Studies on energetic compounds: Part 40. Kinetics of thermal decomposition of some bis(propylenediamine)metal perchlorate complexes

Article abstract of DOI:10.1007/s10973-005-0902-4

Bis(propylenediamine)metal perchlorate (BPMP) complexes like [M(pn) ₂](ClO₄)₂ (where M=Cr, Mn, Ni, Cu, Zn and pn=propylenediamine) have been prepared and characterized by gravimetric methods, infrared and elemental analysis. Thermal properties have been studied using simultaneous thermogravimetry-differential thermal analysis in atmospheres of nitrogen and air to examine the effect of atmospheric change on thermal decomposition of these complexes. Changing of the atmosphere does not cause any measurable changes in the decomposition of complexes. However, as indicated by thermoanalytical techniques, the thermal stability of present complexes decreases in the order: [Cr(pn)₂](ClO₄) ₂>[Mn(pn)₂](ClO₄)₂>[Zn(pn) ₂](ClO₄)₂>[Ni(pn)₂](ClO ₄)₂>[Cu(pn)₂](ClO₄)₂. Isothermal thermogravimetry, over the temperature range of decomposition has been done for all the complexes. An analysis of the kinetics of thermal decomposition was made using a model fitting procedure as well as an isoconversional method, independent of any model. The results of both kinetic approaches have been discussed critically. The explosion delay (D _E) was measured to investigate the trend of rapid thermal analysis.

Full text of DOI:10.1007/s10973-005-0902-4

Journal of Thermal Analysis and Calorimetry, Vol. 82 (2005) 353–360
STUDIES ON ENERGETIC COMPOUNDS
Part 40. Kinetics of thermal decomposition of some
bis(propylenediamine)metal perchlorate complexes
*
G. Singh and D. K. Pandey
Chemistry Department, DDU Gorakhpur University, Gorakhpur 273 009, India
2 4 2
Bis(propylenediamine)metal perchlorate (BPMP) complexes like [M(pn) ](ClO ) (where M=Cr, Mn, Ni, Cu, Zn and pn=propylene-
diamine) have been prepared and characterized by gravimetric methods, infrared and elemental analysis. Thermal properties have been
studied using simultaneous thermogravimetry-differential thermal analysis in atmospheres of nitrogen and air to examine the effect of
atmospheric change on thermal decomposition of these complexes. Changing of the atmosphere does not cause any measurable
changes in the decomposition of complexes. However, as indicated by thermoanalytical techniques, the thermal stability of present
complexes decreases in the order: [Cr(pn)
mal thermogravimetry, over the temperature range of decomposition has been done for all the complexes. An analysis of the kinetics of
thermal decomposition was made using a model fitting procedure as well as an isoconversional method, independent of any model.
The results of both kinetic approaches have been discussed critically. The explosion delay (D ) was measured to investigate the trend
of rapid thermal analysis.
2 4 2 2 4 2 2 4 2 2 4 2 2 4 2
](ClO ) >[Mn(pn) ](ClO ) >[Zn(pn) ](ClO ) >[Ni(pn) ](ClO ) >[Cu(pn) ](ClO ) . Isother-
E
Keywords: bis(propylenediamine)metal perchlorates, explosion delay, isoconversional method, kinetics, TG/DTA
Introduction
ballistic modifiers for composite solid propellants
5–7]. The ultra-fine metal oxide, which is the final
[
Energetic transition metal complexes are well-known
explosives because of the presence of both oxidizing
and reducing group in the same complex molecule.
These complexes may find interesting applications in
pyrotechnic composition. The substances used in the
past in such composition are now avoided since they
lead to environmental and health problems. Some al-
ternative metal complexes have been synthesized to re-
place the conventional oxidizers like lead azide, potas-
sium nitrate, etc., in view of their inherent drawbacks
such as friction sensitivity, lesser stability to moisture
and incompatibility with other materials used in am-
munition. Nickel hydrazine nitrate [1] has been pre-
pared and found insensitive to impact, friction or elec-
trostatic charge but more sensitive to flame [2]. It is a
suitable replacement for lead azide, as an intermediate
charge in commercial detonators. Also, the reaction li-
quor, unlike lead azide, does not contain any useless
ion and thus makes possible the repeated use of the li-
quor in continuous preparation of this primary explo-
sive. N,N-bis(2,4,6-trinitrobenzoyl)lead hydrazine,
synthesized from lead acetate and bis(2,4,6-trinitro-
benzoyl)hydrazine with better heat resistance proper-
ties is found to be a good substitute for lead styphnate
product of thermal decomposition of these complexes,
may find broad spectrum of applications. Thus, in view
of exciting potential for various applications, the ther-
mal studies were carried out in our laboratory. From
the theoretical point of view, the interest is focused on
the kinetics of thermal decomposition and from practi-
cal perspective; the study is aimed to explore the possi-
bilities of using some energetic coordination com-
pounds in pyrotechnic compositions.
Experimental
Materials
The following AR grade commercially available
chemicals (obtained from the sources given in paren-
theses) were used as received without any further pu-
rification: Carbonates of copper, chromium, manga-
nese (BDH), nickel, zinc (Thomas Baker), 70%
perchloric acid, methanol (Ranbaxy), ethanol (Hay-
man), propylenediamine, silica gel, iodine (s.d. fine
chemicals) and petroleum ether (Merck).
Preparation of complexes
[
3]. Cobalt perchlorate complex with diaminourea has
been proved to be a quite good initiator for use as pri-
mary explosive [4]. Also, such complexes are potential
Various BPMP complexes were prepared following a
two-step procedure:
*
Author for correspondence: gsingh4us@yahoo.com
1
388–6150/$20.00
Akadémiai Kiadó, Budapest, Hungary
Springer, Dordrecht, The Netherlands
©
2005 Akadémiai Kiadó, Budapest

SINGH, PANDEY
Step I: in the first step, the metal carbonates
MCO ) were treated with 70% perchloric acid (HClO )
the form of their nujol mulls. The deduced molecular
formulae of the complexes and their physical, elemen-
tal and spectral parameters are reported in Table 1.
(
3
4
to produce the metal perchlorate, i.e. M(ClO4)2
MCO +2HClO →M(ClO ) +H O+CO
3
4
4 2
2
2
TG-DTA
The perchlorates thus obtained were washed
with petroleum ether, recrystallized from distilled wa-
ter and dried in a desiccator over fused CaCl2.
The simultaneous TG-DTA curves are presented in
Fig. 1 and the corresponding data are listed in Table 2.
All these BPMP complexes are decomposing in a sin-
gle step. Mass loss occurs in the temperature range of
230–345°C, which corresponds to simultaneous
Step II: BPMP complexes were prepared by re-
acting an ethanolic solution of M(ClO ) from step I
4
2
with propylenediamine following standard proce-
dures [8–12]:
losses of two molecules of ligands (pn) and counter
–
anion (ClO ) and approaching 60.5–81% of the ini-
M(ClO ) +H N−(CH ) −NH →[M(pn) ](ClO )
4
4
2
2
2
3
2
2
4 2
tial mass. The mass of the residue corresponds to the
formation of metal oxides. The rate of the reaction is
fast and highly exothermic that is evident by accom-
panying sharp exothermic DTA peaks.
(
pn)
(BPMP)
The precipitated complexes of different colours
were separated from the mother liquor by decanting
and washing with methanol. All these perchlorates
were recrystallized from aqueous solution and dried
Non-isothermal TG and DTA in air
over fused CaCl in a desiccator.
2
In order to detect the effect of changing the atmosphere
on thermal decomposition, TG and DTA were used sep-
arately in static and flowing air. Non-isothermal TG and
DTA curves are demonstrated in Figs 2 and 3, respec-
tively. All of these complexes undergo decomposition
in a single step and produce exothermicity in DTA.
Thermal decomposition studies
All the non-isothermal analyses were done at a heating
–1
rate of 10°C min . The simultaneous TG-DTA curves
on the complexes (mass≈1–2 mg) were obtained on a
Mettler Toledo Star system in an inert atmosphere (N2
–
1
Isothermal TG
flowing at 100 mL min ). Non-isothermal TG curves
were recorded on our indigenously fabricated TG ap-
paratus [13] in static air (sample’s mass≈10 mg,
Isothermal TG thermal curves were obtained over an
optimal temperature of decomposition because of
faster and slower decomposition at higher and lower
temperatures, respectively. The desired temperature
was maintained within ±1°C and mass loss readings
were taken after suspending the sample into the fur-
nace. The curves are shown in Fig. 4.
1
00–200 mesh). Non-isothermal DTA curves were
–1
taken in flowing air (100 mL min ) using an instru-
ment supplied by Universal Thermal Analysis Instru-
ments, Mumbai (mass of sample≈10 mg). Isothermal
TG on the complexes (mass≈10 mg) was done in static
air using the indigenously fabricated TG [13] at appro-
priate temperatures of decomposition. The explosion
Mathematical treatment of isothermal TG data
delay (D
E
) of a complex (mass≈10 mg) was measured
using the tube furnace (TF) technique [14–16].
Two methods were used to evaluate the kinetic pa-
rameters. A general equation for analyzing the kinet-
ics of a thermally induced solid state reaction is,
Results
dα/dt=k(T)f(α)
(1)
Characterization
where α is the degree of conversion, t represents time,
T is the absolute temperature, k(T) is the temperature-
dependent rate constant and f(α) is a function called
the reaction model. Various commonly used reaction
models are known. It is assumed that the rate constant
obeys the Arrhenius expression: k(T)= Aexp(–E/RT),
where A is the pre-exponential (Arrhenius) factor, E
denotes the activation energy and R is the gas constant.
The integral form of Eq. (1) is generally used in kinetic
analysis giving
The purity of all these complexes was checked by thin
layer chromatography (TLC) using a mixture of
n-butanol, chloroform and glacial acetic acid in vol-
ume ratios of 2:1:1 as mobile phase (eluent). A yellow
coloured spot was obtained in all the cases the R value
f
of which is presented in Table 1. The metal content (%)
was estimated gravimetrically by well established
methods [17]. The percentage mass of other elements
(
C, H, N) was determined on Fission Instruments
DP 200 series 2 systems. The complexes were further
characterized by their infrared spectra (Impact 400) in
354
J. Therm. Anal. Cal., 82, 2005

STUDIES ON ENERGETIC COMPOUNDS
Fig. 2 Non-isothermal TG curves of complexes recorded in air
Fig. 3 DTA curves obtained in air; 1 – [Cr(pn)
– [Mn(pn) ](ClO , 3 – [Ni(pn) ](ClO
4 2
– [Cu(pn) and 5 – [Zn(pn) ](ClO )
2 4 2
](ClO ) ,
2
2
4
)
2
2
4 2
) ,
4
2
](ClO
4
)
2
2
α
−1
g(α)≡ [ f (α)] dα=k(T )t
(2)
∫
0
at a constant temperature. Here the term g(α) repre-
sents an integral. Thus, substitution of a particular re-
action model in Eq. (2) permits one to estimate the cor-
responding rate constant, obtained from the slope of a
plot of g(α) vs. t. For every reaction model selected, the
rate constants can be determined at several tempera-
tures and the Arrhenius parameters were derived.
In the isoconversional method, it is assumed that
the reaction model in Eq. (1) is independent of tem-
perature, in which case
ln{g(α)/t}=lnA−E /RT
(3)
α
where E (activation energy for a particular α) was
α
–
1
determined from the slope of a plot of –lnt vs. T .
α
Thus, the values of E for all the complexes were
α
evaluated at various α . The dependencies of E on
i
α
the extent of conversion (α) are shown in Fig. 5.
Fig. 1 TG-DTA curves of BPMP complexes in N
2
J. Therm. Anal. Cal., 82, 2005
355

SINGH, PANDEY
356
J. Therm. Anal. Cal., 82, 2005

STUDIES ON ENERGETIC COMPOUNDS
Fig. 4 Isothermal TG curves of BPMP complexes in air at the temperatures (°C) shown
Table 2 TG-DTA phenomenological data on BPMP complexes under N
2
atmosphere
TG
DTA peak temperature
Complex
(
exothermic)/°C
i
T /°C
s
T /°C
f
T /°C
decomposition/%
[
[
[
[
[
Cr(pn)
2
](ClO
4
)
2
269
258
238
230
245
310
298
275
266
284
345
331
318
307
322
60.5
81.0
79.5
78.0
78.5
307
295
277
270
279
Mn(pn)
2
4 2
](ClO )
Ni(pn)
Cu(pn)
Zn(pn)
2
4 2
](ClO )
2
](ClO
4 2
)
2
](ClO )
4 2
BPMP complexes under N
2
atmosphere; T
i s f
=onset temperature, T =inflection temperature, T =endset temperature
Explosion delay measurement
D =Aexp(E*/RT )
(4)
where E* is the activation energy for thermal explosion.
Equation (4) in its logarithmic form, is used to deter-
E
Explosion delays (D ) at various high temperatures
E
were measured for the complexes and the values are
summarized in Table 3. The measurements were fit-
ted [18–20]
�
–1
mine E* from the slope of a plot of lnD vs. T . Plots of
E
–1
lnD vs. T for these BPMP complexes are presented in
E
Fig. 6 whilst calculated E* are reported in Table 3.
J. Therm. Anal. Cal., 82, 2005
357

SINGH, PANDEY
Table 3 Explosion delay (D
E
), activation energy for thermal explosion (E*) and correlation coefficient (r) for BPMP complexes
D
E
(s) at temperature/°C
400
–1
Complex
E*/kJ mol
r
3
00
350
450
500
[
[
[
[
[
[
Cr(pn)
2
](ClO
4
)
2
118.3
117.0
113.5
110.0
115.7
–
102.5
99.9
98.2
92.8
98.7
99.4
56.6
54.8
49.0
46.4
51.9
56.3
24.4
22.3
20.3
19.1
21.0
23.0
18.9
18.5
17.0
15.5
17.7
16.8
33.9
32.0
30.3
29.7
31.5
31.7
0.9997
0.9990
0.9998
0.9999
0.9989
0.9995
Mn(pn)
2
4 2
](ClO )
Ni(pn)
Cu(pn)
Zn(pn)
Cu(pn)
2
4 2
](ClO )
2
](ClO
](ClO
](ClO
4 2
)
2
4 2
)
2
4 2
) *
*
sample’s mass≈10 mg
Discussion
It is clear from the analytical data given in Table 1
that estimated values of percentage mass of each ele-
ment are in good agreement to those of calculated and
thus confirming the formation of these complexes. In
addition, the characteristic absorption frequencies of
different groups in the complexes match well with
those reported in the standard texts [21, 22]. All these
complexes are anhydrous and metal:ligand ratio is
found to be 1:2.
TG-DTA curves (Fig. 1) and data (Table 1) indi-
cate that all the present complexes decompose in sin-
gle step. The fast decomposition is attributable to a
chain type explosive reaction due to simultaneous
Fig. 5 Dependencies of activation energy on conversion for
these complexes of the elements shown
presence of oxidizing (ClO ) and reducing (pn) group
4
in the same complex molecule. It seems that an
intramolecular solid phase redox reaction occurring
between pn and ClO , is responsible for rapid decom-
4
position. The formation of respective metal oxide as
product of decomposition was confirmed by its col-
–
our, insolubility and negative test for Cl . These ob-
servations are similar to those reported for thermal de-
composition of some amine complexes of copper(II)
nitrate [23] and nickel(II) nitrate [24, 25].
Changing of the atmosphere (from N to air)
2
does not cause any significant change in the mode of
thermal decomposition. However, a lower value of
endset temperature of decomposition (T ) in air
f
(
Fig. 2) than that in N is indicative of some what fast
2
decomposition of the complexes in air and producing
single exothermicity in DTA. Since, the thermal de-
composition of such compounds involves complex
processes, it may be speculated that the first step in
the thermal decomposition may be dissociation of the
Fig. 6 Plot of ln(D ) vs. 1/T for BPMP complexes of the ele-
E
ments shown
which would decompose instantaneously by exother-
mic reactions. The expected endothermic dissociation
process may thus be completely overshadowed by exo-
thermic process resulting in an overall exothermic ef-
fect. It was found appropriate to ascertain the contribu-
tions of endothermic dissociation and exothermic de-
composition processes and thus DTA curves were re-
corded under various conditions with a constant sam-
ple mass. As the nature of the DTA curves were found
compounds into pn and metal perchlorates, M(ClO
)
4 2
[
M(pn) ](ClO ) º 2pn+M(ClO )
2
4 2
4 2
However, at normal pressure such a dissociation
occurring in these perchlorates is difficult to detect by
TG and DTA. The reason for this being the unstable
nature of the metal perchlorates at higher temperatures,
358
J. Therm. Anal. Cal., 82, 2005

STUDIES ON ENERGETIC COMPOUNDS
The isoconversional method is known to permit
estimation of apparent activation energy, independent
of the model. In our case, we have adopted the isocon-
versional method suggested by Vyazovkin [26, 27].
This approach indicates that the decomposition of
these complexes is not as simple as indicated by the
model-fitting approach. The values of E for the com-
plexes of Cr, Mn, Ni and Zn are lower initially
(
Fig. 5), but increase gradually when α increases from
.6 to 1. The initial low value of E may be attributed
0
to the removal of pn at early stage of decomposition
which is partially governed by dissociation process
while finally higher value may correspond to decom-
–
position of anionic part (ClO ) to respective metal
4
oxides. For the complex of Cu, a fairly constant value
of E may be due to highly explosive reaction and
overlapping of different processes during heating. A
period of induction (at lower α) and a period of accel-
eration (at higher α) controlled by nucleation and nu-
clei growth has been found to operate as general
mechanism during thermal analysis.
Fig. 7 DTA curves of Cu complex in various conditions
to be similar for all complexes, that of Cu is presented
in Fig. 7 as representative. The reduction in the exo-
thermic peak intensity under vacuum than that in air
may be due to predominance of dissociation over exo-
thermic decomposition. Thus, it seems that removal of
pn molecules precedes the exothermic decomposition
reactions. An increase of exothermic peak intensity in
sealed cups than that in open may be due to decompo-
sition of the complex at early stage and an increasing
contribution of decomposition of gaseous products in
later stages. Similar is the case with other complexes.
The thermal stability of these complexes, as indicated
by TG, decreases in the order:
In order to examine the response of the complexes
in a condition of rapid heating, D was measured. The
E
time required for thermal explosion at a particular tem-
perature decreases in the order (Table 3)
[
Cr(pn) ](ClO ) >[Mn(pn) ](ClO ) >
2 4 2 2 4 2
[
Zn(pn) ](ClO ) >[Ni(pn) ](ClO ) >[Cu(pn) ](ClO )
2 4 2 2 4 2 2 4 2
Thus, it should be noted that D data also show a
E
trend similar to the thermal decomposition result. The
relative thermal stability of the complexes are in the
same order under the condition of rapid heating.
Moreover, there appears to be a direct correlation be-
tween thermal decomposition and explosion. The val-
ues of E and E* are in agreement with this order. The
values of the decomposition temperature, E, time for
[
Cr(pn)
Zn(pn) ](ClO ) >[Ni(pn) ](ClO ) >[Cu(pn) ](ClO )
4 2
2 4 2 2 4 2
](ClO ) >[Mn(pn) ](ClO ) >
[
2
4 2
2
4 2
2
It was recorded that the exothermic peak temper-
ature in DTA decreases in the same order.
The analysis of kinetics of isothermal TG using
model fitting method results some uncertainty about
mechanism because of composite nature of decomposi-
tion of these complexes. Out of various reaction models
(Table 3), a ‘best fit’ model is selected on the basis of
statistical parameter ‘r’, the model resulting r~1 being
the ‘best fit’. As it was observed that there are many
models having equal values of ‘r’ hence the selection of
‘
best fit’ model becomes difficult. Also all these models
result nearly equal values of E for a particular sample,
irrespective of the equations used. Average values of
–1
163.8, 155.4, 140.7, 118.9 and 148.3 kJ mol have been
obtained as E from different equations for isothermal
decomposition of the complexes of Cr, Mn, Ni, Cu and
Zn, respectively. It is difficult to assign this single value
of activation energy to a particular process in complex
decomposition reactions. A plot (Fig. 8) of all the values
of E vs. the respective lnA obtained from different mod-
els indicates that these values fall in an almost straight
line and hence show the existence of kinetic compensa-
tion effect.
Fig. 8 The linear dependence of lnA on E for all the com-
plexes of the elements shown
J. Therm. Anal. Cal., 82, 2005
359

SINGH, PANDEY
explosion at a particular temperature and E* are low-
3 D. Sheng and F. Ma, Huogonpin, 41 (1997) 36.
4
5
S. A. Dehrle, J. Energ. Mater., 15 (1997) 125.
G. Singh, I. P. S. Kapoor and D. K. Pandey, J. Energ. Mater.,
0 (2002) 223.
G. Singh and D. K. Pandey, J. Indian Chem. Soc.,
0 (2003) 361.
G. Singh and D. K. Pandey, Propellants, Explos. Pyro.,
8 (2003) 231.
est for Cu and highest for that of the Cr complex. The
ionic size of the central atom, their electron affinity,
oxidation number etc., may be the contributing factor
for this trend, but in absence of any firm data, these
explanations remain conjectural. A decrease of sam-
ple mass (from 20 to 10 mg) causes an increase of
time required for thermal explosion at a particular
temperature (Table 3), which is indicative of self-
heating of the samples. A similar variation of explo-
sion time with the amount of the sample taken was
studied with all the complexes.
2
6
7
8
2
8 H. Nakai and Y. Deguchi, Bull. Chem. Soc. Jpn.,
48 (1975) 2557.
9 S. Pal and L. Jansonne, Magy. Kem. Foly., 81 (1975) 70;
CA 83, 21077j.
1
1
1
1
0 R. J. Fereday, P. Hodgson, S. Tyagi and B. J. Hathaway,
J. Chem. Soc., Dalton Trans., 2070 (1981).
1 E. D. Estes, W. E. Estes, W. E. Hatfield and D. J. Hodgson,
Inorg. Chem., 14 (1975) 106.
Conclusions
2 E. Luukkonen and A. Pajunen, Suom. Kemistilehti,
B46 (1993) 292; CA 80, p. 75240
The thermal studies carried out using TG-DTA (in
3 G. Singh and R. R. Singh, Res. Ind., 23 (1978) 92.
N ) and non-isothermal TG and DTA in air, provide
2
14 G. Singh, I. P. S. Kapoor and S. K. Vasudeva,
Indian J. Technol., 29 (1991) 589.
5 G. Singh, I. P. S. Kapoor and S. Jacob, J. Sci. Ind. Res.,
9 (2000) 575.
an understanding of the nature of energetic complexes
during thermal analysis. These complexes decompose
in single step which are highly exothermic. The rate
of decomposition is somewhat fast in air in contrast to
nitrogen. A conventional model fitting approach fails
to describe any change in the mechanism of the iso-
thermal decomposition. The isoconversional method
shows that the mechanism of thermal decomposition
changes as the reaction proceeds. Measurements of
1
1
1
5
6 G. Singh, I. P. S. Kapoor and S. Jacob,
Indian J. Eng. Mater. Sci., 5 (1998) 140.
7 A. I. Vogal, in J. Bassett, R. C. Denny, G. H. Jeffery and
J. Mendham (Eds), Text Book of Quantitative Inorganic
th
Analysis, Longman, 4 Edn., London 1985.
18 N. Semenov, Chemical Kinetics and Chemical Reactions,
Clarendon Press, Oxford 1935, Chapter 2.
D
E
indicate that the mechanism of thermal explosion
19 E. S. Freeman and S. Gordon, J. Phys. Chem., 60 (1956) 867.
2
2
0 J. Zinn and R. N. Rogers, J. Phys. Chem., 66 (1962) 2646.
1 K. Nakamoto, Infrared and Raman Spectra of Inorganic
and Coordination Compounds, Wiley and Sons,
New York 1978, p. 206.
is the same for all these complexes.
Acknowledgements
2
2
2
2
2 C. W. Robert, Handbook of Physics and Chemistry,
CRC Press, Vol. 66, Florida 1996, p. 197.
We are thankful to Head, Chemistry Department, DDU
Gorakhpur University, Gorakhpur for laboratory facility,
DRDO, New Delhi for financial support and Dr. Santosh
Kumar Pandey, New Custom House Laboratory, Mumbai for
IR and elemental analysis. The Director, RSIC Nagpur is also
thanked for TG-DTA analysis.
3 L. S. Prabhumirashi and J. K. Khoje, Thermochim. Acta,
3
83 (2002) 109.
4 T. D. George and W. W. Wendlandt, J. Inorg. Nucl. Chem.,
5 (1963) 395.
5 K. Nagase and H. Yokobayash, Bull. Chem. Soc. Jpn.,
7 (1974) 2036.
6 S. Vyazovkin, Thermochim. Acta, 355 (2000) 155.
7 S. Vyazovkin and C. A. Wight, Annu. Rev. Phys. Chem.,
8 (1997) 125.
2
4
2
2
References
4
1
B. Hariharanath, A. G. Rajendran, S. K. Chandrabhanu,
rd
M. Ravindran and C. B. Kartha, in: Proceedings of 3 Inter-
Received: February 19, 2005
In revised form: June 2, 2005
national High Energetic Materials Conference and Exhibit,
HEMCE-2000, p. 469.
2
Z. S. Guan, Y. Chen, Z. W. Yi and M. J. Yan, Propellants,
Explos. Pyro., 22 (1997) 36.
DOI: 10.1007/s10973-005-6625-8
360
J. Therm. Anal. Cal., 82, 2005