150
A DSC Study on the Effect of RDX and HMX on the Thermal
Decomposition of Phase Stabilized Ammonium Nitrate
Suresh Mathew, K. Krishnan, and K. N. Ninan
Propellant & Special Chemicals Group, PCM, Vikram Sarabhai Space Centre, Trivandrum 695 022 (India)
Eine DSC-Studie uÈber die Wirkung von RDX- und HMX-ZusaÈtzen
auf die thermische Zersetzung von phasenstabilisiertem Ammo-
niumnitrat
Phasenstabilisiertes Ammoniumnitrat (PSAN) wurde hergestellt
durch Einarbeitung von Kupfer(II)diamminnitrat in das Kristallgitter
von AN. Die Wirkung der beiden energiereichen Verbindungen RDX
und HMX auf die thermische Zersetzung von PSAN wurde untersucht
mittels DSC. Die Zersetzungstemperaturen von PSAN und RDX lie-
gen fast im gleichen Temperaturbereich. Die Zersetzung von PSAN ist
endotherm und die von RDX exotherm, waÈhrend sich ihre Mischung
im VerhaÈltnis 1:1 exotherm zersetzt mit einer hoÈheren WaÈrmeent-
wicklung als bei den Einzelreaktionen, was zuruÈckzufuÈhren ist auf die
Reaktion zwischen den Zersetzungsprodukten von PSAN und RDX.
Obwohl sich HMX bei einer hoÈheren Temperatur zersetzt, wird es bei
Gegenwart von PSAN zu einem wesentlichen Teil bei einer nie-
drigeren Temperatur zersetzt zusammen mitt PSAN und wieder mit
hoÈherer WaÈrmefreisetzung. Die kinetischen Parameter der beiden
exothermen Zersetzungsreaktionen wurden berechnet unter Verwen-
dung zweier Gleichungen mit variabler Zersetzungsgeschwindigkeit
nach der Methode von Kissinger und Ozawa. Die nach Ozawa erhal-
tene Aktivierungsenergie wurde durch ein Iterationsverfahren ver-
bessert. Die nach den drei Methoden erhaltenen Werte zeigen eine
gute U È bereinstimmung. Die kinetischen Parameter fuÈr die
PSAN=HMX-Mischung sind niedriger, wahrscheinlich aufgrund ihrer
hoÈheren WaÈrmefreisetzung.
Summary
Phase stabilized ammonium nitrate (PSAN) was prepared by
incorporating copper(II) diammine nitrate in the ammonium nitrate
(AN) crystal lattice. The effect of two energetic materials viz., RDX
and HMX on the thermal decomposition of PSAN was investigated
using DSC. The decomposition temperatures of PSAN and RDX are
almost in the same temperature range. The decomposition of PSAN is
endothermic and that of RDX is exothermic, while that of a 1:1
mixture of the two is exothermic with a net heat release in excess of
that of the individual reactions, which is attributed to the combustion
reaction among the decomposition products of PSAN and RDX.
Though HMX decomposes at a higher temperature, in presence of
molten PSAN a substantial portion of it decomposes at a lower tem-
perature along with PSAN with a net excess heat release, again due to
the combustion reaction. The kinetic parameters of the two exothermic
decompositions were computed using two equations based on variable
heating rate method viz., Kissinger and Ozawa equations. The acti-
vation energy obtained from Ozawa method was re®ned by an iteration
procedure. There is a close agreement among the values obtained by
the three methods. The kinetic parameters for PSAN-HMX mixture are
lower, probably due to the effect of its higher heat release.
1. Introduction
Composite propellants based on ammonium perchlorate
(AP) as oxidizer are extensively used in rockets and satellite
launch vehicles. However, the HCl exhaust from AP is an
adverse factor from the global environmental point of view.
# WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1998
Propellants, Explosives, Pyrotechnics 23, 150±154 (1998)
Une eÂtude DSC sur l'effet d'additifs RDX et HMX sur la deÂcom-
position thermique de nitrate d'ammonium stabilise en phase
Le nitrate d'ammonium stabilise en phase (PSAN) a eÂte fabrique par
introduction de nitrate diammine de cuivre (II) dans le reÂseau cristallin
de AN. L'effet des deux composeÂs eÂnergeÂtiques RDX et HMX sur la
deÂcomposition thermique a eÂte eÂtudie au moyen de DSC. Les tem-
peÂratures de deÂcomposition de PSAN et RDX se situent presque dans
la meÃme plage. La deÂcomposition de PSAN est endothermique, alors
que son meÂlange dans le rapport 1:1 se deÂcompose de manieÁre exo-
thermique avec un deÂgagement de chaleur plus eÂleve que dans les
reÂactions isoleÂes, ce qui est aÁ imputer aÁ la reÂaction entre les produits de
deÂcomposition de PSAN et RDX. Bien que la tempeÂrature de
deÂcomposition de HMX soit plus eÂleveÂe, cette substance, en preÂsence
de PSAN, se deÂcompose en grande partie aÁ une tempeÂrature plus basse
avec PSAN en deÂgageant aÁ nouveau davantage de chaleur. Les para-
meÁtres cineÂtiques des deux reÂactions de deÂcomposition exothermiques
ont eÂte calculeÂs en utilisant deux eÂquations aÁ vitesse de deÂcomposition
variable suivant la meÂthode de Kissinger et Ozawa. L'eÂnergie d'acti-
vation obtenue selon Ozawa a eÂte ameÂlioreÂe par une meÂthode iteÂrative.
Les valeurs obtenues d'apreÁs les trois meÂthodes preÂsentent une bonne
concordance. Les parameÁtres cineÂtiques du meÂlange PSAN=HMX sont
plus faibles, probablement du fait de leur plus grand deÂgagement de
chaleur.
Therefore, efforts are on to innovate propellants with clean
exhaust. Ammonium nitrate (AN) has, thus, regained
importance in the ®eld of propellants and explosives, more
speci®cally insensitive formulations, because of its HCl free
exhaust and low hazard. However, the stumbling block for
the application of AN as solid propellant oxidizer has been
its dimensional instability caused by polymorphic transi-
tions near the propellant processing and storage tempera-
tures, low energetics and high hygroscopicity. The volume
change of AN, when it is thermally cycled, is undesirable
because of the loss in density and mechanical properties,
unstable combustion, thermal expansion and structural
instability.
The problem of volume change resulting from the phase
transitions can be overcome by the use of phase stabilized
ammonium nitrate (PSAN)(1±4). The phase stabilization of
AN is achieved by the crystal lattice incorporation of metal-
diammine dinitrate complex formed from the reaction of
melt AN and nickel or copper oxide.
The energetic of the PSAN based composite propellant is
lower than that of AP based propellant and therefore war-
rants the incorporation of high energy materials like RDX
or HMX for improving the ballistic performance. As a
preliminary investigation to assess the effect of energetic
materials, we undertook a differential scanning calorimetric
(DSC) study on the thermal behaviour of PSAN with RDX
0721-3115/98/0306±0150 $17.50‡:50=0
Propellants, Explosives, Pyrotechnics 23, 150±154 (1998) A DSC Study on the Thermal Decomposition of PSAN 151

(cyclo-1,3,5-trimethylene-2,4,6-trinitramine) and HMX Table 2. Phenomenological Data and Enthalpy Values of PSAN
(cyclo-1,3,5,7-tetramethylene-2,4,6,8-tetranitramine) as Peak Nature (f ˆ 5 C minÿ1 ) Tm ( C) DH (J gÿ1 ) Process
additives. The study also encompasses the evaluation of the
kinetics of the thermal decomposition of PSAN-RDX and Endotherm 54 20 IV ! II=III
Endotherm 86 3 III ! II
PSAN-HMX mixtures using the DSC peak temperature- Endotherm 125 46 II ! I
program rate relationship by Ozawa(5) and Kissinger(6). An Endotherm 168 58 Melting
iteration procedure(7) for re®ning the activation energy Endotherm 230 1540 Decomposition
values from the Ozawa method was also employed for a
comparison purpose.

enantiotropic changes, depending on whether it is dry or

2. Experimental
2.1 Samples
Phase stabilized ammonium nitrate (PSAN) was prepared
in our laboratory by incorporating copper(II) diammine
nitrate in the AN crystal lattice, by a melt process involving
ammonium nitrate and copper oxide (3%). The prepared
PSAN was sieved and used for the investigation. The
PSAN-RDX and PSAN-HMX samples were prepared by
careful mixing of the two components taken in the weight
ratio of 1:1, in a 5-cm diameter polished-porcelain container
with a polished glass rod.
2.2 Instrumental
The DSC curves were recorded by a Mettler TA 3000
thermal analysis system in conjunction with DSC-20 stan-
dard cell. The heat ¯ow and temperature calibrations of
DSC were done using indium standard. The experiments
were carried out at ®ve heating rates namely 2, 5, 7, 10 and
15 C minÿ1 . Almost constant sample mass of 3  0.1 mg
(PSAN-RDX and PSAN-HMX) was used in all the
experiments. The samples were placed in an encapsulated
aluminium pan (40 ml) with a pierced lid and the atmosphere
was static air.
3. Results and Discussion
The crystallographic details of ammonium nitrate phases
are given(8±12) in Table 1 from which it can be seen that
above ambient temperature AN exhibits either two or three
moist. The presence of moisture even at 0.2% levels results
in the appearance of phase III. The transition temperature
IV ! III, however, does not drop below 50 C for PSAN.
This observation distinguishes the PSAN from pure AN
whose transition temperature IV ! III drops below 50 C at
these moisture levels(13).
Table 2 summarizes the data of DSC peak temperature
and enthalpy of transition recorded for the PSAN sample.
There are ®ve endothermic transitions, corresponding to
three enantiotropic changes followed by melting and
endothermic decomposition with DSC peak maximum
(Tm) ˆ 230 C. The small endothermic peak (DH ˆ 3 J gÿ1 )
at 86 C shows the appearance of phase III due to the pre-
sence of traces of moisture in the sample. However, the
occurrence of the ®rst endothermic peak at 55 C clearly
shows that the sample is phase stabilized and the presence
of the diammine complex in AN crystal lattice as a solid
solution is effective(14). The solid solution formation
restricts the occurrence of phase III and keeps the transition
temperature above 50 C, avoiding caking and preserving
the free ¯ow of the material(13).
The DSC trace of pure RDX shows one sharp endotherm
(Tm ˆ 204 C) corresponding to its melting, followed by an
exothermic peak due to the decomposition of RDX
(Tm ˆ 235 C). The DSC curve of pure HMX shows three
peaks. The weak endothermic peak (Tm ˆ 185 C) is due to
the transformation of the low temperature phase (b) to the
high temperature phase (d) of HMX. The sharp endothermic
peak at 280 C corresponds to melting which is followed by
a strong exothermic peak. This peak immediately after the
melting is due to the self decomposition of HMX(15±16). The
enthalpy change (DH) and the peak temperature for the
exothermic decomposition of RDX and HMX at different
heating rates are shown in Table 3. With increasing heating

Table 1. Crystallographic Details of Ammonium Nitrate Phases

Phase V IV III II I
Crystal system Orthorhombic Orthorhombic Orthorhombic Tetragonal Cubic
Space group Pccn Pmmn Pnma  1m
P42 Pm3m
Z 8 2 4 2 1
Cell parameter a ˆ 7.943 a ˆ 5.745 a ˆ 7.677 a ˆ 5.7193 a ˆ 4.366
b ˆ 7.972 b ˆ 5.438 b ˆ 5.820 c ˆ 4.9326
c ˆ 9.832 c ˆ 4.942 c ˆ 7.140
Stability ÿ100 C 22 C 24 C 82 C 150 C
Moist < ÿ18 C ÿ18±32 C 32±84 C 84±125 C >125 C
Dry < ÿ18 C ÿ18±55 C 55±125 C >125 C
Density (g cmÿ3 ) 1.76 1.72 1.68 1.60 1.55
152 S. Mathew, K. Krishnan, and K. N. Ninan Propellants, Explosives, Pyrotechnics 23, 150±154 (1998)

Table 3. Enthalpy and Peak Temperature of the Exothermic dence of phase III and the dry nature of the sample. The ®rst
Decomposition of RDX and HMX three peaks have been assigned to the orthorhombic to tet-
Heating Rate RDX HMX ragonal, tetragonal to cubic transitions and the melting of
( C minÿ1 ) PSAN. The weak endotherm at 185 C due to the b ! d
DH (J gÿ1 ) Tm ( C) DH (J gÿ1 ) Tm ( C)
transition of HMX is followed by two exothermic peaks
2 2300 223.0 1400 276.0 with Tm at 231 C and 282 C, respectively. The second peak
5 2100 234.0 1200 278.5 (282 C) tallies with the exothermic decomposition of HMX.
7 2200 238.3 1310 282.7
In the temperature region of the ®rst peak (231 C), PSAN
10 2030 241.3 1000 283.3
15 2050 245.0 1010 291.2 decomposes endothermically. Hence the exothermicity of
this peak for the PSAN-HMX sample can be attributed to
the partial decomposition of HMX happening at a lower
temperature in presence of molten PSAN. The endothermic
peak from melting of HMX is not observed in the mixture
showing that the decomposition of HMX takes place before
its melting in presence of molten PSAN. The DSC results of
enthalpy change and peak temperature of the exothermic
decomposition of both PSAN-RDX and PSAN-HMX are
given in Table 4.
It is interesting to calculate the net enthalpy change of the
decomposition reactions of PSAN-RDX and PSAN-HMX.
(DH values corresponding to 5 C minÿ1 are taken for the
calculations since the DSC of PSAN is recorded at this
heating rate). Referring to Tables 2 and 3, the enthalpy
change for the decomposition of PSAN is 1540 J gÿ1 (endo),
for RDX ˆ 2100 J gÿ1 (exo) and for HMX ˆ 1200 J gÿ1
Figure 1. DSC curve of PSAN-RDX. (exo). A 1:1 (by weight) mixture of PSAN and RDX should
result in a net enthalpy change of 280 J gÿ1 (exo), i.e., 770 J
(endo) for 0.5 g of PSAN ‡ 1050 J (exo) for 0.5 g of
rate there is an upward shift in the peak maximum of the RDX ˆ 280 J for 1.0 g of mixture. The observed (Table 4)
exothermic peak and a slight decrease in the DH values. higher value of 1390 J gÿ1 (exo), therefore, corresponds to
The DSC trace of the PSAN-RDX mixture shows ®ve an excess heat release of 1110 J gÿ1 . This indicates gas
endothermic peaks due to the three enantiotropic changes of phase oxidation reaction (combustion) among the decom-
AN, the melting of AN and the melting of RDX, followed position products of PSAN and RDX. A similar trend is
by an exotherm as shown in Fig 1. The peak due to III ! II seen in the case of PSAN-HMX system also. For a 1:1 mix,
(86 C) is very feeble showing evidence of traces of the expected enthalpy change is 170 J gÿ1 (endo). However,
moisture in the sample. DSC shows that the endothermic from Table 4 it can be seen that the combined DH for peaks
decomposition of PSAN is masked by the high exothermic 1 and 2 corresponding to the two-stage exothermic
decomposition of RDX occurring at the same temperature decomposition of PSAN-HMX is 1640 J gÿ1 . In order to
range and the net effect is seen as an exotherm. surpass the expected endotherm (170 J gÿ1 ) to the observed
The DSC curve of PSAN-HMX (Fig. 2) shows four exotherm (1640 J gÿ1 ), a heat release of 1810 J gÿ1 is
endothermic peaks with Tm at 55 C, 125 C, 170 C and required, which must be coming from the oxidation reaction
185 C. Here the peak at 86 C is absent showing no evi- among the decomposition products of PSAN and HMX
happening in peak 1. Comparable values of heat release are
obtained for both the systems (950 J gÿ1 for PSAN-RDX
and 1720 J gÿ1 for PSAN-HMX) when the mean values of

Table 4. Enthalpy and Peak Temperature of the Exothermic

Decomposition of PSAN-RDX and PSAN-HMX
f PSAN:RDX (1:1) PSAN:HMX (1:1)
( C minÿ1)
DH (J gÿ1 ) Tm ( C) DH (J gÿ1 ) Tm ( C)

Peak 1 Peak 2 Peak 1 Peak 2

2 1140 222.4 687 583 218 278
5 1390 232.0 1230 410 231 282
7 1290 238.0 1430 224 236 284
10 1220 242.8 1130 470 240 286
15 1190 248.3 1240 283 246 288
Figure 2. DSC curve of PSAN-HMX.
Propellants, Explosives, Pyrotechnics 23, 150±154 (1998)
DH for the exothermic decomposition of RDX and HMX
and their mixtures with PSAN (from Tables 3 and 4) are
used. The higher range of temperature for the exotherm
suggests HMX as a safer additive in PSAN based pro-
pellants. However, the net gain in speci®c impulse will
depend on the propellant formulation involving other
ingredients such as the polymeric binder and metallic fuel.
3.1 Kinetic Analysis of DSC Data
Since the exothermic peak of PSAN-RDX and ®rst exo-
thermic peak of PSAN-HMX correspond to oxidation
reactions with a synergetic effect of heat release, the kinetic
parameters viz., energy of activation, E and pre-exponential
factor, A for these reactions were evaluated. The Ozawa,
re®ned Ozawa and Kissinger methods were employed for
the purpose, using the data from DSC experiments at ®ve
heating rates between 2 and 15 C minÿ1 . The variation of
peak temperature Tm with heating rate for the exothermic
reaction of PSAN-RDX and PSAN-HMX is given in
Table 4.
3.1.1 Ozawa method(5)
The popularly used Ozawa method is based on the plot
of log (heating rate) vs. reciprocal of the DSC peak
temperature in absolute (1=Tm). The plots for the PSAN-
RDX and PSAN-HMX (stage 1) systems are shown in Figs.
3 and 4, respectively. The slope of the straight line plot is
used for the calculation of activation energy (E) using the
equation:
E ˆ 2:19R d‰log f=d…1=Tm †Š …1†
where d[log f=d(1=Tm)] is the slope of the curve. The
values of A are calculated with the equation:
A ˆ …f E exp E=RTm †=RTm 2 …2†
Figure 3. The Ozawa plot for the exothermic reaction of PSAN-RDX.
A DSC Study on the Thermal Decomposition of PSAN 153
Figure 4. The Ozawa plot for the exothermic reaction of PSAN-
HMX.
3.1.2 Kissinger method(6)
The Kissinger method is basically the plot of ln (f=Tm2)
vs.1=Tm. The Kissinger plots for the exothermic reaction of
PSAN-RDX and PSAN-HMX are shown in Figs. 5 and 6,
respectively. Activation energy (E) is calculated from the
slope of the above plots using the equation:
E ˆ R d‰ln…f=Tm †2 Š=‰d…1=Tm †Š …3†
2
where d‰ln…f=Tm † =d…1=Tm †Š is the slope. The pre-expo-
nential factor (A) was also calculated for ®ve heating rates
using Eq. (2). The E and the computed average values of A
from Ozawa and Kissinger methods are given in Table 5.
The kinetic parameters computed by both the methods are
comparable.
3.1.3 Refinement of activation energy (E) from Ozawa
method
The E value obtained from the Ozawa method is
approximate and therefore requires re®nement(7) which is
done by a series of iterations using the relationship
g(a) ˆ (AE=fR) p(x) where p(x) ˆ Arrhenius temperature
Figure 5. The Kissinger plot for the exothermic reaction of PSAN-
RDX.
154 S. Mathew, K. Krishnan, and K. N. Ninan Propellants, Explosives, Pyrotechnics 23, 150±154 (1998)

additives to PSAN. The decomposition temperature of

HMX is lowered in presence of molten PSAN. The exo-
thermic decomposition of RDX and HMX occurring at the
same temperature range of the endothermic decomposition
of PSAN results in an overall exothermic DSC peak for 1:1
mixture of PSAN-RDX and PSAN-HMX. The net heat
release is in excess of that of the sum of the individual
decomposition reactions, indicating combustion reaction
among the decomposition products of PSAN and
RDX=HMX. This synergetic effect is more for HMX;
however the actual gain in speci®c impulse of a propellant
with this system would depend on all the ingredients and
their formulation.

Figure 6. The Kissinger plot for the exothermic reaction of PSAN-

HMX.
4. References
Table 5. Kinetic Parameters for the Exothermic Decomposition of (1) K. R. V. Szarmes and J. M. Ramaradhya, Can. Patent, 879,586,
PSAN-RDX and PSAN-HMX (stage 1) 31 August, 1971.
(2) W. Engel, Explosivstoffe 1, 9 (1973).
Method PSAN-RDX PSAN-HMX
(3) E. D. Guth, U.S. Patent, 4,552,736, November, 1985.
ÿ1) ÿ1) (4) A. E. Oberth, U.S. Patent, 5,071,630, December, 1991.
E (kJ mol A (s E (kJ molÿ1) A (sÿ1)
(5) T. Ozawa, J. Therm. Anal., 2, 301 (1970).
Ozawa 158.6 1.42461014 144.9 6.17161012 (6) H. E. Kissinger, Anal. Chem., 29, 1702 (1957).
Ozawa 158.5 1.39761014 144.2 5.15561012 (7) ASTM Test Method E 698, Part 41, 79, 1012 (1982).
(Re®ned) (8) M. Ahtee, K. Kurki-Suonio, B. W. Lucas, and A. W. Hewat,
Kissinger 158.2 1.23661014 144.0 4.95461012 Acta. Cryst., A 35, 591 (1979).
(9) B. W. Lucas, M. Ahtee, and A. W. Hewat, Acta Cryst., B 35,
1038 (1979).
(10) B. W. Lucas, M. Ahtee, and A. W. Hewat, Acta Cryst., B 36,
integral, derived by a two-term approximation(17), reported 2005 (1980).
earlier. From Table 5 it can be seen that the values of the (11) C. S. Choi and J. E. Mapes, Acta Cryst., B 28, 1357 (1972).
(12) M. Ahtee, K. J. Smolander, B. W. Lucas, and A. W. Hewat, Acta
re®ned activation energy of the exothermic reactions Cryst. C 39, 651 (1983).
obtained by the iteration methods are very close to the (13) W. Engel, Propellants, Explos., Pyrotech. 10, 84 (1985).
`approximate' E values obtained by the Ozawa method, (14) S. Mathew, N. Eisenreich, and W. Engel, Thermochim. Acta.
showing that the re®nement is unwarranted for these reac- 269=270, 475 (1995).
(15) P. G. Hall, J. Chem. Soc. Faraday Trans, Part 2, 67, 556 (1971).
tions. The kinetic parameters for PSAN-HMX are lower, (16) M. Herrmann, W. Engel, and N. Eisenreich, Propellants, Explos.,
suggesting a more rapid reaction of the mixture due to its Pyrotech. 17, 190 (1992).
higher net heat release. (17) P. M. Madhusudanan, K. Krishnan, and K. N. Ninan, Thermo-
chim. Acta 97, 189 (1986).

4. Conclusions
Incorporation of copper(II) diammine nitrate in the AN
crystal lattice results in the formation of phase stabilized
ammonium nitrate. RDX and HMX can be used as energetic
Acknowledgements
The authors are thankful to the Deputy Director, PCM and the
Director, VSSC for the kind permission to publish this work.
(Received November 11, 1996; Ms 68=96)