ISSN 1070-4272, Russian Journal of Applied Chemistry, 2008, Vol. 81, No. 5, pp. 748!751. + Pleiades Publishing, Ltd.

d., 2008.
Original Russian Text + G.F. Klyakin, V.A. Taranushich, 2008, published in Zhurnal Prikladnoi Khimii, 2008, Vol. 81, No. 5, pp. 714 !717.
INORGANIC SYNTHESIS
ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ
AND INDUSTRIAL INORGANIC CHEMISTRY

Phase Stabilization of Ammonium Nitrate with Binary Additives

Consisting of Potassium Nitrate and Complexone Salts
G. F. Klyakin and V. A. Taranushich

South-Russian State Technical University, Novocherkassk, Rostov oblast, Russia

Received August 2, 2007

Abstract-The paper deals with the search for and optimization of a method for preparing phase-stabilized
ammonium nitrate as oxidant for solid propellants with environmentally friendly combustion products.
The effect exerted on the energy of the V 6 IV and IV 6 III polymorphous transitions of ammonium
nitrate by the total content of the binary additive potassium nitrate3disodium tetrahydrogen nitrilotris-
(methylenephosphonate), component ratio, and temperature and time of the cocrystallizate treatment
was examined.
DOI: 10.1134/S1070427208050030
The principal possibility of prepaing phase-stabi- EXPERIMENTAL
lized ammonium nitrate (PSAN) undergoing no
polymorphous transitions in the temperature range A wide test tube made of heat-resistant glass was
from 350 to +100oC by cocrystallization of ammo- charged with analytically pure grade ammonium
nium nitrate (AN) with binary additives consisting nitrate dried to a moisture content not exceeding
of potassium nitrate and sodium or potassium salts 0.05% (according to Fischer titration). The test tube
of complexones was demonstrated in [1]. However, was placed in an oven and heated to melting. Dehy-
the total content of the binary additive in AN drated NTPNa2 was added to the AN melt at 1753
(7 wt %) appreciably decreases the rated specific 180oC and dissolved with stirring, after which the
impulse of a solid propellant based on the suggested melt was cooled and the fusion cake was finely
PSAN. Therefore, decreasing the concentration of divided. All manipulations with samples after cool-
additives introduced is a topical problem. Prelimi- ing the melt were performed in a box with the rela-
nary experiments showed that the strongest effect on tive humidity of air not exceeding 50%. All the
the phase stability of AN is exerted by the total experiments were duplicated.
content of a binary additive consisting of potassium Differential thermal analysis of the powder (frac-
nitrate and a complexone salt and by the ratio of tion <400 mm) was performed in the temperature
its components. It was also noted that, despite the range from 350oC to melting. The sample weight
measures taken to ensure maximal dehydration of was about 0.1 g, and the heating rate, 3 deg min!1.
the cocrystallizing components and the use of dry The DTA curves were recorded in the coordinates
atmosphere for the subsequent operations, heat sample temperature3difference between the temper-
treatment of the finished cocrystallizates considera- atures of the sample and reference. The energies of
bly decreases the height of the peaks of the V 6 IV the polymorphous transitions J (J g!1) were esti-
and IV 6 III down to their full suppression. There- mated from the areas of the corresponding peaks in
fore, we also examined the effect exerted by the the DTA curve, using a calibration chart.
temperature and time of the heat treatment of the With the aim to gain a general pattern of varia-
cocrystallizates. tion of the PSAN characteristics, the experimental
For a detailed study, as a complexone salt we material was presented in the form of polynomial
chose disodium tetrahydrogen nitrilotris(methylene- mathematical models constructed by standard pro-
phosphonate), NTPNa2, as a substance that shows cedures [2]. When constructing the model, we ex-
the highest inhibiting activity toward polymorphous cluded insignificant (with respect to the Student test)
transitions of AN and is commercially available. terms with the subsequent recalculation, which
748
 PHASE STABILIZATION OF AMMONIUM NITRATE WITH BINARY ADDITIVES
allowed us to obtain adequate models with smaller
numbers of terms.
We examined the effect of the above-mentioned
factors on the energy of the key polymorphous tran-
sitions of ammonium nitrate, V 6 IV and IV 6 III.
In the first step, two factors, the total content of the
binary additive in AN and the relative content of
NTPNa2 in the binary additive, were set constant
(3 and 44%, respectively), and the effect exerted on
the energy of the V 6 IV and IV 6 III transitions
by the heat treatment temperature (from 84 to 99oC,
four levels of variation) and time (from 0.5 to 6 h,
five levels of variation) was examined.
The dependence of the energy of the PSAN V 6
IV polymorphous transition on the temperature and
time of the heat treatment is adequately described
by the equation
JV!IV = 174.1 3 3.974t + 0.0226t2,
where t is the heat treatment temperature (oC).
The statistical insignificance of the coefficients
at terms taking into account the time factor [Eq. (1)]
indicates that the transition energy is independent of
the heat treatment time varied within the examined
range. The graphical interpretation of Eq. (1) is
shown in Fig. 1. The curves in Fig. 1 and the subse-
quent figures are lines of equal energy of the corre-
sponding polymorphous transition (J g!1).
As follows from Fig. 1, degradation of the PSAN
structure with the V 6 IV polymorphous transition
starts at the heat treatment temperature exceeding
90oC practically within 30 min after the sample
reaches the preset temperature, and the energy of the
transition increases in proportion with the temper-
ature squared.
The dependence of the energy of the IV 6 III
polymorphous transition on the temperature and
time of the heat treatment is more complex and is
adequately described by the equation
JIV!III = 342.5 3 7.9t 3 12.07t + 0.137tt + 0.0463t2. (2)
Analysis of the graphical interpretation of Eq. (2)
(Fig. 2, nonshaded area) shows that the energy of
the IV 6 III transition also nonlinearly increases
with an increase in the heat treatment temperature.
The dependence of JIV!III on the heat treatment
time is complex. The temperature of 90oC is a
threshold of a sort, above which the energy of the
IV 6 III transition nonlinearly increases, and below
RUSSIAN JOURNAL OF APPLIED CHEMISTRY
749
t,
h
o
t, C
Fig. 1. Two-dimensional section of the response surface
of model JV!IV [Eq. (1)]. (J) Heat treatment time and
(t) temperature; the same for Fig. 2.
(1)
t,
h
o
t, C
Fig. 2. Two-dimensional section of the response surface
of model JIV!III [Eq. (2)].
which, decreases in the entire range of heat treat-
ment times examined. The lowest energy of the tran-
sition is attained at the lowest temperature and the
longest heat treatment time. Extrapolation of the
two-dimensional section toward lower heat treat-
ment temperature (75oC; Fig. 2, shaded area) al-
lowed us to find the area of zero energies of the
transition.
At the boundary of this area (heat treatment tem-
perature 80oC, time 6 h), we performed a series of
experiments to reveal the dependence of the energy
of the IV 6 III polymorphous transition on the
total content c of the binary additive (from 2 to
4 wt %, three levels of variation) and relative content
of NTPNa2, cNTP, in the binary additive (from 0 to
75 wt %, four levels of variation). Adequate models
of the energies of the V 6 IV and IV 6 III poly-
morphous transitions have the form
JV!IV = 0.83 3 0.0149c cNTP + 0.000075c2NTP. (3)
JIV!III = 17.03 3 2.93c 3 0.411cNTP + 0.0075c2NTP. (4)
Vol. 81 No. 5 2008
750 KLYAKIN, TARANUSHICH
cNTP, wt %
c, wt %
Fig. 3. Two-dimensional section of the response surface
of model JV!IV [Eq. (3)]. (cNTP, c) Content; the same for
Fig. 4.
cNTP, wt %
c, wt %
Fig. 4. Two-dimensional section of the response surface of
model JIV!III [Eq. (4)].
J, J g!1
cNTP, wt %
Fig. 5. Energy of the IV $ III polymorphous transition
as a function of the relative content of NTPNa2, cNTP, in
the binary additive (total content 5 wt %).
Analysis of the graphical interpretation of Eqs. (3)
and (4) (Figs. 3, 4) shows that, at a total content of
the binary additive exceeding 3 wt %, there are areas
of the zero energy of the transition, bounded by
certain values of cNTP.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY
The area of zero values of the V 6 IV transition
energy (Fig. 3) starts at a lower total content of the
bonary additive and exists in a wider range of rela-
tive amounts of NTPNa2 in the additive, compared
to the IV 6 III transition (Fig. 4, nonshaded area).
Extrapolation of the two-dimensional section
(Fig. 4) toward an increase in the total content of
the binary additive from 4 to 5 wt % (Fig. 4, shaded
area) demonstrates the possibility of considerably
expanding the area of the zero energy of the transi-
tion. The synergistic effect of the binary additive is
confirmed experimentally (Fig. 5).
Figure 5 shows that, within the range of relative
content of NTPNa2 in the binary additive from 10
to 40 wt %, the IV 6 III polymorphous transition
is suppressed. The V 6 IV transition in this series
of experiments is observed only at NTPNa2 concen-
trations of 0 and 90%. The PSAN sample with a
total content of the binary additive of 5% and rela-
tive NTPNa2 content of 20% stood ten cycles of
heating and cooling from 350 to +50oC and thermo-
stating at 350oC for 24 h without deterioration of
the phase stability.
We performed experiments on the cocrystalliza-
tion of AN with the binary additive from highly con-
centrated aqueous solutions of AN containing from
1 to 5 wt % water. We found that the presence of
water in an amount exceeding 1 wt % fully sup-
presses the synergistic effect on introducing the
binary additive. The pattern of polymorphous tran-
sitions of the samples obtained does not noticeably
differ from that for AN without additives.
Recent studies [3] showed that the mechanism of
IV $" III polymorphous transitions of AN, including
An containing a KNO3 additive, can be considered
as a chain of several successive events. Prior to the
onset of the phase transition, crystallites and sep-
arate blocks are broken down. This is followed by
transition of the initial phase into a certain inter-
mediate X-ray amorphous state which subsequently
transforms into the new phase. The limiting step is
the transition of the initial phase into the intermedi-
ate X-ray amorphous state, rather than the nuclea-
tion and growth of centers of the new phase.
Based on this pattern, the mechanism of the syn-
ergistic effect in the system under consideration can
be presented as follows. Like any topochemical reac-
tion, the transformation of the initial phase starts
on active centers located on defects of the external
or internal surface of a crystal. In the salt NTPNa2,
the anion size is too large to form a substitution
Vol. 81 No. 5 2008
 PHASE STABILIZATION OF AMMONIUM NITRATE WITH BINARY ADDITIVES
solid solution with ammonium nitrate. Therefore,
in the course of cocrystallization with ammonium
nitrate, NTPNa2 and products of exchange reactions
with system components are adsorbed on defects
of the crystal structure of AN or solid solution of
KNO3 in AN. Interaction of phosphonic acid groups
of the complexone with potassium ions results in
formation of a fairly strong structure suppressing
the active centers and thus impeding the transition
of the initial phase into the X-ray amorphous state.
The same reasoning can also be applied to the V 6
IV polymorphous transition.
CONCLUSIONS
(1) Heat treatment of cocrystallizates of ammo-
nium nitrate with modifying additives is the neces-
sary step for ensuring phase stabilization of ammo-
nium nitrate.
(2) Exceeding the threshold temperature of 90oC
in the heat treatment of phase-stabilized ammonium
nitrate containing the binary additive potassium
nitrate3disodium tetrahydrogen nitrilotris(methyl-
enephosphonate) is exceeded, the structure of phase-
stabilized ammonium nitrate ensuring its phase
stability is broken down.
(3) Phase-stabilized ammonium nitrate contain-
ing 5 wt % binary additive KNO33NTPNa2 and
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 81
751
undergoing no polymorphous transitions V 6 IV
and IV 6 III can be obtained at a relative content
of NTPNa2 in the binary additive of 6 3 48 wt %.
(4) Analysis of the mathematical models describ-
ing the dependences of the energy of the polymor-
phous transition in ammonium nitrate on the con-
centration characteristics of the binary additive and
on the temperature and time of the heat treatment
allowed determination of the conditions for prepara-
tion of phase-stabilized ammonium nitrate exhibiting
phase stability in the range from 350 to +100oC.
REFERENCES
1. Klyakin, G.F., Issledovanie vliyaniya binarnykh doba-
vok na svoistva nitrata ammoniya (Effect of Binary
Additives on Properties of Ammonium Nitrate),
Novocherkassk, 2004, Available from VINITI, Janu-
ary 19, 2004, no. 77-V2004.
2. Ruzinov, L.P., Statisticheskie metody optimizatsii
khimicheskikh protsessov (Statistical Methods for
Optimization of Chemical Processes), Moscow: Khi-
miya, 1972, p. 45.
3. Golovina, N.I., Manelis, G.B., Lempert, D.B., et al.,
in Vysokoenergeticheskie materialy: Demilitarizatsiya
i grazhdanskoe primenenie: Doklady Mezhdunarod-
noi konferentsii [HEMs-2004] (Highly Energetic
Materials: Demilitarization and Civilian Applications:
Proc. Int. Conf. [HEMs-2004]), Belokurikha (Altai
krai), September 6 39, 2004, Biisk: Altai, 2004, p. 37.
No. 5 2008