Combustion and Flame 162 (2015) 2686–2692

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Combustion and Flame

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c o m b u s t fl a m e

New HAN-based mixtures for reaction control system and low toxic
spacecraft propulsion subsystem: Thermal decomposition and possible
thruster applications
Rachid Amrousse a,b,⇑, Toshiyuki Katsumi c, Noboru Itouyama a, Nobuyuki Azuma b, Hideshi Kagawa b,
Keigo Hatai b, Hirohide Ikeda b, Keiichi Hori a
a
ISAS/JAXA, Japan Aerospace Exploration Agency, 3-1-1 Yoshinodai, Chuo-ku, Sagamihara, 252-5210 Kanagawa, Japan
b
TKSC/JAXA, Japan Aerospace Exploration Agency, 2-1-1 Sengen, Tsukuba, 305-8505 Ibaraki, Japan
c
Nagaoka University of Technology, 1603-1, Kamitomioka, Nagaoka, 940-2188 Niigata, Japan

a r t i c l e i n f o a b s t r a c t

Article history: HAN-based liquid monopropellant has been studied for its possible substitution of hydrazine toxic com-
Received 27 February 2015 ponent. The onset temperature of decomposition was provided by DTA-TG thermal analysis. Moreover,
Received in revised form 31 March 2015 the effect of 5 M HNO3 and 5 M NH2OH addition on catalytic decomposition was also examined. The
Accepted 31 March 2015
major products measured by mass spectrometer were N2, NO, N2O, NO2, H2O and NH3. Otherwise, the
Available online 17 April 2015
burning rates of HAN-based monopropellants were measured from the strand burner videos taken by
high speed camera. The effect of methanol addition; as fuel; on the burning rates was demonstrated.
Keywords:
On the other hand, HAN-based liquid monopropellant was tested and decomposed in 20 N thruster
HAN-monopropellant
High speed camera
and different catalysts were compared. Honeycomb catalysts were tested instead Shell 405 catalysts,
Combustion flame the obtained data demonstrate the improvement of burning reactions and pressure slopes after
Decomposition HAN-based decomposition.
Ó 2015 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

1. Introduction conducted to characterize the ignition and combustion behavior

Hydroxyl ammonium nitrate (HAN, NH3OHNO3) is a promising
substitute for hydrazine because of its low toxicity, high density,
high specific impulse, and low freezing point. As known, the con-
ventional monopropellant is hydrazine (N2H4), but the high vapor
pressure of hydrazine and its high toxicity cause high storage and
handling costs. Thus, the substitution of hydrazine by a less toxic
monopropellant is desired [1,2] in order to investigate low toxic
spacecraft propulsion subsystem with green propellant. In artillery
guns, one of the significant advantages of using liquid propellants
rather those solid propellants is the capacity to control the
combustion by metering the propellants [3]. Few years ago, among
possible hydrazine substitutes, aqueous energetic ionic liquids
comprising an ionic oxidizer, an ionic or molecular fuel, and
water as solvent, are often proposed and investigated as new
monopropellants [1,2]. Moreover, extensive studies have been
⇑ Corresponding author at: JAXA, Japan Aerospace Exploration Agency, 3-1-1
Yoshinodai, Chuo-ku, Sagamihara, 252-5210 Kanagawa, Japan. Fax: +81 42 759
8284.
E-mail addresses: rachid.amrousse@yahoo.fr, rachid.amrousse@jaxa.jp
(R. Amrousse).
of HAN. Pressure effects on the burning rates as well as flame
structures of HAN and HAN-based liquid propellants were investi-
gated [4–10]. The behavior of the propellant droplets was observed
in terms of micro-explosion and gasification characteristics
[11,12], the phenomenon that occurred between the liquid and
gas phase under high pressure and temperature environments
[13,14], and droplet combustion [15]. The decomposition products
of HAN were detected by employing various diagnostic techniques
[15–19]. Chemical kinetic studies on HAN have been performed in
order to determine reaction mechanisms and global kinetic rates.
Reactions for dilute HAN in the presence of a large excess of
HNO3 were investigated [20–28]. N2 and NO formation reactions
in HAN decomposition were also studied [23,29,30]. However,
the experiments were conducted with very low concentrations of
HAN at low temperatures to maintain isothermal conditions.
Based on the previous reaction studies [20–30] and experimental
observations, two reaction mechanisms were proposed for fused
HAN [31] and concentrated HAN mixtures [32].
However, the adiabatic temperature of several liquid propel-
lants are very high and in order to lower these temperatures, a
lot of mixtures were tested such as HAN with methanol and

http://dx.doi.org/10.1016/j.combustflame.2015.03.026
0010-2180/Ó 2015 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
 R. Amrousse et al. / Combustion and Flame 162 (2015) 2686–2692
ethanol [33], HAN in the presence of TEAN (triethanol ammonium
nitrate) [34], HAN with hydrazinium nitrate (HN) [35] for reaction
control systems and green propellant for low toxic spacecraft
propulsion subsystem. Moreover, the army has developed XM45
(LGP1845) and XM46 (LGP1846) for gun applications, which are
homogeneous mixtures of HAN, TEAN and water [36].
In an attempt to develop a new rocket propellant, many
formulations have been considered. The most recent application
of green propellant was developed by Ball Aerospace and
Technology corporation which it used AF-M315E, it demonstrates
stable performance of a flightweight attitude control thruster for
at least 10,000 total pulses [37–39]. The most recent formulation
in Japan consists of HAN 73.6%, water, methanol as fuel and ammo-
nium nitrate (AN) as additive to stabilize the mixture for long-term
storage [40]. Our previous research data showed that Shell 405
catalyst was very active of HAN decomposition. However, this cata-
lyst deactivate after several firing tests due to high exhaust gas
temperatures and oxidation medium [41]. Then, the use of struc-
tured catalysts as those supported on honeycomb monoliths has
been long considered in chemical industry and it has increased
with the significance of environmental catalysis in pollution abate-
ment applications [42]. For reaction control systems (RCS), cata-
lysts with high attrition resistance and a low pressure drop are
required. In addition, the thin catalytic coating allows high effi-
ciency and selectivity [42–44]. The honeycomb monoliths can be
made of ceramic or metallic materials. More extensive studies on
ceramic monoliths were performed due to their wide use in
three-way automobile catalysts, mainly cordierite, commonly
used, among others, owing to its large-scale production based on
extrusion which is quite cheap. Cordierite offers high mechanical
strength, high resistance to elevated temperatures and tempera-
ture shocks due to its low thermal expansion coefficient.
Moreover, it presents great adhesion stability, which is a very
important property for monolithic catalysts [43,45]. The most
usual way to coat structured supports such as honeycomb mono-
liths is the well known washcoating procedure. The monolith is
dipped in the slurry prepared with the catalytic material and after
a certain time withdrawn carefully. The characteristic of the final
coating are a complex function of monolith properties, slurry prop-
erties and preparation conditions [43]. To ensure good perfor-
mances of propellant-catalyst systems, highly active catalysts
were prepared and tested for HAN decomposition at low tempera-
tures [40,41,46–48]. The main purposes of this paper are: (i) to
determine the temperature onset and gas phase temperatures of
HAN-based monopropellant by DTA-TG analysis; (ii) the analysis
of outlet gas products was performed by online mass spectrometer
(MS); (iii) the burning rates and combustion temperatures were
measured at constant pressures, the effect of methanol addition
on the burning rates was carefully examined; because it is quasi-
impossible to apply HAN–H2O binary solution into reaction control
systems (RCS) due to its high adiabatic temperature and instable
combustion characteristics. On the other hand, HAN-based mono-
propellant solution contains methanol as fuel and AN as stabilizer
was decomposed by injection of known mass flows controlled by
electrovalve into preheated catalytic bed in vacuum chamber.
2. Experimental
2.1. Monopropellant solution
HAN-based liquid monopropellant was prepared by Hosoya
Company (Tokyo, Japan). The solution composition is HAN
73.6 wt.% – AN 3.9 wt.% – H2O 6.2 wt.% – MeOH 16.3 wt.% (HAN/
AN/H2O/MeOH = 95/5/8/21; stoichiometric conditions); which AN
is ammonium nitrate and MeOH is methanol. AN was added to
HAN solution in order to decrease the freezing point. However,
2687
the methanol was used to control the burning rate of the
monopropellant.
2.2. Thermal analysis
HAN decomposition was followed by differential thermal analy-
sis-thermal gravimetric (DTA-TG) apparatus (Riken) coupled to
mass spectrometer (MS) at 1 atm (±1–2 °C as uncertainty analysis).
Known masses of catalyst (±0.2 mg as uncertainty mass measure-
ment) were put into aluminum cell holder followed by spray
injection of known volumes of liquid monopropellant. The mass
and temperature were recorded versus time, under helium flow
(50 ml min1) and heating rates were fixed at 5 °C min1 for ther-
mal decomposition and 1 °C min1 for catalytic decomposition.
The analyses by DTA-TG enable to obtain the following informa-
tion: (i) evaporation of different solvents (endothermic peak); (ii)
onset temperature of decomposition given by the inflexion point
of the temperature curve; (iii) concentration of the HAN mixtures
at decomposition; (iv) efficiency of the catalyst (exothermic peak)
and (v) detection of emitted products by MS.
2.3. Strand burner
The combustion data of HAN-based liquid monopropellant at
elevated pressures were obtained from strand burner experiments
in a pressure vessel. The open-button strand burner was located in
the center of pressure vessel, into which the glass tube equipped
with wire and prefilled with HAN propellant as illustrated in Fig. 1.
The gas products vented out and the vessel was equipped with
an electrical feedthrough as resource to provide the required
energy for ignition of the propellant. A pressure regulator was used
for monitoring the static pressure into the vessel and windows for
light access. High-speed graph motion pictures were recorded with
a high-speed camera (Roper Scientific, CR Imager, Model 2000);
with 250 fps as framing rate; equipped with Nikon lens at maxi-
mum of 2200 frames per second. In a typical experiment, the
strand burner was equipped with prefilled glass tube with HAN
propellant and placed into pressure vessel. The vessel was then
pressurized with nitrogen. Ignition of the propellant was accom-
plished by an electrical discharge. After test, the vessel was safely
depressurized, opened, cleaned and moved to another test. In order
to measure the burning rate, short intervals of images were
obtained from video files. Then, Image J program was used to
measure the surface of liquid varied versus time.
Wire
Glass tube
Solution
Fig. 1. Glass tube contains HAN solution and equipped with wire igniter.
2688 R. Amrousse et al. / Combustion and Flame 162 (2015) 2686–2692

2.4. Thruster tests 100 0

191 °C
The HAN thruster 20 N was already described in previous
papers [41,49], in which the pressure slope was placed in the com-

Diff. temperature (ºC mg-1)

75
bustion chamber (after catalytic bed). It was developed in JAXA
several years ago as part of research project. The upper part of 201 °C -5

Weight (%)
HAN-based propellant tank was filled with N2 gas from a gas cylin-
der. The N2 pressure in the tank was fixed for HAN catalytic 50
decomposition reaction in order to give an almost constant feeding
rate of HAN. The monolithic catalyst was charged into the thruster.
- 10
Then, the catalyst bed was preheated before test at 210–300 °C.
The preheating of catalyst was performed by flexible sheath heater 25 154 °C
manufactured by SAKAGUCHI E.H VOC CORP with 88 W as power
and 35 VDC as power-supply voltage.
When the electromagnetic valve was opened, HAN-based 0 - 15
monopropellant was pressed by the N2 gas into the thruster. 0 5 10 15 20 25 30 35 40
Ignition delay, catalyst bed temperatures, chamber pressures and Time (min)
feeding rate of HAN were recorded by Lab-view software (NI
USB-6229) with the sampling rate of 1000 Hz. The accuracy of Fig. 2. Thermal decomposition of 95/5/8/21 HAN-based mixture.

pressure sensor is ±0.5% FSO (Full Scale Output) which is equal to

0.076 MPa.
0 0
The opening time of the electromagnetic valve was varied from
1 to 5 s. The average mass flow for each thruster firing test is
around 12.0 g s1 (±0.05 ml as electrovalve accuracy) and -20
1.2 MPa as initial pressure. After tests, the catalytic bed was purged -5
by N2 flow, which to remove the produced gases and to decrease

Weight (wt.%)
ΔΤ (°C mg )

temperatures.
-1

-40

-10
3. Results and discussion
-60

The tree different experiments carried out in this study can be

-15
distinguished by their heating method and initial pressure condi- -80 65 °C
tions. Firstly, during the thermal analysis, the propellant was trea-
ted under gradual increase of temperature at 1 atm. Secondly; the
combustion flame structure was performed under external electric -100 -20
power at different pressures. Finally, HAN monopropellant was 0 10 20 30 40 50 60 70
injected into preheated catalytic bed. The presented results were Time (min)
showed the possibility to apply HAN-based as green monopropel-
Fig. 3. Catalytic decomposition of 95/5/8/21 HAN-based mixture over Ir-based
lant into space applications; such as reaction control systems (RSC) catalyst.
and low toxic spacecraft propulsion subsystem.

3.1. Thermal analysis
Thermal and catalytic decomposition processes of HAN-based
liquid monopropellant with additives; followed by online
exhausted gas analysis; were carried out by DTA-TG/MS. The evo-
lutions of temperature and weight loss as a function of time during
the thermal decomposition process are represented in Fig. 2. The
thermal decomposition of HAN-based has been started around
154 °C after a large endothermic reaction which demonstrated by
total evaporation of methanol and water as additives. The thermal
decomposition occurs in two short steps: (i) highly exothermic
reaction with a maximum at 191 °C, which correspond to the high
loss of HAN weight, while (ii) the second step was less exothermic
and reach maximum at 201 °C.
During the thermal decomposition process, an endothermic
peak corresponding to the evaporation of methanol and water
has been observed and resulted in concentration of solution.
Then a second, rapid weight loss happens, correspond to exother-
mic decomposition of HAN/AN.
Figure 3 shows obtained temperature and weight loss profile
versus time in the presence of catalyst. The temperature profile
was changed in the case of catalytic decomposition process to a
violent exothermic reaction of HAN-based in one step at low tem-
perature onset. Moreover, the preliminary low exothermic process
has been observed in the case of HAN–water [33], however, this
phenomenon was absent by methanol addition that can accelerate
the evaporation process. Based on experimental results, methanol
appears to play a very major role in the decomposition of HAN-
based.
Therefore, in both cases, the decomposition starts only when
the solvents have been quantitatively removed leading to almost
pure liquid HAN (melting point 48 °C). From these results, we
can conclude that solvents exhibit, as expected, a stabilizing effect
on HAN, which is the consequence of dispersed ions (NH3OH+ and
NO3 ) in solutions. The ionic reagents must therefore be in contact
with each other for decomposition to engender.
The decomposition rates of HAN–H2O solution were signifi-
cantly influenced by the amount of methanol. Indeed, the metha-
nol was added to HAN/H2O solution in order to decrease its
burning rate, obtain higher Isp than hydrazine even in no-
detonation region. Moreover, the methanol addition makes HAN
solution in category 4 (harmful and swallowed) of GHS (Globally
Harmonized System) of classification and labeling of chemicals;
which is defined by LD50rat (Lethal Dose). LD50 of HAN solution
estimated to 300–2000 mg kg1, which is much lower in the case
of hydrazine (60 mg kg1).
It should be noted that the catalytic performance varied from
catalyst to other due to nature of noble metal, preparation, metal
 R. Amrousse et al. / Combustion and Flame 162 (2015) 2686–2692 2689

2,5 10
4 Table 2
m/z = 17 Synthesized HAN-based mixtures with 5 M NH2OH addition.
m/z = 18
m/z = 28 Mixtures Final Ratio HAN- NH2OH HAN-based
2 10
4 m/z = 30 volume based:NH2OH volume volume (ml)
m/z = 44 (ml) (ml)
m/z = 46
Absolute intensity (a.u.)

m/z = 63 HAN-based 5.0 0 0.0 5.0

4 HAN-based + 1:10 5.5 1:10 0.5 5.0
1,5 10
HAN-based + 2:10 6.0 2:10 1.0 5.0
HAN-based + 3:10 6.5 3:10 1.5 5.0
HAN-based + 4:10 7.0 4:10 2.0 5.0
4
1 10 HAN-based + 5:10 7.5 5:10 2.5 5.0

5000

140
HNO3 (5M)
0 HNO3 addition
NH2OH (5M)
0 5 10 15 20 25 120
Time (min)

Onset temperature (°C)

100 NH OH addition
Fig. 4. MS-online analysis of thermal decomposition of 95/5/8/21 HAN-based 2

mixture.
80

content etc. The present catalyst based on iridium was highly 60

active and represents similar temperature onset as well as com-
mercial Shell 405 catalyst (70 °C). The chemical reaction products 40
were detected by online MS analyzer. Figure 4 shows the most
relevant mass fragmentations (m/z) after catalytic decomposition
20
of HAN-based mixture as a function of time and absolute intensity.
The error bars represent a 95% confidence interval. It has been
0
reported that N2 can be formed by following reactions [17,25,50]:

HAN-based + 1:10

HAN-based + 2:10

HAN-based + 3:10

HAN-based + 4:10

HAN-based + 5:10
HAN-based

NH2 OHðgÞ þ HNO ! N2 ðgÞ þ 2H2 OðgÞ

HNO þ HAN ! N2 ðgÞ þ 2H2 OðgÞ þ HNO3 ðgÞðrecombinationÞ

Otherwise, N2O and NO gaseous phases were reported to be
formed by the possible reactions of NH2OH or NH3OH+ with insta-
Fig. 5. Catalytic decomposition of 95/5/8/21 HAN-based mixture in the presence of
ble intermediates HONO and HNO. NO2 probably formed from HNO3 and NH2OH additional volumes.
HNO3 decomposition.
In addition, it was not possible to explain all the measured
decomposition products in this study, which are shown in Fig. 4, showed the effect of additional 5 M HNO3 on onset temperature
by these mechanisms. Therefore, some reactions obtained from delay, however, additional 5 M NH2OH accelerates the onset tem-
the literature survey were added to the previous reaction mecha- peratures of decomposition. According to these data, the chemical
nisms. It is agreed upon that the first step of HAN decomposition reactions of HAN-based monopropellant without addition and
proton (H+) transfer from NH3OH+ to NO 3 producing NH2OH and HAN-based with additional species were reacted differently into
HNO3. Since NH2OH is a much stronger base than water [51], any the catalytic surface. The analysis of online gas products showed
protons that HNO3 releases will associate with NH2OH, not water. similar product species; it means that the catalytic decomposition
Consequently, HNO3 dissociation releasing a proton will simply even with additional species does not have effect on the thermal
reverse, leading to no net reaction. decomposition process of HAN-based. Nevertheless, from these
In addition, Tables 1 and 2 lists detailed information of two pre- results, may present Ir catalyst was selective to decompose totally
pared series of HAN-based. The purpose was to understand the NH2OH. However, it was not active to decompose HNO3 totally in
effect of addition of 5 M HNO3 and 5 M NH2OH on the catalytic the gas phase.
decomposition behavior of HAN-based in the presence of Ir-based In Fig. 5, representative results of onset temperatures of
catalyst. The obtained results were presented in Fig. 5, which decomposition are illustrated for HAN-based after addition of dif-
ferent amounts of HNO3 and NH2OH.
Table 1 In order to verify the selectivity of Ir-based catalyst, two differ-
Synthesized HAN-based mixtures with 5 M HNO3 addition. ent tests: (i) the decomposition of 60% HNO3 and (ii) 50% NH2OH
were performed. NH2OH totally decomposed at very low tempera-
Mixtures Final Ratio HAN- HNO3 HAN-based
volume based:HNO3 volume volume (ml) ture (45–50 °C). Though, HNO3 was only evaporated due to large
(ml) (ml) endothermic reaction. Therefore, the catalytic decomposition of
HAN-based 5.0 0 0.0 5.0
HAN-based monopropellant was started by total decomposition
HAN-based + 1:10 5.5 1:10 0.5 5.0 of NH2OH to form intermediate species such as HNO and HNO2
HAN-based + 2:10 6.0 2:10 1.0 5.0 acids. These instable acids reacted with non reacted HAN and
HAN-based + 3:10 6.5 3:10 1.5 5.0 non reacted HNO3 to form more stable species as well as gas outlet:
HAN-based + 4:10 7.0 4:10 2.0 5.0
NO, N2, N2O, NO2, H2O etc. [52]. Moreover, HNO3 can be a good sta-
HAN-based + 5:10 7.5 5:10 2.5 5.0
bilizer of HAN-based mixtures.
2690 R. Amrousse et al. / Combustion and Flame 162 (2015) 2686–2692

3.2. Combustion flame structure 1.0e+02

The ignition of HAN-based monopropellant was carried out on

Burning rate (mm s-1)

strand burner by external electric power at constant pressures. 1.0e+01
Figure 6 shows different pictures of HAN-based combustion tests
taken by high speed video camera. According to the obtained 1.0e+00
results, the burning rates have been influenced by initial pressures.
In fact, small and white generated bubbles were observed in the
case of P = 1 MPa may due to the evaporation of water. However; 1.0e-01
from P = 3 MPa; the bubble volumes increased and the color of
transparent solution became brown, this phenomenon may caused
by the formation of NO2 gas, evaporation of water, and partial and 1 2 3 4
slow decomposition of HAN-based. At P = 4 and 6 MPa, the bubble Pressure (MPa)
diameter became smaller when we increased initial pressure. It
means that the bubbles of decomposition were generated but the Fig. 7. Effect of methanol addition on the calculated burning rates of HAN/AN-
high pressure assumes their decrepitating (more clear in case of based mixture in the strand burner.

P = 8 MPa).
On the other hand, Fig. 7 shows the measured burning rates of
HAN solutions with different mass percents of methanol. 1.0e+02
: 95/5/8/21
According to those data, the burning rates of 95/5/8/0, 95/5/8/29
: 95/5/8/21 + Ir
and 95/5/8/50 mixtures jumped from the moderate rates to extre-

Burning rate (mm s-1)

mely high rates. The burning jump was absent in the case of 95/5/ 1.0e+01
8/21 mixture which present the best linear burning rate equation.
In fact, the initial mass of methanol has a strong effect on the
stability of burning rates. 1.0e+00
For other mixtures, they can be applied as propellant mixtures
according to their high burning rates. However, the jump of the
burning rates to high regions cannot be demonstrated by combus- 1.0e-01
tion mechanism, but rather by hydrodynamic stability [53]; which
was explained by Landau–Levich instability theory for liquid pro-
pellants by adding reactive/diffusive instability and applied the
1 10
extended theory to an HAN-based monopropellant. Otherwise,
Pressure (MPa)
supported Ir-particles were mixed with HAN-based liquid mono-
propellant at room temperature. Figure 8 presents the measured Fig. 8. Effect of iridium particles on the calculated burning rates of HAN-based
burning rates of HAN-based solution (95/5/8/21) mixed with sup- mixture in the strand burner.
ported iridium particles on alumina (as catalyst). The results
showed that the measured burning rates are higher than those
bed temperature above 210 °C, but in order to obtain a nominal
obtained after combustion of HAN-based mixture alone and these
start 350 °C is preferred for honeycomb catalysts.
data can be explained through the following reason: before igni-
Figure 9a and b (zoom) illustrate the evolution of pressure as a
tion, the electric power activates the Ir-particles at the surface by
function of time during the burning reaction processes of HAN-
temperature increasing; and the hot Ir-particles decrepitate the
based. The burning reactions of HAN-based liquid monopropellant
generated bubbles.
were conducted over honeycomb catalysts using 20 N thruster
showed that the pressure slopes in the case of Ir honeycomb cata-
3.3. Thruster tests lysts 400 and 600 cpsi were higher than commercial Shell 405 cata-
lyst. In fact, the pressure slope in the case of commercial Shell 405
It should be mentioned that before firing the thruster, the reac- catalyst was around 1.5 MPa s1, while this value was doubled
tor is pre-heated to a sufficient temperature, typically 210–350 °C to 3.5 MPa s1 in case of 30 wt.% Ir honeycomb catalysts.
(depending on bed load). The reaction will start already with a heat Moreover, the three curves showed second pressure slopes due

P = 1 MPa P = 3 MPa P = 4 MPa P = 6 MPa P = 8 MPa

Fig. 6. Pictures taken by high speed camera during combustion of 95/5/8/21 HAN-based mixture in the strand burner.
 R. Amrousse et al. / Combustion and Flame 162 (2015) 2686–2692 2691

0.5 0.4

0.4
0.3

Pressure (MPa)
Pressure (MPa)

0.3
0.2
- S405 (Shell catalyst)
- Ir-CuO/honeycomb 600 cpsi
0.2 - Ir/honeycomb 400 cpsi
- S405 (Shell catalyst)
- Ir/honeycomb 600 cpsi 0.1
- Ir/honeycomb 400 cpsi
0.1

0 0.5 1.0 1.5 2.0

0 0.5 1.0 1.5 2.0 Time (s)
Time (s) (a)
(a)
0.4
0.5

0.3

Pressure (MPa)
0.4
Pressure (MPa)

0.3 0.2

0.2 0.1

0.1
0 0.05 0.1 0.15 0.2
Time (s)
0 0.1 0.2 0.3 0.4 (b)
Time (s)
Fig. 10. (a) Burning reaction tests of 95/5/8/21 HAN-based mixture over 3 different
(b) catalysts with different active phases on 20 N thruster and (b) zoom of reaction
timing.
Fig. 9. (a) Burning reaction tests of 95/5/8/21 HAN-based mixture over 3 different
Ir-based catalysts on 20 N thruster and (b) zoom of reaction timing.

to second reactions of gas phase products over catalysts. The sec-
ond pressure slope has been started earlier (after 1 s of monopro-
pellant injection) in the case of Ir honeycomb catalyst 600 cpsi.
Contrariwise, slopes were delayed in the case of commercial cata-
lyst and honeycomb 400 cpsi. The difference could be demon-
strated by the size of channels of catalyst surfaces; honeycomb
600 cpsi has small size channels compared to honeycomb 400 cpsi.
Indeed, the generated gas products have more contact or longer
residence time within 600 cpsi catalyst surface; that mean gaseous
phase undergoes fast reaction with solid catalyst surface in this
case.
We can conclude that HAN-based monopropellant mixture can
be applied as candidate of hydrazine replacement due to high and
sudden pressure slopes. In fact, the obtained results can be
improved by modifying some parameters such length of catalytic
bed, injection system and heater performance.
In order to improve the delay of second pressure slopes, new
honeycomb catalyst 600 cpsi based on Ir and CuO active phases.
Obviously, the honeycomb catalyst was successively impregnated
by Ir- and then Cu-precursors in order to file 20 wt.% and 10 wt.%
of both active phases; respectively. From the firing test results pre-
sented in Fig. 10a and b (zoom) in which the pressure was pre-
dicted as a function of time, Ir–CuO biphasic catalyst has two
advantages compared to Ir monophasic catalysts: (i) same value
of pressure slope than other Ir honeycomb catalysts but economi-
cally more cheaper, and (ii) accelerates the second pressure slope
for about 1–1.5 s. Thus, the maximum pressure value (0.4 MPa)
has been reached in a short time. This catalyst may be active for
HNO3 decomposition in the gas phase state that is why the second
slope was accelerated and it was faster. Moreover, it is well known
that the decomposition of HNO3 is very slow and requires high
activation energy; for this, the temperature of preheated catalytic
bed reactor was varied between 210 and 350 °C. On the other hand,
Kajiyama et al. studied the effect of CuO on the thermal
decomposition of AN [54]. In fact, during the thermal process, they
assumed that CuO allows the formation of copper complexes such
as [Cu(NH3)2](NO3)2, which increases the reaction rate of AN pre-
sent in HAN-based monopropellant as stabilizer with the intention
to decease its freezing point.
4. Conclusion
According to the synthesized HAN-based solution properties
that present several advantages such as high density and high
specific pulse, this monopropellant can be applied for reaction con-
trol system instead toxic hydrazine:
– The present (20%) Ir catalyst showed high performance on the
HAN-based decomposition and it can substitute Shell 405 cata-
lyst. However, Ir active phase was selective to decompose
totally NH2OH and same catalyst suffered against HNO3 gas.
– The burning rates measured from strand burner tests were
involved by addition of methanol on HAN/AN mixtures. 95/5/
8/21 mixture presents most acceptable burning rates.
However, the burning rates of other mixtures have been jumped
after attend 4 MPa as pressure. The burning rates have been
increased after mixing HAN-based propellant with supported
Ir-particles.
2692 R. Amrousse et al. / Combustion and Flame 162 (2015) 2686–2692
– The new synthesized Ir–CuO monolithic catalyst showed high
performance for HAN-based decomposition. In fact, the burning
reactions and the pressure slopes were improved comparing
data to those obtain by Shell 405 commercial catalyst. Also,
the cost of honeycomb catalysts was much lower than commer-
cial catalyst.
Acknowledgments
Authors would like to thank Japan Aerospace Exploration
Agency for the project support. Dr. Rachid Amrousse presents his
thank to JAXA (Sagamihara branch and Tsukuba branch) for the
grant of research project, Yokohama and Tokyo universities for
different experimental devices.
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