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Proceedings of the Combustion Institute 35 (2015) 21992206

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Hypergolic ignition and ame structures of

hydrazine/nitrogen tetroxide co-owing plane jets
Hiroumi Tani a,, Hiroshi Terashima b, Mitsuo Koshi c, Yu Daimon a
a

JAXA Digital Innovation Center, Japan Aerospace Exploration Agency, 2-1-1 Sengen, Tsukuba, Ibaraki 305-8505, Japan
b
School of Engineering, The University of Tokyo, 2-11-16 Yayoi, Bunkyo, Tokyo 113-8656, Japan
c
Graduate School of Environment and Information Science, Yokohama National University, 79-7 Tokiwadai,
Hodogaya, Yokohama, Kanagawa 240-8501, Japan
Available online 5 August 2014

Abstract
Hydrazine (N2H4)/nitrogen tetroxide (NTO) co-owing plane jets were simulated to explore the hypergolic ignition processes and ame structures in N2H4/NTO bipropellant thrusters. The NavierStokes
equations with a detailed chemical kinetics mechanism were solved in a manner of direct numerical simulation to reveal the inuence of the distinct chemical reaction, i.e., hydrogen abstraction by nitrogen dioxide (NO2) and the thermal decomposition of N2H4. In the ignition processes, the hydrogen abstraction
sequence played a signicant role in preheating the mixture gases. Further, the ignition eventually occurred
in the region where both N2H4 and NTO were suciently supplied for preheating. Hence, the ignition position and delay strongly depended on the uid-mixing conditions. After the ames reached a steady state,
the combustion ames uniquely comprised two types of ames, the outer diusion ame and the inner
decomposition ame. The outer diusion ame came from the oxidization by NTO. The inner decomposition ame was caused and maintained by the heat transfer from the outer diusion ame and a high rate
of heat release from the thermal decomposition of N2H4. Because of the decomposition ame, the decomposition products such as NH3 and H2 were the major constituents of the downstream combustion gases.
2014 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
Keywords: Hypergolic ignition; Hydrazine; Nitrogen tetroxide; Computational uid dynamics; Detailed chemical
reaction

1. Introduction
Bipropellant thrusters containing hydrazine
(N2H4) and nitrogen tetroxide (NTO) which
means the nitrogen dioxidedinitrogen tetroxide
(NO2N2O4) system, are widely used in space
propulsion. N2H4/NTO bipropellant systems
Corresponding author.

E-mail address: tani.hiroumi@jaxa.jp (H. Tani).

Fig. 1. Schematics of complicated multi-physics phenomena in N2H4/NTO bipropellant thrusters.

http://dx.doi.org/10.1016/j.proci.2014.07.053
1540-7489/ 2014 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

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H. Tani et al. / Proceedings of the Combustion Institute 35 (2015) 21992206

possess the advantage of retaining hypergolic

characteristics even in low-temperature and
vacuum environments. Hence, pulse mode operations, i.e., cyclic operations of the ignition and
quenching at 10100 ms intervals, are possible
without ignition devices. Furthermore, the hypergolic ignition characteristics of N2H4/NTO are
important as they have a signicant impact on
the combustor performance, such as combustion
eciency and stability, in pulse mode operations
[13]. Another chemically distinct characteristic
is the thermal decomposition of N2H4. This
decomposition is an exothermic reaction; therefore, it can only be sustained by consuming
N2H4 after its initiation. Although the reaction
only occurs in high-temperature environments, it
may have a considerable inuence on the ame
structures of N2H4/NTO systems rather than the
ignition at the initiation of the thruster operations
in low-temperature environments. Hence, owing
to their hypergolic and thermal decomposition
characteristics, the ignition phenomena and ame
structures of N2H4/NTO systems may dier from
those of general industrial fuels. However, little is
known about the hypergolic ignition and ame
structures of N2H4/NTO systems because practical bipropellant thrusters are subjected to complicated multi-physics phenomena such as liquid jet
atomization and spray formation [4], liquid-phase
reaction at impinging regions [5], droplet combustions [6,7], and gas-phase reactions [8,9] as shown
in Fig. 1. Currently, the fundamental sub-processes are still mainly investigated by experiments
designed to understand the ow, ignition, and
combustion behavior of N2H4/NTO impinging
liquid jets.
Miyajima et al. [10] conducted hot-re tests on
the coaxial injection of gas phase N2H4/NTO to
understand the hypergolic ignition characteristics
in a gas phase. Although only photographs of
the steady-state ames were obtained and little
was reported on the ignition processes, it was
noted that N2H4/NTO coaxial gas jets could
auto-ignite even in low-temperature (300400 K)
and low-pressure (0.0050.01 MPa) environments.
While the hypergolic ignition of gas mixtures at
low temperatures was veried experimentally, no
detailed chemical kinetic mechanism that can
explain the low-temperature ignitions has been
proposed in years. Sawyer and Glassman [8]
described a global kinetic reaction model, including two reaction steps, and correlated it to the
results obtained in their experiment. However,
the global kinetic model was insucient to explain
the chemical kinetics of the low-temperature ignitions. In a recent study, Daimon et al. [9] searched
possible reaction pathways between N2H4 and
NTO, and their rate coecients using quantum
chemical calculations and transition state theory.
Eventually, they constructed a new detailed chemical kinetic mechanism for the hypergolic ignition

of a N2H4/NTO gas mixture at low temperatures.

The mechanism comprises 39 species and 261
reactions. They also revealed that low-temperature ignitions are caused by the following reaction
sequence of the hydrogen abstraction from N2H4
by NO2.
N2 H4 NO2 N2 H3 HONO or HNO2

R1

N2 H3 NO2 N2 H2 HONO

R2

N2 H2 NO2 N2 H HONO

R3

N2 H NO2 N2 HONO

R4

This reaction sequence releases a large amount

of heat and accelerates the temperature rise of the
gas mixtures, resulting in auto-ignition. Their
chemical reaction model also contains a kinetic
mechanism for N2H4 decomposition. Hence, the
model is also sucient for investigations into the
ame structures of N2H4/NTO systems.
To reveal the combustion phenomena in
N2H4/NTO bipropellant thrusters, the present
study investigated the hypergolic ignition processes and ame structures of N2H4/NTO systems when their distinct chemical kinetics was
coupled with the uid-mixing phenomena.
N2H4/NTO co-owing plane jets in the gas
phase were numerically simulated based on the
experiments by Miyajima et al. Further, the
inuence of the distinct chemical reaction of
N2H4/NTO systems onto the ignition processes
and the ame structures were explored. In the
present simulations, a detailed chemical kinetic
mechanism, proposed by Daimon et al. [9],
was directly calculated. This study is challenging
from the perspective of coupling the computational uid dynamics (CFD) with large chemical
kinetic models.
2. Numerical methods
2.1. Governing equations
The governing equations are the two-dimensional, compressible NavierStokes (NS)
equations that include the conservation equations
of chemical species. In order to avoid the stiness
of the chemical reaction terms, the uid and
chemical reaction terms were solved separately
and explicitly with dierent time steps. More
detailed formulae used in the present study can
be seen in the reference [11].
When solving the uid terms, the chemical
reaction was assumed to be frozen, and the explicit 3rd-order TVD RungeKutta method [12] was
employed for time integration. Spatial dierence
terms were evaluated by a modied HLLC scheme
[13] with a 3rd order MUSCL including the minmod limiter. The single-component and mixture

H. Tani et al. / Proceedings of the Combustion Institute 35 (2015) 21992206

averaged viscosities were calculated using the

standard kinetic theory expressions of Hirschfelder [14] and Bird [15], respectively. The single
component and mixture averaged thermal conductivities were obtained using the Warnatz
model [16] and Mathur et al.s formula [17]. The
binary and mixture diusion coecients were
evaluated using Hirschfelders expression [14]
and Birds formula [15].

2201

Fig. 2. Computational domain, boundary and initial

conditions.

2.2. Chemical reactions

When solving the chemical reaction terms,
the spatial gradient of the variables was
neglected and the volume and internal energy
in the NS equations were assumed to be constant. In order to eciently conduct the time
integration of the chemical reaction equations,
the Extended Robust Explicit Numerical Algorithm (ERENA) [18] was applied. ERENA is a
robust and fast explicit time integration method
based on automatic time step control using mass
conservation. For unsteady multidimensional
reacting ow problems, implicit ordinary dierential equation (ODE) integration methods,
e.g., variable coecient ODE (VODE) [19],
may be inecient because of the startup costs
and matrix operations. In contrast, ERENA
can directly and eciently handle the detailed
chemical reaction mechanisms proposed by Daimon et al. [9] with 39 species and 261 reactions.
Note that, for two-dimensional simulations of
N2H4/NTO co-owing jets described below, the
computational time of ERENA for the chemical
reaction and uid terms was about four times
faster than that of VODE under the time step
size of 1104 ms without loss of accuracy.
Only for the chemical reaction terms, the computational time of ERENA was about seven
times faster than that of VODE. Detailed formula and performance of ERENA such as
robustness and accuracy are provided in the reference [18].
3. Numerical conditions
In the reference experiment [10], N2H4 and
NTO were coaxially injected under low-pressure
and low-temperature environments. In the present
study, co-owing plane jets, instead of coaxial
jets, were simulated to explore the hypergolic ignition and ame structures while keeping the computational costs reasonable. Figure 2 shows a
schematic conguration of the co-owing plane
jets along with a denition of the streamwise (x)
and transverse (y) coordinates. The height of the
N2H4 inow boundary is set to be the same as
the injector diameter in the experiment.
Table 1 illustrates the injection conditions. The
injection pressure and temperature are set to be

similar to the experimental conditions under

which the hypergolic ignition was conrmed.
The mole fractions of NO2 and N2O4 were specied by estimating the equilibrium state at the
injection temperature. In the present conditions,
almost all the NTO is NO2. In the experiment,
the velocity dierences between the N2H4 and
NTO jets were almost zero. However, velocity
conditions may inuence the hypergolic ignition
and ame structures. Hence, the present simulations were conducted under three dierent velocity
conditions. The N2H4 jet was injected at a constant velocity in all cases, whereas the upper and
lower NTO jets were injected at three dierent
velocities to vary the uid-mixing conditions. In
Case 1, NTO was injected at the same velocity
with N2H4. In Case 2, the velocity of the NTO jets
was set to be lower than that of the N2H4 jet. In
Case 3, the NTO jets were set to be faster than
the N2H4 jet. The magnitudes of the velocities
were about ve times higher than those in the
experiment to avoid stiness due to low Mach
ow simulations.
The boundary conditions are as follows: Uniform proles of the pressure, temperature, mole
fraction, and velocity are imposed at the inow
boundary. At the outow boundary, the pressure
is specied to be equal to the ambient value. The
ambient pressure is also imposed at the upper
and lower boundaries. The simulations start
under the condition that the whole domain lls
with NTO ows at the injection velocities.
Notably, no articial heat source is imposed during the calculations. A computational grid of
911  411 points is used as a baseline grid. The
grid is clustered near the inlet and the jet shear
layer with the minimum grid spacing of
0.14 mm. The CFL number is 0.6, which corresponds to a time step size of about 104 ms for
the baseline grid. In this study, two other grids
(for which the number of grid points increases
or decreases approximately by a factor of square
of two in each direction) were additionally used
for a grid converged study. The results (although
not shown here) demonstrated that all grids provide almost similar results in terms of ignition timings and ame structures discussed in the
following sections.

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H. Tani et al. / Proceedings of the Combustion Institute 35 (2015) 21992206

Table 1
Injection conditions.
Case 1
Case 2
Case 3

Pressure

Temperature

VelocityN2 H4

VelocityNTO (m/s)

Mole fractions of NO2 and N2O4

0.01 MPa
#
#

400 K
#
#

50 m/s
#
#

50
30
70

0.990:0.010
#
#

4. Chemical kinetics of N2H4 and NTO

4.1. Auto-ignition of N2H4/NTO gas mixtures
Prior to the CFD simulations, zero-dimensional simulations of the N2H4/NTO mixture ignition were conducted to investigate the hypergolic
characteristics of N2H4/NTO systems from a
chemical kinetics view point. The time histories
of the stoichiometric mixture gas were calculated
with adiabatic and constant volume conditions.
The initial pressure and temperature were
0.01 MPa and 400 K, respectively. The ratio of
N2O4 and NO2 was also set to be the same value,
as shown in Table 1.
Figure 3 shows the time histories of the temperature and heat-release rate. Preheating and a temperature rise occur before the thermal ignition.
The preheating appears most signicantly from
0.5 ms, and the thermal ignition occurs at about
1.8 ms. Figure 3 also shows the time histories of
the mole fractions of the major species. During
the preheating time, the concentrations of N2H2
and HONO signicantly increase owing to the
hydrogen abstraction sequence of NO2 from
N2H4. The increase of N2H2 indicates that the
hydrogen abstraction from N2H3, i.e., the second
reaction (R2) of the hydrogen abstraction
sequence, is dominant during the preheating time.
Actually, Daimon et al. [9] reported that this reaction is largely exothermic and does not have an
energy barrier. Upon thermal ignition, the major
species from the preheating are consumed and
almost disappear. The N2H4 is consumed in the
induction period by the hydrogen abstraction
sequence, and the thermal decomposition plays
no role in the ignition.
4.2. Thermal decomposition of N2H4
Zero-dimensional simulations of the thermal
decomposition of N2H4 were also conducted.
The initial pressure and temperature were
0.01 MPa and 1000 K, respectively.
Figure 4 shows the time histories of the temperature and heat release rate. Even though the
initial gas is only N2H4, ignition occurs because
of thermal decomposition. The temperature after
the ignition is lower than that of N2H4/NTO mixture reaction but is still over 2400 K, and the maximum heat release rate is comparable to that of

the mixtures. Figure 4 also shows the time histories of the major species. The concentration of
NH3 is higher than those of H2 and N2 before
and during the ignition. After the ignition, the
concentration of N2 and H2 increase instead of
NH3. The ignition delay at 1000 K is also similar
to that of the mixtures. Calculations at the initial
temperature of 900 K were also conducted. However, the ignition did not occur for 20 ms.
5. Hypergolic ignition
Figure 5 displays the instantaneous contours
of the temperature and mole fraction of the major
species before and after the hypergolic ignition in
Case 1. In this case, the N2H4 and NTO jets were
not mixed by the velocity shear stress but instead
by the molecular diusion because the N2H4 and
NTO jets were injected at the same velocity.
Hence, the interface between N2H4 and NTO
was stable, and the preheating occurred near the
leading edge of the N2H4 jets, as shown in the left
column of Fig. 5. In fact, the temperature near the
interface increased gradually. The high concentration of HONO on the interface before the ignition
proves the occurrence of the hydrogen abstraction
sequence, which plays a major role in the preheating as discussed in the zero-dimensional simulations. Once the temperature near the interface
reached over about 1000 K, the hypergolic ignition immediately occurred near the leading edge
of the N2H4 jets, as shown in the right column
of Fig. 5. In the region where the ame propagates, N2H4 and HONO were rapidly consumed.
Compared to the major species of the hydrogen
abstraction sequence, the concentration of NH3,
which was one of the major species of the thermal
decomposition as also explained in the
zero-dimensional simulations, was very low before
the ignition. This indicates that the thermal
decomposition had less impact on the ignition
processes. The ignition delay in this case was
about 4.8 ms; this means that owing to the uid
mixing, the ignition delay was about 2.7 times
longer than the delay based on chemical kinetics.
Figure 6 illustrates the instantaneous contours
in Case 2. In this case, the N2H4 jet was injected at
a higher velocity than the NTO jets. Hence, large
scale vortices appeared ahead of the N2H4 jet, and
the NTO gas was captured in the large scale vortices. At rst, the temperature and mole fraction

H. Tani et al. / Proceedings of the Combustion Institute 35 (2015) 21992206

2203

Fig. 3. Time history of the temperature, heat release rate and mole fractions of the major species of the N2H4/NTO
mixture ignition.

Fig. 4. Time history of the temperature, heat release rate and mole fractions of the major species of the N2H4 thermal
decomposition.

Fig. 6. Instantaneous contours before ignition (left) and

after ignition (right) in Case 2.

Fig. 5. Instantaneous contours before ignition (left) and

after ignition (right) in Case 1.

of HONO in the vortices increased because the

preheating process proceeded inside the vortices
for a while. However, ignition eventually occurred

in the upstream boundaries of the vortices, not in

the center of the vortices. This is because as the
vortices largely developed, the outer boundaries
of the vortices blocked the NTO supply from
the surroundings, whereas NTO inside the vortices was kept consumed. Then, the concentration
of NTO inside the vortices was insucient for

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H. Tani et al. / Proceedings of the Combustion Institute 35 (2015) 21992206

Fig. 7. Schematics of the blockage mechanism of NTO

supply by N2H4 vortices in Case 2.

Fig. 8. Instantaneous contours before ignition (left) and

after ignition (right) in Case 3.

Fig. 10. Time-averaged contours of the temperature and

the major species after the ame reached steady state in
Case 1.

Fig. 9. Time-series contours of the temperature after the

ignition in Case 1.

maintaining the preheating process. Instead, the

upstream boundaries of the vortices provided a
better environment for the preheating process.
Therefore, the ignition occurred at the upstream

Fig. 11. The ignition delay in the three cases with

comparison to the experimental correlation.

H. Tani et al. / Proceedings of the Combustion Institute 35 (2015) 21992206

boundaries. Figure 7 shows the schematics of the

blockage mechanism of the NTO supply owing to
the development of the N2H4 vortices. The ignition delay was about 5.5 ms, which was longer
than the delay in Case 1. This is because the
strongly preheated region changed as the vortices
were developing. It is interesting that the vortices
that generally enhance the uid mixing increased
the ignition delay when they were coupled with
the chemical kinetics of preheating.
Figure 8 shows the instantaneous contours in
Case 3. In this case, the faster NTO jets induced
wake-like ows in front of the N2H4 jet, and the
mixing of N2H4 and NTO was enhanced in this
region. Because N2H4 and NTO were continuously supplied in this region, the preheating process in front of the N2H4 jet continued until
ignition. The ignition delay was about 3.9 ms,
which is the shortest time of the three cases.
Hence, it was found that the hypergolic ignition
of N2H4/NTO systems depend on the mixing
behaviors between N2H4 and NTO jets. A key
for the present hypergolic ignition mechanisms is
the presence of a sucient supply of NTO to
regions preheated by the hydrogen abstraction
sequence.

2205

was maintained by its high rate of heat release

and the heat transfer from the diusion ame.
Double ame structures were also reported in
the experimental works on N2H4 droplet combustions [6,7]. The present study showed that the double ame structures also appear in the N2H4/NTO
co-owing jets and that the combustion products
strongly depend on the decomposition ames.
After the ame structures reach a steady state,
the concentrations of the preheating major species
such as N2H2 and HONO are very small inside the
ames (Fig. 10e and f). This means that the hydrogen abstraction sequence plays a small role in
maintaining the ame structures.
Figure 11 plots the ignition delay of the three
cases in comparison to the experiments [10].
Miyajima et al. reported from their photographs
that the ignition delay of the N2H4/NTO coaxial
jets can be correlated to the following equation:


sP 2
4550  120
20
s atm2 K4 

3:04

10
exp
T
T4
Here, the ignition delay, s, is dened as the time
calculated by dividing the distance from the inlet
to the ame edge by the averaged velocities. It
can be conrmed that the present results are comparable to their measured data and correlations.

6. Flame structure
7. Conclusions
Because the characteristics of the ame structures after ignition are similar in all three cases,
only the results of Case 1 are displayed. Figure 9
displays the time series contours of the temperature after ignition in Case 1. The ame propagated
mainly downstream from the ignition regions.
Figure 10 shows the time averaged contours of
the temperature and major species after the ame
reached a steady state. The ame structures
uniquely comprised two types of ames, the outer
diusion ame and inner decomposition ame.
The outer diusion ame came from the oxidation
of hydrazine and its decomposition products by
the NTO gas. The ame temperature is over
3000 K, which is similar to the zero-dimensional
simulations of the N2H4/NTO mixtures. The
inner decomposition ame was surrounded by
the outer diusion ame and appeared downstream of the N2H4 jet core. The high concentration of NH3 and H2 and relatively low ame
temperature oer evidence that the inner ame
comes from the thermal decomposition of N2H4.
Similarly with the zero-dimensional simulation
of the decomposition of N2H4, the concentration
of NH3 rst increases, and the concentration of
H2 secondly increases downstream. Because the
ame structures begin with the high-temperature
diusion ame as shown in Fig. 9, the decomposition ame is primarily induced by the heat transfer from the diusion ame. After the ame
reached a steady state, the decomposition ame

The N2H4/NTO co-owing plane jets were

simulated under low-pressure and low-temperature conditions to explore the hypergolic ignition
processes and ame structures of N2H4/NTO systems. Additionally, the inuence of the distinct
chemical reaction, hydrogen abstraction by NO2
and thermal decomposition of N2H4, was investigated by the methodology of direct numerical simulation with the detailed chemical kinetics
mechanism of N2H4/NTO.
In the hypergolic ignition processes, the hydrogen abstraction sequence, especially the reaction
of N2H3 and NO2, plays a signicant role in preheating the mixture gases ahead of the N2H4 jets.
The ignition eventually occurs in the region where
both N2H4 and NTO are suciently supplied for
preheating. Hence, interestingly, it was found that
the ignition position and delay strongly depend on
whether the ow elds provide appropriate environments for the preheating chemical reaction.
The decomposition of N2H4 has less inuence
on the ignition processes.
After the ame reaches a steady state, the combustion ames uniquely comprise two types of
ames, the outer diusion ame and the inner
decomposition ame. The outer diusion ame
comes from the oxidization by NTO. The inner
decomposition ame is caused and maintained
by a high rate of heat release of the thermal
decomposition of N2H4 and the heat transfer

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H. Tani et al. / Proceedings of the Combustion Institute 35 (2015) 21992206

from the outer diusion ame. Because of the

decomposition ame, the decomposition products
such as NH3 and H2 were the major constituents
of the downstream combustion gases.

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