45th AIAA/ASME/SAE/ASEE Joint Propulsion Conference & Exhibit
2 - 5 August 2009, Denver, Colorado
AIAA 2009-4963
Improvement of catalytic decomposition of ammonium
nitrate with new bimetallic catalysts
Kamal Farhat,* Weimin Cong†, Yann Batonneau,‡ and Charles Kappenstein§
Université de Poitiers, LACCO, Laboratoire de Catalyse en Chimie Organique, UMR CNRS 6503, F-86022
Poitiers, France
Ammonium nitrate NH4NO3 (AN) is a proposed candidate for energetic ionic liquids and
solid propellants. The decomposition of aqueous NH4NO3 (50-55 wt-%), in the thermal
condition and in the presence of various mono- and bimetallic catalysts, was investigated
using thermal analysis (DTA-TGA), batch reactor and dynamic flow reactor with on-line
MS analysis. The first results are as follows: heating in the absence of catalyst shows the
quantitative only endothermic vaporization of water and AN have been evidenced into
ammonia and nitric acid even at high temperature. In the presence of catalysts, a dramatic
change is observed. All monometallic catalysts (supported Pt, Fe, Cu or Zn) present a true
catalytic decomposition reaction linked to exothermic peaks. However, only Pt-based
catalyst was able to trigger the decomposition at lower temperature (210 °C). Nevertheless,
tests in batch reactor reveals mediocre results associated to very slow AN decomposition.
Bimetallic catalysts M-M’/Al2O3-Si (M, M’ = Fe, Cu, Zn, Pt) have been evaluated too. The
catalytic decomposition depends on the active phase and on the preparation method of the
bimetallic catalysts. The addition of zinc or copper on non-reduced platinum catalyst
(PtCuAl-NR and PtZnAl-NR) increases the catalytic effect of platinum and the results
display a beneficial effect disclosed by a violent one-step decomposition. On the contrary, the
addition of zinc or copper on reduced platinum metal leads to less active catalysts and the
decomposition occurs in two steps. This activity difference could be mainly related to the
formation zinc-platinum and copper-platinum alloys when adding the second metallic
precursor on non-reduced platinum, followed by a final reduction. Whatever the catalyst
(PtAl, PtCuAl-NR or PtZnAl-NR), the results obtained using a dynamic reactor reveal the
presence of the same gaseous and condensed products: major nitrogen and nitric acid and
no oxygen; the formation of nitrogen oxides NO and N2O depends on the catalyst nature:
minor for PtAl and medium for PtCuAl-NR and PtZnAl-NR.
I - Nomenclature
Cp
=
S0(298) =
M
=
Tadia
=
=
Tm
∆P
=
n
=
Tdecomp
=
∆rH0(298) =
ADN
=
AN
=
HAN
=
HNF
=
molar heat at constant pressure (J·mol-1·K-1)
standard entropy at 298 K (J·mol-1·K-1)
molecular weight (g·mol-1)
adiabatic temperature after decomposition (°C)
melting temperature (°C)
pressure variation
molar quantity (mol)
decomposition temperature (°C)
standard enthalpy of reaction (kJ·mol-1)
Ammonium DiNitramide (NH4)+(N(NO2)2)Ammonium Nitrate (NH4)+(NO3)HydroxylAmmonium Nitrate (NH3OH)+(NO3)Hydrazinium NitroFormate (N2H5)+(C(NO2)3)-
*
Ph. D. student, Chemistry Department, [email protected].
Master student, Chemistry Department, Weimin [email protected].
‡
Assistant Professor, Chemistry Department, [email protected], AIAA member.
§
Professor, Chemistry Department, [email protected], AIAA Member.
†
1
American Institute of Aeronautics and Astronautics
Copyright © 2009 by the American Institute of Aeronautics and Astronautics, Inc. All rights reserved.
I - Introduction
E
nvironmental concerns associated with running cost reduction lead to the replacement of current hydrazinebased propellants (monopropellant for satellite engine, bipropellant for launcher upper-stage) and ammonium
perchlorate (launcher booster).1-6 Hydroxylammonium nitrate NH3OHNO3 (HAN), ammonium nitrate NH4NO3
(AN)7-9, ammonium dinitramide NH4N(NO2)2 (ADN) and hydrazinium hydroformate N2H5C(NO2)3 are proposed,
since about one decade, as oxidizer candidates for energetic aqueous ionic liquids and for new solid propellant
formulation. They have to be associated to efficient and stable catalysts, able to trigger the decomposition at low
temperature and to form selectively the thermodynamic products. Recently, we presented during previous Joint
Propulsion Conferences, the first results concerning the complete reaction mass balance of thermal and catalytic
decomposition of HAN-,4, ADN- and AN-based propellants10 using platinum supported on alumina as catalyst.
AN is the one possible component of industrial explosives, f.i. compositions such as ANFO (ammonium
nitrate-fuel oil) or amatol. However, its use in the field of propellants/pyrotechnics, unlike ammonium perchlorate
(AP) which is the main oxidizer of modern solid propellants, is rather limited. Its principal use in propellants is
restricted to low burning rate (BR), low performance applications, such as gas generators for turbo pumps of liquid
propellant rocket engines or emergency starters for jet aircraft.9 Moreover, based on previous works carried out in
our laboratory4, 10 ammonium nitrate was evidenced to be a decomposition intermediate of ADN and HAN.
Therefore, the main objective of this paper is the control and improvement of the catalytic decomposition of
ammonium nitrate.
II - Experimental part
The procedure describing the decomposition of an aqueous solution of ammonium nitrate using thermal analysis
apparatus and a constant volume batch reactor under argon atmosphere has been already described.3 A dynamic flow
reactor with online mass spectroscopy analysis has been presented too.10. High purity solid AN (Aldrich) was used
to prepare aqueous solutions containing 50 to 56 wt.-% AN. The decomposition has been carried out by using:
(1) Thermal analysis apparatus (TA instrument SD2960), the decomposition reaction has been followed under
argon gas flow (100 mL min-1) with a ramp of 5 or 10 K·min-1 up to 400 °C after an isotherm at 25 °C for 5 or 10
min. Aluminum crucibles with caps have been used; the volume of the solution is about 10 µL; the catalyst mass is
about 15 mg.
(2) Constant volume batch reactor; in this case, the solution (typically 100 µL) is injected in argon atmosphere (1
bar) and heated with a fixed slope at a defined temperature; the catalyst mass is about 160 mg thus keeping the same
propellant/catalyst mass ratio as for thermal analysis.
Various monometallic catalysts M/Al2O3-Si (M = Pt, Cu, Zn and Fe; samples MAl) and bimetallic catalysts MM’/Al2O3-Si (M, M’ = Fe, Cu, Zn, Pt; samples noted M-M'Al) supported on silica-doped alumina were prepared and
then evaluated. All the catalysts are prepared by impregnating the support with metal precursor solutions:
hexachloplatinic acid H2PtCl6 for Pt (to have 10 wt.-%); metal nitrates for Cu, Zn and Fe (to get 5 wt.-% of metal).
The preparation of the Pt-based bimetallic catalysts has been carried out via two procedures: impregnation of the
second metal on the pre-reduced platinum (sample label MPtAl-R, M = Cu or Zn) or impregnating the second metal
on non-reduced platinum-based catalyst (sample label MPtAl-NR, M = Cu or Zn). The catalysts have been
characterized by using X ray diffraction (XRD) and transmission electron microscopy (TEM).
III -
Thermal decomposition of ammonium nitrate
A. Thermal analysis (DTA-TGA)
The thermal behaviour of the aqueous solution of AN (56 wt.- %)-water mixture is presented in Figure 1. The
DTA curve shows only endothermic phenomena: a large endothermic peak with a minimum at 111 °C corresponds
to the full evaporation of water with expected 44 % weight loss. No phase transition of solid AN was observed in
this case but only melting at 170 °C. The second weight loss starts at about 250 °C and is completed at 325 °C, this
weight loss is accompanied by a strong second endothermic peak due to the evaporation of liquid ammonium nitrate.
According to literature data11, 12 this evaporation is initiated by proton transfer, followed by the dissociation into a
gaseous mixture of ammonia and nitric acid.
NH4NO3(aq) NH3(g) + HNO3(g) NH4NO3(g) NH4NO3(s) + NH4NO3(aq)
According to its endothermic behaviour, ammonium nitrate solutions were not tested in batch reactor. Moreover,
the decomposition tests using the dynamic flow reactor have been presented at the previous JPC conference.10
2
American Institute of Aeronautics and Astronautics
120
∆T, °C mg
Weight, %
-1
0.4
100
246 °C
310 °C
277 °C
80
0.2
170 °C
60
0
111 °C
40
-0.2
20
281 °C
Time, min
0
0
20
40
60
80
100
-0.4
120
Figure 1. DTA-TGA curves of the thermal behaviour of AN 56 wt.-%-water mixture (10 µL, 5 K min-1).
IV -
Catalytic decomposition of ammonium nitrate on monometallic catalysts
A. Thermal analysis (DTA-TGA)
The decomposition of AN 50 wt.- %-water in the presence of four MAl monometallic catalysts has been carried
out and an example of DTA-TGA results are presented in Figure 2. All monometallic catalysts (supported Pt, Fe, Cu
or Zn) present a catalytic activity toward AN decomposition reaction evidenced by the presence of exothermic
peaks; the exothermic peak profile depends obviously on the active phase of the catalyst. The decomposition of
liquid AN occurs slowly in one step at temperature higher than 270 °C, except for the Pt-based catalyst (PtAl, 210
°C).
120
Weight / %
0.4
∆ T / °C/mg
-a-
120
Weight / %
110
0.4
∆T / °C/mg
-b-
110
213 °C
100
0.3
0.3
100
274 °C
90
90
80
0.2
0.2
80
70
60
0.1
70
0.1
60
50
Time / min
40
0
10
20
30
40
120
Weight / %
50
60
0
0
0
0.4
∆ T / °C/mg
-c-
Time / min
50
70
10
20
30
50
120
Weight / %
110
40
60
70
∆ T / °C/mg
-d-
0.4
110
284 °C
100
0.3
90
100
0.3
90
80
0.2
70
292 °C
80
0.2
70
60
0.1
50
60
0.1
50
Time / min
Time / min
40
0
0
10
20
30
40
50
60
70
40
0
10
20
30
40
50
60
70
80
90
0
100
Figure 2. Decomposition of AN 50 wt.- %-water mixture in the presence of the catalysts PtAl (a), FeAl10 (b),
CuAl (c) and ZnAl (d); 10 µL of the mixture, ramp 5 °C min-1.
3
American Institute of Aeronautics and Astronautics
The DTA profile show slow energy release due to AN decomposition. Accordingly, Pt-based sample appears to
be the most active catalyst (lower onset decomposition temperature) and from these results, we can sort the catalysts
According to their activity:
PtAl > CuAl > FeAl10 > ZnAl.
Therefore, only the Pt-based monometallic catalyst (PtAl) was tested in batch reactor.
B. Batch reactor
Decomposition of AN (50 wt.-%)-water mixture in the presence of Pt-based catalyst (PtAl) in temperature
increase mode was investigated; the results are presented in Figure 3. Despite the catalytic activity demonstrated by
thermal analysis, the Pt-based catalyst (PtAl) leads to disappointing results; the decomposition occurs very slowly
with low temperature and pressure increases, in agreement with the DTA-TGA profiles and a slow decomposition
rate and heat release during AN decomposition reaction.
350
1800
T / °C
P / mbar
1700
300
1600
250
1500
200
1400
150
1300
100
1200
50
1100
Time / s
0
0
500
1000
1500
1000
2000
Figure 3. Decomposition of AN 50 wt.- %-water in the presence of PtAl using batch reactor in argon
atmosphere (1 bar, 100 µL, 10 K min-1).
V - Catalytic decomposition of ammonium nitrate on bimetallic catalysts
A. Thermal analysis (DTA-TGA)
For the bimetallic catalysts M-M’/Al2O3-Si (M, M’ = Fe, Cu, Zn, Pt), the decomposition depends on the active
phase and on the preparation method. All DTA-TGA results are summarized in Figure 4; the temperature
decomposition and decomposition steps with the corresponding weight loss are presented. From this figure the
bimetallic catalysts based on Fe, Cu and Zn show similar low activity toward AN decomposition, this low activity is
mainly linked to the high decomposition temperatures, despite their ability to decompose AN in one step.
However, the addition of zinc or copper to reduced platinum metal (noted PtCuAl-R and PtZnAl-R) leads to an
improvement of the catalytic activity by comparison with Pt-monometallic sample, despite the two-step AN
decomposition (max. at 178 and 210 °C) (Figure 5-a). On the contrary, the addition of zinc or copper to non-reduced
platinum catalyst (noted PtCuAl-NR and PtZnAl-NR) increases drastically the catalytic effect of platinum with a
violent one-step decomposition starting at 173 °C (close to the melting point of AN) and an exothermic maximum at
180 °C (Figure 5-b).
4
American Institute of Aeronautics and Astronautics
100 %
ZnCu-SR
ZnCu-NR
100 %
100 %
100 %
57 %
43 %
100 %
34 %
51 %
66 %
200
49 %
77 %
23 %
250
FeCu-SR
FeCu-NR
T2
100 %
T1
T / °C
300
CuFe-SR
CuFe-NR
350
150
PtZn-SR
PtZn-NR
PtZn-R
PtZn-AR
PtCu-SR
PtCu-NR
FePt10
PtFe5
0
PtCu-AR
PtCu-R
50
CuZn-SR
CuZn-NR
100
Catalysts
Figure 4. DTA-TGA results of the AN 56 wt.-%-water mixture in the presence of different bimetallic
catalysts: decomposition temperature (T1, T2) and mass loss of each observed step.
From the Figure 5, it appears that the catalyst made without intermediate reduction (PtCuAl-NR and PtZnAl-NR)
displays the best activity by decomposing AN rapidly in one step at low temperature (173 °C). Moreover, the
reaction decomposition appears more exoenergetic (more energy released). For the catalyst prepared with an
intermediate reduction step (PtCuAl-R and PtZnAl-R), the decomposition occurs slowly in two steps, thus showing
a moderate catalytic activity. These activity differences can be linked to the presence of platinum-copper alloys in
PtCuAl-SR sample and to the distribution of the metallic particles (see characterization part).
120
∆T, °C mg -1
Weight, %
110
178 °C
90
120
80
0.5
110
0.4
100
0.3
90
0.2
80
0.1
70
60
0
60
50
-0.1
50
-0.2
40
173 °C
Time, min
40
0
10
20
30
40
50
60
70
0.6
0.5
0.4
-b0.3
210 °C
70
∆ T, °C mg -1
Weight, %
180 °C
-a-
100
0.6
173 °C
0.2
0.1
Time, min
0
10
20
30
40
50
60
0
70
Figure 5. DTA-TGA curves of the catalytic decomposition of AN (56 wt.-%)-water mixture in the presence
(a) PtCuAl-R and (b) PtCuAl-NR catalysts (10 µL, 10 °C min-1).
B. Batch reactor
Based on the DTA-TGA results, only the bimetallic catalysts PtCuAl-NR and PtZnAl-NR have been selected to
be tested using the batch reactor in temperature increase mode. Figure 6 shows the temperature and pressure
evolution versus time for the decomposition of AN 50 wt.-%-water mixture in the presence of PtCuAl-NR (Figure
6-a) and in the presence of PtZnAl-NR (Figure 6-b). The curves show a rapid temperature increase at the
decomposition temperature for both catalysts; this temperature increase is accompanied by a sharp pressure increase
indicating a very fast decomposition reaction rate.
Moreover, the good catalytic activity obtained in the presence of the bimetallic samples PtCuAl-NR and PtZnAlNR, was evidenced by rapid temperature and pressure increases. These results agree well with the thermal analysis
data showing high exothermic and rapid decomposition.
5
American Institute of Aeronautics and Astronautics
400
350
1600
P / mbar
-a-
T / °C
400
1600
-b-
T / °C
1500
P / mbar
350
1500
300
300
1400
250
200
1300
1400
250
200
1300
150
150
1200
1200
100
100
1100
50
Time / s
Time / s
0
0
1000
0
200
400
600
800
1000
1100
50
0
1200
300
600
900
1200
1000
1500
Figure 6. Catalytic decomposition of AN (50 wt.-%)-water in the presence of PtCuAl-NR (a) and PtZnAl-NR
(b) as catalysts using batch reactor in argon atmosphere (1 bar, 100 µL, 10 K min-1).
All batch reactor results including decomposition temperature, pressure increase, reaction rate and quantity
released of gaseous products are gathered in Table 1. From these results we can deduce that, the bimetallic catalyst
based on copper (PtCuAl-NR) presents again a better activity than the Zn-based sample (PtZnAl-NR); this activity
differences is mainly linked to the lower decomposition temperature (174 °C for PtCuAl-NR and 202 °C for
PtZnAl-NR) and higher decomposition reaction rate (236 mbar s-1 for PtCuAl-NR and 103 mbar s-1 for PtZnAl-NR).
However, both catalysts show identical pressure increase revealing the formation of the similar quantity of gaseous
products, leading thus to the conclusion that the same decomposition reaction occurred.
Table 1. AN 50 wt.-% onset decomposition temperature, pressure increase and slope for the decomposition
reaction in the presence of various bimetallic catalysts.
Catalyst
Tdec /°C
Tmax /°C
∆P /mbar
Slope /mbar s-1
ngas /mmol
ngaz/nAN
PtCuAl-NR
174
327
78
236
0.352
0.460
PtZnAl-NR
202
327
77
103
0.327
0.427
VI -
Catalysts characterization
The bimetallic catalysts have been characterized by using XRD and TEM. A typical XRD example
corresponding to the bimetallic catalysts based on Pt and Zn is presented in Figure 7. The XRD results show that the
preparation method of the catalysts has an important impact on the catalyst structure and surface distribution.
Indeed, the addition of zinc (or copper) on reduced platinum based catalyst leads to weak platinum-zinc interactions
by formation of two well-defined crystalline phases Pt and ZnO (PtZnAl-R catalyst); these phases are well dispersed
on catalyst surface. On the contrary, when adding zinc (or copper) on non reduced platinum precursor, other phases
have been detected, mainly the formation of Pt-Zn alloy for PtZnAl-NR catalyst sample (or Pt-Cu alloy for PtCuAlNR sample). The formation of such alloys is linked to the strong zinc-platinum (or copper-platinum) interactions. In
these catalysts, the absence of strong platinum diffraction peaks can be explained by the presence of small Pt-Zn
alloy particles displaying a good dispersion on the surface.
6
American Institute of Aeronautics and Astronautics
Pt
PtZn
Pt
Pt
ZnO
PtZn-R
PtZn Pt
PtZn
PtZn
Pt
PtZn-NR
20
30
40
50
60
70
80
90
2 th e ta / °
Figure 7. XRD patterns of PtZnAl-NR and PtZnAl-R bimetallic catalysts.
The transmission electronic microscopy (TEM) results (Figure 8) of the catalysts based on platinum and zinc
show an important difference on the particles distribution on the catalysts surface. The TEM image of PtZnAl-R
sample shows the presence of very big isolated platinum particles and small Pt-Zn alloy particles, thus disclosing a
heterogeneous particle distribution on the catalyst surface. However, in the case of PtZnAl-NR catalyst, only Pt-Zn
alloy nanoparticles are observed, showing thus a homogeneous particle distribution on the catalyst surface.
Particles number
200
150
100
50
0
0
(a)
(b)
(c)
2
4
6
8
10
12
14
Particles size
Figure 8. TEM image of: (a) PtZnAl-R sample with large Pt particles and (b) PtZnAl-NR catalyst showing
PtZn nanoparticles; (c) Pt-Zn alloy particle distribution for PtZnAl-NR catalyst.
VII - Thermodynamic considerations
The presence of major nitric acid (kinetic product) beside nitrogen (thermodynamic product) can be explained on
the basis of thermodynamic data13 and equilibrium calculations, using HSC code.14
Table 2 (taken from Ref 10) displays the decomposition enthalpy, entropy (per mol of AN) and the adiabatic
temperature for two decomposition schemes. We can observe that the formation of nitric acid (Eq. 2) leads to higher
energy release and adiabatic temperature by comparison with the formation of the sole thermodynamic products
nitrogen, steam and oxygen (Eq. 1).
The equilibrium composition after the decomposition was calculated in the range 0-1000 °C, including the
following possible thermodynamic and kinetic products: N2(g), N2O(g), NO(g), NO2(g), HNO(g), HNO2(g),
HNO3(g), H2O(g) and O2(g). The thermodynamic products are as expected nitrogen, steam and oxygen in the whole
temperature range. But, if we omit the formation of oxygen, then different kinetic products appear whose amounts
depend strongly on the temperature as can be seen in Figure 9. At low temperature (less than 250 °C), gaseous nitric
acid appears beside major steam and nitrogen, whereas nitric oxide NO2 forms at higher temperature.
7
American Institute of Aeronautics and Astronautics
Table 2. Balanced equations, decomposition enthalpy, decomposition entropy and adiabatic temperature for
two ammonium nitrate (AN) decomposition schemes.
Eq.
∆rH°(298) /kJ.AN-mol-1
Decomposition balanced equation
∆rS°(298) /J.K-1.AN-mol-1
Tadia /°C
(1) 2 NH4NO3(s) = O2(g)+ 4 H2O(g) + 2 N2(g)
-118.1
521
970
(2) 2.5 NH4NO3(s) = HNO3(g) + 4.5 H2O(g) + 2 N2(g)
-123.3
257
989
kmol
File: E:\2007-JPC-ionic-liquids\GibbsAN.OGI
2.0
H2O(g)
1.5
1.0
N2(g)
NO2(g)
0.5
HNO3(g)
NO(g)
0.0
0
200
400
600
800
1000
Temperature
C
Figure 9. Product equilibrium composition versus temperature after the decomposition of 1 kmol of
ammonium nitrate. The formation of oxygen is omitted.
VIII - Conclusion
In this work, the decomposition of aqueous ammonium nitrate (AN) solutions, in the thermal condition and in
the presence of various mono- and bimetallic catalysts, was investigated using thermal analysis (DTA-TGA), batch
reactor and dynamic flow reactor (presented in 44th JPC conference10).
In the presence of catalysts, a dramatic change of the decomposition behaviour of AN is observed compared to
the thermal decomposition. All monometallic catalysts (supported Pt, Fe, Cu or Zn) present a true catalytic
decomposition reaction linked to exothermic peaks. However, only Pt-based catalysts were able to trigger the
decomposition at low temperature (about 210 °C). Nevertheless, tests in batch reactor reveal mediocre results
associated to very slow AN decomposition (weak temperature and pressure increases).
Bimetallic catalysts M-M’/Al2O3-Si (M, M’ = Fe, Cu, Zn, Pt) have been evaluated too. The catalytic
decomposition depends on the active phase and on the preparation method of the bimetallic catalysts. Bimetallic
catalysts based only on Fe, Cu and Zn show similar low activity (high decomposition temperature), despite their
ability to decompose AN in one step.
The addition of zinc or copper on non-reduced platinum catalyst (PtCuAl-NR and PtZnAl-NR) increases the
catalytic effect of platinum and the results display a beneficial effect with violent one-step decomposition. On the
contrary, the addition of zinc or copper on reduced platinum metal leads to less active catalysts and the
decomposition occurs in two steps. This activity difference could be mainly related to the formation zinc-platinum
and copper-platinum alloys when adding the second metallic precursor on non reduced platinum, followed by a final
reduction.
The good catalytic activity obtained in the presence of the bimetallic samples PtCuAl-NR and PtZnAl-NR was
evidenced by rapid temperature and pressure increases in batch reactor. Whatever the catalyst (PtAl, PtCuAl-NR or
PtZnAl-NR), the DR-MS results reveal the presence of the same gaseous and condensed products: major nitrogen
8
American Institute of Aeronautics and Astronautics
and nitric acid; whereas, NO and N2O amounts depend on the catalyst nature: minor for PtAl and medium for
PtCuAl-NR and PtZnAl-NR.
From all these results, the following balanced equations are proposed:
In the presence of PtA catalyst:
Major decomposition reaction producing N2 and HNO3:
5 NH4NO3(aq) 4 N2(g) + 2 HNO3(g) + 9 H2O(g)
Minor reactions producing NO and N2O:
2 NH4NO3(aq) N2(g) + 2 NO(g) + 4 H2O(g)
NH4NO3(aq) N2O(g) + 2 H2O(g)
In the presence of PtCuAl-NR or PtZnAl-NR catalysts:
12 NH4NO3(aq) 8.5 N2(g) + 4 HNO3(g) + N2O(g) + NO(g) + 22 H2O(g)
Acknowledgements
We want to thank ESA and CNES for their constant interest in this study. KF acknowledges the Région PoitouCharentes for a Ph.D. fellowship.
References
1
Eloirdi, R., Rossignol, S., Duprez, D., Kappenstein, C., Pillet, N., and Melchior, A., "Decomposition of different
monopropellants at laboratory level methodology, experimental results and performance calculations. Application to
HAN based propellants and H2O2," European Space Agency, [Special Publication] SP, Vol. SP-484, 2001, pp. 148155.
2
Courthéoux, L., Rossignol, S., Kappenstein, C., and Pillet, N., "improvement of Catalysts for the Decomposition of
HAN-Based Monopropellant - Comparison Between Aerogels and Xerogels," AIAA-2003-4645, 39th
AIAA/ASME/SAE/ASEE Joint Propulsion Conference and Exhibit, Huntsville, Alabama, USA, July 20-23, 2003.
3
Eloirdi, R., Rossignol, S., Kappenstein, C., Duprez, D., and Pillet, N., "Design and use of a batch reactor for
catalytic decomposition of propellants," Journal of Propulsion and Power, Vol. 19, No. 2, 2003, pp. 213-219.
4
Farhat, K., Amariei, D., Batonneau, Y., Kappenstein, C., and Ford, M., "Reaction Balance of Thermal and Catalytic
Decomposition of Nitrogen-Based Ionic Monopropellant," 2007, AIAA paper -2007-5642.
5
Farhat, K., Batonneau, Y., Florea, O., and Kappenstein, C., "Preparation and use of ammonium and sodium azide as
a fuel additive to ionic oxidizer," European Space Agency, [Special Publication] SP, Vol. SP-635, No. 3rd
International Conference on Green Propellant for Space Propulsion and 9th International Hydrogen Peroxide
Propulsion Conference, 2006, 2006, pp. 1-6.
6
Courtheoux, L., Amariei, D., Rossignol, S., and Kappenstein, C., "Thermal and catalytic decomposition of HNF
and HAN liquid ionic as propellants," Applied Catalysis, B: Environmental, Vol. 62, No. 3-4, 2006, pp. 217-225.
7
Ikuta, K. "Engine using ammonium nitrate as oxygen source," Patent N° 99-337694
2001152867, 19991129., 2001.
8
Zhao, X.-B., Hou, L.-F., and Zhang, X.-P., "Thermal decomposition and combustion of GAP/AN/nitrate ester
propellants," Progress in Astronautics and Aeronautics, Vol. 185, No. Solid Propellant Chemistry, Combustion, and
Motor Interior Ballistics, 2000, pp. 413-424.
9
American Institute of Aeronautics and Astronautics
9
Oommen, C., and Jain, S. R., "Ammonium nitrate: a promising rocket propellant oxidizer," Journal of Hazardous
Materials, Vol. 67, No. 3, 1999, pp. 253-281.
10
Farhat, K., Kappenstein, C., and Batonneau, Y., "Thermal and Catalytic Decomposition of AN-, ADN and HNFBased Ionic Monopropellants," 44th AIAA/ASME/SAE/ASEE Joint Propulsion Conference and Exhibit,, July 21-23,
2008, Hartford, CT, 2008, AIAA-2008-4938.
11
Simoes, P. N., Pedroso, L. M., Portugal, A. A., and Campos, J. L., "Study of the decomposition of phase stabilized
ammonium nitrate (PSAN) by simultaneous thermal analysis: determination of kinetic parameters," Thermochimica
Acta, Vol. 319, No. 1-2, 1998, pp. 55-65.
12
Singh, G., Kapoor, I. P. S., Mannan, S. M., and Kaur, J., "Studies on energetic compounds: Part 8 : Thermolysis of
Salts of HNO3 and HClO4," Journal of Hazardous Materials, Vol. 79, No. 1-2, 2000, pp. 1-18.
13
Kappenstein, C., Pillet, N., and Melchior, A., "New nitrogen-based monopropellants (HAN, ADN, HNF, ...).
Physical chemistry of concentrated ionic aqueous solutions.," Proceeding 16-125, Intern. Conf. on Space
Transportation for the XXI Century,, Versailles, May 2002, 2002.
14
Roine, A., Mansikka-aho, J., and Björklund, P., "HSC," Outokumpu HSC chemistry for windows, version 6.0,
2006, pp.
10
American Institute of Aeronautics and Astronautics