone (24.3 J) is lower than composition C4 (21.1 J) and Semtex 10 (15.7 J) al-
though BCHMX is more sensitive than RDX and at the same level of PETN. Regarding to the
friction sensitivity, plastic BCHMX-silicone has lower friction sensitivity than the original
Composition C4 and Semtex 10.
Fig. 3 shows the results of the impact and friction sensitivities of the studied samples. It is
clear that the different plastic matrices decrease the impact and friction sensitivities of the pure
explosives. BCHMX-silicone has the lowest impact and friction sensitivities of the studied
samples. The three plastic explosives have friction sensitivity close to each other while the dif-
ference between them is higher in case of impact sensitivity. These results prove the efficiency
of the silicone binder to decrease the sensitivity of BCHMX to a level lower than Composition
C4.
6500
Calculated detonation energy/J g-1

BCHMX
6200

PETN
RDX
5900

BCHMX-silicone
5600

5300
Compostion C4
Semtex10
5000
0 2 4 6 8 10 12 14 16 18 20 22 24 26
Impact energy / J

Figure 3: Results demonstrating effect of adding polymeric matrix on sensitivities of pure explosives

From the DTA results of the studied samples, it is obvious from Fig. 1 that the peak tem-
perature of Semtex 10 is lower than that of pure PETN; this is mostly due to the presence of the
inert plasticizer in the polymeric matrix which acts as a solvent for the pure explosives and de-
creased its thermal stability as reported in [15].
Composition C4 has approximately the same exothermic peak temperature as pure RDX
although it was concluded that C4 matrix decrease the stability of the explosives as reported in
[5, 16]. This might be due to melting of pure RDX just before the decomposition as well as its
melting at nearly the same temperature in Composition C4.
BCHMX-silicone has higher exothermic decomposition temperature than pure BCHMX;
this indicates that silicone binder enhances the thermal stability of BCHMX.

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New Trends in Research of Energetic Materials, Czech Republic, 2011 [Content]

Table 4: Measured and calculated detonation characteristics.

CHEETAH code
Detonation
Density velocity Detonation
No. Sample Code Dcalc-Dexp Detonation Detonation
(g cm-3) experiment velocity Energy
Dexp/100 pressure
(m/s) calculated
(%) (GPa) (kJ kg-1)
(m/s)
1 BCHMX cryst. 1.790* 8650* 8832 2.1 33.24 6175
BCHMX-
2 1.626 7994 8140 1.8 25.27 5750
silicone
3 pure RDX 1.760** 8750** 8812 0.7 31.73 5868
4 Composition C4 1.610 8055 7956 -1.2 24.42 5278
5 PETN 1.700** 8400** 8429 0.3 28.88 5994
6 Semtex 10 1.500 7416 7388 -0.4 20.39 5182

* Reference [2] ** Reference [7]

Results of measuring the detonation velocity of the plastic explosives showed that Com-
position C4 has slightly higher detonation velocity than BCHMX-silicone by nearly 60 m s-1
and much higher than Semtex 10 (more than 600 m s-1 difference) as reported on Table 4.

9000
-1
Experimental detonation velocity /m s

8800
RDX BCHMX
8600 3% vitonB

8400 PETN

8200

8000 composition C4
BCHMX-silicone
7800

7600

7400 Semtex 10

7200

7000
160 170 180 190 200 210 220 230 240 250

Peaks of exothermic decomposition / oC

Figure 4: Results demonstrating effect of adding polymeric matrix on thermal stability

and D of the pure explosives

Fig. 4 shows the results of the detonation velocity measurements and the thermal stability
of all the samples. Semtex 10 has the lowest thermal stability and lowest detonation velocity of
the studied plastic explosives. This is due to presence of PETN as explosive filler as well as
lower content of explosive in the mixture. While BCHMX-silicone has the best thermal stabil-
ity of the used samples and its detonation velocity is nearly in the same level of Composi-
tion C4. The measured detonation velocity of BCHMX is in presence of 3% fluorel as phleg-
matizer. To apply the safety precaution, we didn’t press BCHMX as a pure explosive.

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New Trends in Research of Energetic Materials, Czech Republic, 2011 [Content]

Regarding to the calculated detonation parameters, a linear relationship represented by

straight line was found between the calculated detonation pressure according to CHEETAH
code and the experimentally measured ρD2 of the studied explosives as shown in Fig. 5. This
relation shows the compatibility of the experimental and the calculated results. It is clear from
the figure that BCHMX-silicone has higher calculated detonation pressure than composition
C4 and much higher detonation pressure and detonation velocity than Semtex 10. It is pre-
dicted that measuring of the detonation velocity for BCHMX as a pure explosive should en-
hance this relation in Fig. 5.

36
Calculated Detonation Pressure/ GPa

34 y = 0.2355x + 0.6121 BCHMX

R 2 = 0.9841
32
RDX
30
PETN
28

26 BCHMX-silicone

24 Composition C4

22

20 Semtex 10

18
70 80 90 100 110 120 130 140 150

Experimental ρD 2 / GPa

Figure 5: Relationship between the calculated detonation pressure by EXPLO 5 code and
experimental square of detonation velocity multiply by initial density

6500
Calculated detonation energy/J g-1

BCHMX
6200

PETN
RDX
5900

BCHMX-silicone
5600

5300
Compostion C4
Semtex10
5000
0 2 4 6 8 10 12 14 16 18 20 22 24 26
Impact energy / J

Figure 6: Results demonstrating effect of adding polymeric matrix on calculated Detonation

energy and impact energy needed for initiation of explosives

It is clear from Fig. 6 that the calculated detonation energy of BCHMX-silicone

(5750 kJ mol-1) is much higher than both Composition C4 (5278 kJ mol-1) and Semtex 10
(5182 kJ mol-1), also its impact sensitivity is lower. This figure proves that BCHMX-silicone is
interesting plastic explosive. In the case of pure explosives, the detonation energy of PETN is
higher than RDX and both are lower than BCHMX.

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New Trends in Research of Energetic Materials, Czech Republic, 2011 [Content]

4 Conclusion
From this study it was concluded that the new plastic explosive containing BCHMX as
explosive filler and silicone matrix as a binder has lower sensitivity to impact and friction than
both composition C4 and Semtex 10. According to DTA measurements BCHMX-silicone has
higher thermal stability than composition C4 and Semtex 10. The experimental measurements
showed that the detonation velocity of the plastic BCHMX-silicone is slightly lower than that
of composition C4 (by 60 m s-1) and much higher than Semtex 10 (by 600 m s-1). Regarding to
the calculated results by CHEETAH code, the detonation characteristics of BCHMX-silicone
are higher than composition C4 and Semtex 10. CHEETAH code gave a good results compar-
ing with the measured values. All the results indicate that BCHMX-silicone is an interesting
plastic explosive has low sensitivity and high detonation characteristics.

References
[1] R. Gilardi, J.L., Flippen-Anderson, R. Evans, “cis-2,4,6,8-tetranitro-1H,5H-2,4,6,8- tetraazabicy-
clo [3.3.0] octane, the energetic compound (bicyclo-HMX) ”, Acta. Cryst., sect. E 58 (2002)
0972.
[2] D. Klasovity, S. Zeman, A. Ruzicka, M. Jungova, M. Rohac, “cis-1,3,4,6-
tetranitrooctahydroimidazo-[4,5-d]imidazole (BCHMX), its properties and initiation reactivity”,
J. Hazard. Mater., 164 (2009) 954–961
[3] A. Elbeih, J. Pachman, , S. Zeman, Z. Akštein, W. Trzciński “Detonation characteristics of
BCHMX and HNIW with two different binders”, 13th seminar NTREM, Pardubice, April 2010.
[4] A. Elbeih, J. Pachman, W. Trzciński, S. Zeman, Z. Akštein, J. Šelešovský “Study of Plastic Ex-
plosives based on Attractive Cyclic Nitramines; Part I. Detonation Characteristics of Explosives
with C-4 Binder”, J. Hazard. Mater.
[5] A. Elbeih, J. Pachman, S. Zeman, W. Trzciński, M. Suceska, Z. Akštein, “Thermal stabil-
ity and detonation characteristics of pressed and elastic explosives on the basis of se-
lected cyclic nitramines”, CEJEM. Volume 7, number 3, 2010.
[6] A. Elbeih, J. Pachman, S. Zeman, Z. Akštein “Replacement of PETN by bicyclo-HMX in
semtex 10” 8th International armament conference on scientific aspects of armament &
safety technology, Pultusk, Poland, 2010
[7] R. Meyer, J. Kohler, A. Homburg, “Explosives”, fifth, completely revised edition.
[8] Fried L. E., CHEETAH 1.39 User’s Manual, UCRL-MA-117541 Rev. 3, Lawrence Livermore
National Laboratory, 1996.
[9] M. Krupka, “Devices and equipments for testing of energetic materials”, New Trends in Research
of Energetic Materials, Univ. Pardubice, April 2001, p. 222.
[10] H. E. Kissinger, “Reaction kinetics in differential thermal analysis”, Anal. Chemistry 29 (1957)..
[11] S. Zeman, “Sensitivity of high energy compounds”, in: T. Klapoetke(Ed), High energy density
Materials, Series: Structure & Bonding, 125, Springer, New York, 2007, pp. 195-271..
[12] S. Zeman, “New aspects of initiation reactivities of energetic materials demonstrated on nitra-
mines”, J. Harzard Materials, 132 (2006) 155.
[13] M. Suceska, “Test methods for Explosives”, Springer, Heideleberg, 1995.
[14] D. J. Finney, “Probit analysis”, Cambridge University, third edition 1971.
[15] K. Lucanova. “Plastic explosives on the basis of HMX and bicyclo-HMX” Diploma project,
Univ. of Pardubice, June 2009.
[16] A. Elbeih, J. Pachman, S. Zeman, M. Jungova, “Performance and Detonation Characteristics of
BCHMX in three different plastic matrices”, 37th annual international conference of explosives
engineers, San Diego, Feb. 2011

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New Trends in Research of Energetic Materials, Czech Republic, 2011 [Content]

Low Sensitive HNIW

Ahmed Elbeih, Adela Husarova, Svatopluk Zeman
Institute of Energetic Materials, Faculty of Chemical Technology, University of Pardubice,
532 10 Pardubice, Czech Republic.

elbeih.czech@gmail.com

Abstract:
The aim of this study was to obtain crystals of HNIW with high purity, regular shape,
without sharp edges, and relatively small particle size to improve its sensitivity to impact.
New method was applied to purify the crystals and obtain low sensitive HNIW. For com-
parison, different published methods were applied for the recrystallization of HNIW based
on solvent-antisolvent technique. The optimum parameters affect the crystal size and
shape, types of solvent and anti-solvent, rate of addition, speed of stirring as well as using
ultrasound device in stead of stirrer, were used. Fourier transform infrared spectroscopy
(FTIR) was used to confirm the HNIW polymorphs. Thermal stability of the samples was
studied by using Differential thermal analysis technique (DTA). Qualitative analysis of the
crystal size and shape was done using scanning electron microscope devise. Laser scatter-
ing particle size distribution analyzer was used for the determination of the particle size
distribution. Impact sensitivity was measured for all the obtained samples. The results con-
firmed that the impact sensitivity of HNIW decreases by obtaining small particles with
regular shape but it is still more sensitive than other nitramines. While the obtained crys-
tals from the new method has small particle size, regular shape, smooth surface without
crack and lower impact sensitivity than RDX and HMX.
Keywords: HNIW; crystallization; purification; sensitivity; SEM

1 Introduction
The sensitivity of explosives depends on properties of their crystals as well as their purity.
Reduced sensitivity (RS) is desired to ensure safe load, assemble, and pack operations to meet
safe handling requirements of the end user. 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-
hexaazaisowurtzitane (HNIW, CL-20) is a high-energy material with a cage structure. Today it
is considered as the most powerful explosive and displays the most promising performance da-
ta. It has four used structural isomers (α, β, γ and ε-form of crystal), the crystal of ε-form is
thermodynamically and mechanically most stable due to its high symmetric configuration of
molecules in the structure [1, 2]. ε- HNIW has high TMD (>2 g cm-3), positive heat of for-
mation (~ 419 kJ mol-1) and high performance [3, 4]. It is often obtained in the form of poly-
crystalline particles with sharp edges and microscopically visible defects while it is possible to
control the particle size of HNIW by optimizing the crystallization process [5]. It was reported
that ε-HNIW has high sensitivity to impact more than RDX and HMX [6, 7].
Many publications were reported about the crystallization of HNIW to obtain ε-form with
high purity, high yield, regular particle shape and small particle size [8-11]. At the Institute of
Energetic Materials we have a new method (unpublished) to obtain HNIW with low sensitivity
and good physical properties.
In this work, we studied the different published methods used for obtaining ε-HNIW with
high quality and compared the results with our product obtained from the new method.

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New Trends in Research of Energetic Materials, Czech Republic, 2011 [Content]

2 Crystallization of HNIW
HNIW was obtained in the α-form from the pilot plant of Explosia Company, Pardubice,
Czech Republic. Different kinds of solvents (ethyl acetate, methyl ethyl ketone, acetone) and
antisolvents (n-heptane, toluene, xylene, Chloroform) were used for the crystallization process.
The best result obtained from our study, regarding to the impact sensitivity and the crystal
shape, was by using ethyl acetate as a solvent and n-heptane as antisolvent. Although n-
heptane didn’t give the highest yield of HNIW. Three published techniques were used to obtain
ε-HNIW and compared with the product of our new method.

2.1 Crystallization by adding the solvent to HNIW solution [9]

10 g of α-HNIW was dissolved in 30 ml ethyl acetate, and 10 ml solution of 5% K2CO3
was added during continuous stirring. Separation of the layers was done where the water layer
washed twice with 10 ml ethyl acetate and separated each time. The ethyl acetate solution
(50 ml) was placed in rotary evaporator to evaporate around 20 ml. of eutectic mixture (ethyl
acetate/water) then the rest of the solution (30 ml) was placed on 3 neck bottle under stirring by
mechanical stirrer and 150 ml of n-heptane was added to the solution drop by drop during 4
hours, the stirring rate was 400 rpm. The sample obtained from this method has the symbol
HNIW-1.

2.2 Crystallization by inverse precipitation technique [10]

10 g of α-HNIW was dissolved in 40 ml ethyl acetate, 2 g of silica gel was added to the so-
lution and stirred for 30 min. The solution was filtrated and placed on rotary evaporator for
evaporating the eutectic mixture (ethyl acetate/water) until the solution reached 20 ml. The so-
lution was added drop by drop from dropping funnel to 100 ml of n-heptane with stirring. It
takes around 2 hours under stirring rate 400 rpm. The sample obtained from this method has
the symbol HNIW-2.

2.3 Crystallization by the assistant of ultrasound [11]

The same procedure as the inverse precipitation technique was applied, with the removing
of the mechanical stirrer and placing the flask containing n-heptane on ultrasound device. The
addition process takes around 20 min. After filtration, the sample was placed under vacuum for
one day at 45 oC to get rid of any residual solvent present inside the crystal after the recrystalli-
zation process. The sample obtained from this method has the symbol HNIW-3.

2.4 HNIW from a new method

Our new method is based on dissolving of HNIW in particular solvent, then doing some
reactions with the impurities and the water content. The products were removed by filtration.
Then HNIW crystals were obtained by crystallization process. The sample obtained from this
method has the symbol HNIW-4.

3 Spectral studies
Nicolet protege 460 FTIR spectrometer was used to record the IR spectra of the samples
using transmition technique in KBr matrix. FTIR spectra for α-HNIW shows absorption at
3600-3700 cm−1; also it has different absorptions at 3000-3100 cm−1, 1550-1650 and 1200-
1350 cm−1 compared with ε-HNIW as shown in Fig 1. The IR absorption stretching of CL-20
at 3000-3100 cm−1 is due to six cage (C–H) and around both 1600 and 1300 cm−1 are attributa-

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New Trends in Research of Energetic Materials, Czech Republic, 2011 [Content]

ble to asymmetric and symmetric stretching of NO2 groups [12]. FTIR spectra for all the pre-
pared samples showed the same characteristic peaks as that for standard ε-HNIW.

Figure 1: IR spectra of HNIW samples.

4 Thermal studies
A DTA 550 Ex apparatus was used for thermal analysis of the samples [13]. The meas-
urements were carried out at atmospheric pressure, with the tested sample in a direct contact
with the air. The tested sample (0.05 g) was placed in a test tube made of Simax glass, 5 mm in
diameter and 50 mm long. The reference standard was 0.05 g aluminum oxide. A linear heating
rate of 5 oC min-1 was used. The results are reported in Table 1. Fig. 2 shows the exothermic
peaks of the thermal decomposition of the samples. α-HNIW showed a maximum peak at 222
o
C while the other samples showed maximum peaks at temperatures higher than α-HNIW. The
exothermic peaks temperature of all the prepared samples is close to each other with nearly the
same shape. This proves that the method of crystallization hasn’t significant effect on the ther-
mal stability. Fig. 3 shows the endothermic peaks of changing the polymorph of HNIW. The
α-HNIW didn't show any endothermic peak while the other samples have endothermic peaks
with in the range between 167 -172 oC maximum peaks temperatures.

Figure 2: exothermic peaks of samples measured by DTA

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Figure 3: endothermic peaks of samples measured by DTA

5 Analysis of particle size distribution

The obtained samples were measured by using particle size distribution analyzer Partica
LA-950. The particle size of CL-20 was determined on the principle based on laser light scat-
tering. It uses Mie Scattering Theory (laser diffraction) to measure particle size over the range
of 0.01-3000µm. Fig. 4 shows the particle size distribution of all the prepared samples. The
particles size of HNIW-1 is in the range of 27-76 µm, with mean size of 50 µm. HNIW-2 has
particles size in the range of 13-54 µm with mean size of 28 µm. The crystals of HNIW-3 ob-
tained by the sonication process are smaller in size with 13 µm mean size of the particles and
falls in a narrow range of 7-22 µm. While the particles size of the HNIW-4 obtained by the
new method is in the range of 2-16 µm and has mean size of 8 µm with few quantity on the
nano-scale. This study reveals that HNIW particles obtained from both the sonication process
and the new method have a narrow range of particle size. In the case of normal reprecipitation
and the inverse precipitation, the particles fall in wider range.

Figure 4: the particles size distribution of the samples

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6 Scanning electron microscope (SEM) studies

The crystal morphology has been studied by scanning electron microscope (SEM) JEOL
JSM-5500LV. SEM photographs of the alpha-HNIW at Fig. 5 showed random crystals have
different shapes and sizes, full of cracks and porosities with high degree of agglomeration. Af-
ter the recrystallization, the sample HNIW-1 showed also random crystals with a high degree
of agglomeration. It has irregular shape of crystals with different particles size as well as full of
cracks but much lower porosity than α-HNIW (Fig. 6). HNIW-2 has also irregular crystal
shape and different particle size with cracks but slightly lower crystal size than HNIW-1
(Fig.7). HNIW-3 precipitated in the presence of ultrasound showed regular crystal shapes and
small size. Further, the particles are in a good distribution but still there are cracks at the sur-
face of the crystals (Fig. 8). HNIW-4 has regular uniform shape of crystals; it has very small
particle size without sharp edges (Fig. 9). Also it is clear that HNIW-4 has a good smooth crys-
tal surface which is the main advantage compared with crystals of HNIW-3.

Figure 5: SEM photos of α-HNIW

Figure 6: SEM photos of HNIW-1

Figure 7: SEM photos of HNIW-2

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Figure 8: SEM photos of HNIW-3

Figure 9: SEM photos of HNIW-4

7 Impact sensitivity measurements

The standard impact tester (Julius Peter [14]) was used with exchangeable anvil, the
amount of tested substance being 40 mm3, 2 and 5 kg weight drop hammers were used. The
probit analysis [15] was used to determine the probability levels of the initiation. The obtained
sensitivity was expressed as the drop energy (Ed) versus percentage of initiation. Only the 50%
probability of initiation is used in this article and is reported in Table 1.

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Table 1: Measured data of the prepared samples

DTA exothermic peak Mean particle size Impact energy
Sample
(oC) (µm) (J)
HNIW-1 222.4 51.7 1.86
HNIW-2 223 31.8 2.34
HNIW-3 225.4 14.2 4.12
HNIW-4 224 9.1 10.83

The samples obtained by the normal recrystallization and the reverse methods show high
sensitivity to impact, while the sample obtained by the sonication process gives better impact
sensitivity 4.1 J. This might be due to enhancing the particle shape as well as decreasing its
size. Another reason might be due to the removing of any residual solvent inside the crystal.
HNIW-4 obtained by the new method showed lower impact sensitivity (10.8 J) than all the
other samples. This fact mostly due to the enhancement of the physical characteristics of the
crystals (regular smooth particles without cracks and have small size) as well as the highly pu-
rified technique used in this method based on removing the impurities by chemical reactions.

8 Conclusion
It was concluded that HNIW sample obtained by the new method is epsilon-HNIW. It has
small particle size with smooth surface and regular shape without cracks. The impact sensitivi-
ty of the sample is lower than RDX and HMX (our measurements are 5.6 and 6.4 J respective-
ly). The published methods of obtaining pure epsilon HNIW based on the solvent-antisolvent
technique aren't suitable for obtaining low sensitive HNIW. The new method used based on
removing the impurities and the water content by chemical reactions showed better influence
on the impact sensitivity of HNIW.

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