Aerospace Science and Technology 49 (2016) 209–214

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Aerospace Science and Technology

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Demonstration of 500 N scale bipropellant thruster using non-toxic

hypergolic fuel and hydrogen peroxide
Hongjae Kang, Dongwook Jang, Sejin Kwon ∗
Department of Aerospace Engineering, School of Mechanical and Aerospace Engineering, Korea Advanced Institute of Science and Technology, KAIST 291,
Daehak-ro, Yuseong-gu, Daejeon, 34141, Republic of Korea

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

Article history: While shedding light on green space propulsion, the development of non-toxic hypergolic bipropellants
Received 15 May 2015 has provided alternatives to the conventional, highly toxic propellants. Non-toxic energetic hydrocarbon
Received in revised form 11 November 2015 fuels promoted by sodium borohydride were produced, and their hypergolicity with rocket grade
Accepted 22 November 2015
hydrogen peroxide was confirmed. Ignition delays ranged from 4 ms to 17 ms, depending on the oxidizer
Available online 4 December 2015
concentration. A 500 N scale thruster utilizing a non-toxic hypergolic bipropellant combination was also
Keywords: developed. With an oxidizer-to-fuel ratio of 5.48, the injector was designed with pentad unlike-impinging
Hypergolic ignition jets, one fuel jet orifice and four oxidizer jet orifices for enhancing the mix and atomization of the
Non-toxic hypergolic fuel hypergolic propellants. The operation test was performed, and burning time was established to be 3.5 s.
Sodium borohydride For the demonstrator, the rising time was approximately 158 ms, and the pressure oscillation inside
Hydrogen peroxide the combustion chamber was approximately ±7.69%. These results indicate the feasibility of this novel
Ignition delay concept engine for future space missions.
© 2015 Elsevier Masson SAS. All rights reserved.

1. Introduction
Liquid-fueled propulsion systems have been developed over
the past 100 years, and monopropellant or bipropellant chemi-
cal propulsion thruster systems have undergone several specific
changes. The latter is the most commonly used in a variety of
civilian and military applications, and in an attempt to increase
its performance, various propellant combinations have been tested
since Robert Goddard’s first rocket. Above all, the hypergolic igni-
tion system has been widely adapted for space propulsion applica-
tions, where reliable and repetitive ignition is essential.
A hypergolic bipropellant is a particular combination of fuel and
oxidizer that ignites spontaneously upon contact. However, in the
existing hypergolic propulsion systems, the use of hydrazine or its
derivatives as a fuel, along with nitrogen tetroxide or nitric acids
as an oxidizer, is indispensable, even if they are extremely toxic,
corrosive, potently carcinogenic to humans and detonable. These
utmost dangers that stem from the toxicity of the propellants sig-
nificantly increase the cost and time required for development and
launch of a rocket. The cost penalties are made up of diverse parts:
the propellant, its handling, health surveillance, decontamination
and disposal of residuals [1,2]. Furthermore, a curtailment in the
* Corresponding author.
E-mail addresses: newkhj878@kaist.ac.kr (H. Kang), menat87@kaist.ac.kr
(D. Jang), trumpet@kaist.ac.kr (S. Kwon).
budget of national space agencies for space missions, along with
stricter environmental and safety regulations, emphasizes the need
for non-toxic hypergolic propellants. Thus, extensive research has
been conducted on non-toxic hypergolic bipropellants to remedy
the drawbacks reported from the existing hypergolic propulsion
systems, although follow-up implementation continues to remain
relatively scarce [3–5].
The principal goal of this research is to demonstrate a novel
concept of 500 N scale bipropellant thruster using a non-toxic
hypergolic bipropellant combination. This paper then presents ex-
perimental demonstrations with respect to hypergolic interactions
and thruster operation. The focus is placed on the use of high test
hydrogen peroxide (HTP) as a green oxidizer, considering its envi-
ronmentally benign nature, and the search for non-toxic energetic
hypergolic fuels comparable to conventional toxic fuels.
In general, there are two different types of additives for grant-
ing hypergolicity in a rocket fuel: catalyst or strong reducer. A cat-
alyst dispersed in fuel can vigorously decompose an oxidizer when
they are brought into contact. This process represents a rapid
exothermic reaction that generates enough energy to ignite the re-
actants. However, this catalyst additive is not directly involved in
the combustion process, which could result in increasing ignition
delay and in degrading performance. Unlike the catalytic additive,
once a strong reducer, such as metal hydrides, comes into contact
with an oxidizer, ignition occurs immediately because the strong
reducer itself can easily combust with a strong oxidizer. Due to its

http://dx.doi.org/10.1016/j.ast.2015.11.038
1270-9638/© 2015 Elsevier Masson SAS. All rights reserved.
210 H. Kang et al. / Aerospace Science and Technology 49 (2016) 209–214
Table 1
Compositions of non-toxic hypergolic reactive fuels.
Name Compositions
Stock 0 Tetraethylene glycol dimethyl ether (Tetraglyme)/Sodium borohydride
Stock 1 Tetraethylene glycol dimethyl ether (Tetraglyme)/Tetrahydrofuran/Sodium borohydride
Stock 2 Tetraethylene glycol dimethylether (Tetraglyme)/Tetrahydrofuran/Toluene/Sodium borohydride
Fig. 1. Molecular structures of hydrocarbon solvents used for non-toxic reactive fuels.
active participation in the ignition process, the fuel promoted by
a strong reducer, commonly referred to as a reactive fuel, provides
faster and more reliable ignition. Therefore, although hypergolic in-
teractions can be caused by the two different types of additives,
reactive fuels promoted by strong reducers are typically preferred.
Three reactive fuels were produced by blending sodium boro-
hydride (NaBH4 ) powder, a strong reducing agent, into energetic
hydrocarbon mixtures. Sodium borohydride was previously used
as an ignition promoter for 90 wt.% hydrogen peroxide by R. Ma-
hakali et al. [6]. In the previous work, although most of the fuels
demonstrated hypergolic properties with the oxidizer, they were
potentially not suitable for practical applications because the sol-
vents used for sodium borohydride had low chemical potential
energy. In addition, there was no attempt to evaluate the non-toxic
hypergolic bipropellant in actual conditions. This work is dedicated
to developing enhanced reactive fuels by using more energetic sol-
vents compatible with sodium borohydride and applying them into
a 500 N scale hypergolic bipropellant thruster with 90 wt.% hy-
drogen peroxide as an oxidizer. Through ground hot-fire tests, the
feasibility and performance of the non-toxic hypergolic bipropel-
lant thruster were evaluated.
2. Materials and experimental methods
2.1. Materials
Metal hydrides are typically introduced as reducing agents in
chemical synthesis and in materials for hydrogen storage appli-
cations. Light metal hydrides, such as lithium or beryllium com-
pounds, are preferred as additives in rocket fuels due to their
low molecular weight, enhancing the rocket performance. They
are, however, extremely expensive and difficult to handle; lithium
compounds react explosively with moisture and water. Practically,
sodium borohydride is a promising alternative when considering
cost and handling, even if it has lower chemical potential energy
than lithium or beryllium compounds. Moreover, the presence of
boron and borane compounds has been reported to act as ener-
getic additives or active promoters in the process of hypergolic
combustion [7,8]. The borohydride is also part of the electron-rich
groups that prefer hypergolic reactions with a strong oxidizer such
as hydrogen peroxide. Other characteristics of sodium borohydride,
which encourage its use, are described below [9]:
– The least expensive metal hydride commercially available (on a hy-
dride equivalent basis).
– Safe with regards to storage and use & handling.
– Industrial implementation requires no or limited equipment invest-
ment.
– Ease of work-up (water soluble boron salts).
Table 1 shows the three different types of non-toxic hypergolic
fuels that were considered in this work. All the candidates are
reactive fuels promoted by sodium borohydride. Stock 0 was pre-
pared by blending sodium borohydride powder into a tetraglyme
solvent. A small Teflon stir bar was used for vigorous mixing for
a minimum of one hour; the product was a colorless liquid. The
composition of Stock 0 was the same fuel previously tested by
R. Mahakali et al. [6]. Tetraglyme is a polar aprotic solvent that is
miscible with sodium borohydride and has excellent chemical and
thermal stability, along with high density (specific gravity: 1.013 at
20◦ C), low vapor pressure (< 0.01 mmHg at 20◦ C) and low toxi-
city [10]. However, its low chemical potential energy leaves room
for improvement.
Stock 1 and 2 are reactive fuels prepared and improved by
adding more energetic solvents, such as tetrahydrofuran and
toluene to Stock 0. Comparing the newly introduced solvents,
tetraglyme has lower chemical potential energy because the heat
of combustion decreases with the rise of the oxygen percentage
in the molecule; their molecular structures are pictured in Fig. 1.
The production methods of Stock 1 and 2 basically followed the
aforementioned method for Stock 0. The only difference between
Stock 0 and the enhanced reactive fuels was the composition of
solvents. The more energetic solvents did not retain the same com-
patibility with sodium borohydride, and thus precipitation was
formed at the end of the process. After leaving the solvents un-
der standard atmospheric conditions for a minimum of one day,
we could finally obtain colorless liquids by collecting the limpid
portion of the solution. Sodium borohydride powder with >98%
purity, 99.8% pure tetrahydrofuran (THF) and 99.8% pure toluene
were purchased from Samchun Chemical Inc. located at Daejeon,
and >99% pure tetraglyme was purchased from Sigma-Aldrich Inc.
Theoretical performance data and physical properties of the re-
active fuels are tabulated in Table 2. Density was measured by
I.S.O 649 Standard Hydrometers, and viscosity was measured with
an SV-10 VIBRO Viscometer. Vapor pressure of the mixtures was
calculated using Raoult’s law. The net energy content from com-
bustion was measured by a Parr 1261 bomb calorimeter. All candi-
dates have higher density than MMH, and Stock 2 is estimated to
be the most energetic material among the candidates, even more
than MMH. The observed unstable chemical behavior of Stock 1
during its storage is associated with its high volatility. Theoretical
vacuum specific impulse (I sp ) and O/F ratio were estimated using
NASA CEA code, where the chamber pressure was set to 30 bar
[11]. Based on the data, the non-toxic bipropellant combination of
Stock 2 fuel and 98 wt.% H2 O2 oxidizer is expected to have a per-
formance comparable to the conventional toxic hypergolic bipro-
pellants, with a volumetric specific impulse (ρ · I sp ) greater than
99% of MMH/RFNA and 97.5% of MMH/NTO. This slightly lower
performance can be compensated by the cost savings and risk re-
duction in terms of handling, storage and environmental impact.
 H. Kang et al. / Aerospace Science and Technology 49 (2016) 209–214 211

Table 2 2.2. Drop test

Theoretical performance data and physical properties of non-toxic reactive fuels.

Fuel Density Viscosity Vapor pressure Net energy content The drop test was implemented to verify the hypergolicity of
(kg/m3 ) (cP) (kPa) (MJ/kg)
the candidates with high test hydrogen peroxide. As shown in
Stock 0 1,013 7.1 1 .3 26.8
Fig. 3, a syringe pump fed the oxidizer through a nozzle and then
Stock 1 953 1.8 14.6 28.9
Stock 2 952 2.3 8 .8 30.8 a small oxidizer droplet fell down on the pool of hypergolic fuel
MMHa 874 0 .8 6 .7 28.3 at a height of 12 cm from the surface of the fuel. The droplet di-
ameter was approximately 3.2 mm. Upon contact of the droplet
Fuel Oxidizer Average density I sp ρ · I sp
(kg/m3 )b (s)c (kg · s/L) with the surface of the pool, the combustion occurred sponta-
Stock 2 98 wt.% H2 O2 1,196 318.1 380.4
neously, and the flame propagated rapidly into air. Ignition delay
MMH RFNA 1,194 319.7 381.7 was defined as the time interval between the contact of the reac-
MMH NTO 1,159 336.5 389.8 tants with the oxidizer droplet and the first detection of a flame.
a
PubChem Public Chemical Database, the PubChem Project, USA: National Center The whole process was recorded by a high speed CCD camera,
for Biotechnology Information. X-StreamTM XS-3 model with 1000 fps, and the delay was iden-
b
Density averaged between fuel and oxidizer. tified using the time marks on the consecutive images. A high-
c
Estimating by NASA CEA code.
powered halogen lamp illuminated the reaction process. All fuels

Infrared spectroscopy is used in research endeavors for both

organic and inorganic chemistry, and it is a simple and reliable
technique to obtain molecular information from a sample. Fig. 2
indicates the infrared spectra of Stock 2, along with its reference
materials: tetraglyme, toluene and tetrahydrofuran. The reference
materials were tested to assess the instruments’ influence. Accord-
ing to the data of Stock 2, with the exception of the weak band
appearing between 2000 and 2500 cm−1 wavenumber, the other
peaks correspond to the observations in reference materials. The
complexity of the infrared spectra is a result of the solvents’ com-
plex molecular structure; the addition of an additive also brings
about a combination of bands and overtones of the fundamental
vibrations, thereby increasing the number of observed absorption
peaks [12]. For Stock 2 fuel, the unusual band might appear due
to the presence of the dissolved sodium borohydride, consider-
ing that Harvey and McQuaker [13] recorded distinct absorption
peaks in the spectra of sodium borohydride in the region of 2200
to 2400 cm−1 at 295 K. Fig. 3. Schematic of drop test apparatus.

Fig. 2. Infrared spectra of Stock 2 fuel and reference materials measured by IS50 ATR with number of scans: 32, data spacing: 0.482 cm−1 , detector: DTGS ATR and range:
400–4000 wavenumber (cm−1 ).
212 H. Kang et al. / Aerospace Science and Technology 49 (2016) 209–214
Fig. 4. Consecutive high speed images of hypergolic reactions between Stock 2 fuel and 90 wt.% H2 O2 .
Fig. 5. Variation of ignition delay depending upon H2 O2 concentration.
experienced hypergolic interactions with hydrogen peroxide. Fig. 4
displays high speed images taken during the period of hypergolic
reaction between Stock 2 and 90 wt.% H2 O2 , and Fig. 5 provides
the variations in the delays, depending on the concentration of
hydrogen peroxide. According to the reported data [14], the ig-
nition delay of the existing hypergolic combinations is normally
less than 5 ms in this type of drop test. Thus, if we use the green
hypergolic combinations of Stock fuels and 98 wt.% H2 O2 as an
oxidizer, the hypergolic start for a thruster is expected to be appli-
cable.
Based on the results from the aforementioned works, Stock 2
was regarded as the best available. Therefore, a 500 N scale hyper-
golic thruster was designed on the basis of the following propellant
combination: Stock 2 fuel and 90 wt.% H2 O2 oxidizer. Instead of
98 wt.% H2 O2 , 90 wt.% H2 O2 was selected as an oxidizer in this
work for safety reasons. The aim of the static firing test was to
evaluate the performance of the thruster using the newly devel-
Fig. 6. Outline of propellant feed system.
oped non-toxic hypergolic bipropellant combination by operating
it under actual operating conditions.
2.3. Configuration of experimental system
Fig. 6 outlines the propellant feed system for the static firing
test. The propellants were fed into the thruster by regulating the
pressurized high purity nitrogen gas. Pneumatic valves controlled
the injection sequence of the propellants. A pressure transducer,
manufactured by Sensor System Technology Co., LTD, was installed
at the end of the chamber, which functioned with ±0.037% fem-
tosecond accuracy. A data acquisition card (DAQ) was used to
record pressure data and a SCXI module from National Instru-
ments was used as a signal conditioning device with a sampling
rate of 1000 Hz and a 100-kHz filter. The mass flow rates of both
the fuel and the oxidizer were measured using orifice-type mass
flow meters (MFMs) with ±0.5% accuracy; these orifice diameters
were 1.2 mm for the fuel and 2.5 mm for the oxidizer. A cavitat-
ing venturi tube was inserted as a passive flow control device into
the oxidizer feed line for the reasons mentioned below. With an
oxidizer-to-fuel ratio of 5.48, the mass flow rate of the oxidizer ac-
counted for the majority of the total mass flow rate. Thus, the total
mass flow rate could then be effectively regulated by exclusively
controlling the oxidizer mass flow rate to prevent the oversupply
of propellants caused by the tremendous pressure difference be-
tween the tank and the chamber during the startup phase [15,16].
As a result, hypergolic ignition could be achieved smoothly in the
condition of a fuel-rich atmosphere, having the advantage of pro-
moting chemical reaction rates for hypergolic ignition, particularly
for hydrocarbon fuels. By contrast, an oxidizer-rich stream, which
could lead to serious damage to the chamber wall or easily initiate
explosion, should be avoided [17,18].
Table 3 contains the design parameters for a ground test model
of 500 N scale non-toxic hypergolic bipropellant thruster. A pentad
unlike-impinging jet type injector was fabricated, having one fuel
injection orifice at the center of the injector face and four oxidizer
 H. Kang et al. / Aerospace Science and Technology 49 (2016) 209–214 213

Table 3
Design parameters of 500 N scale non-toxic hypergolic bipropellant thruster ground
model.

Parameter Value
Oxidizer 90 wt.% H2 O2
Reactive fuel Stock 2
Design thrust 500 N
Design chamber pressure 30 bar
Ideal vacuum specific impulse (I sp ) 306.5 s
Ideal characteristic velocity (C ∗ ) 1579.2 m/s
Theoretical O/F ratio 5.48
Design mass flow rate Oxidizer: 131.4 g/s, fuel: 24 g/s

Combustor
Nozzle type 15◦ conical nozzle
Nozzle throat diameter 10.2 mm
Nozzle expansion area ratio 4
Chamber length without converging section 80.2 mm scale
Chamber diameter 32.5 mm Fig. 8. Demonstration of 500 N scale non-toxic hypergolic bipropellant thruster.
Converging angle 30◦

Injector
Injector type Pentad unlike-impinging jets
Configuration of injection element Single element
(1 fuel orifice + 4 oxidizer orifices)
Impinging oxidizer jet angle 60◦
Fuel orifice diameter 1.2 mm
Oxidizer orifice diameter 1.25 mm

Fig. 9. Pressure curves verse time.

Fig. 7. Cold flow test of pentad unlike-impinging jet injector.

injection orifices surrounding it. The oxidizer liquid jets collided

with the fuel jet at the designated point with a 60◦ inclined angle
as indicated in Fig. 7.

3. Results and discussion

The static firing test was conducted for a total of 3.5 s with
the objective of demonstrating the feasibility of 500 N scale bipro-
pellant thruster using the novel non-toxic hypergolic propellant
combination. As shown in Fig. 8, hypergolic ignition was achieved
without the use of an external ignition system, and the rocket
exhaust plume was stably formed. Mach diamonds in the plume
were clear evidence that the nozzle throat was choked; there-
fore, the combustion gas flew at supersonic speed. Fig. 9 reports
the pressure data measured in the chamber during the test. Al- Fig. 10. Variation on mass flow rate of propellants over time.
though some pressure perturbations were observed in the fuel and
the oxidizer feed injectors at startup, the chamber pressure built dicates that the cavitating venturi functioned well, even under the
up smoothly, and the thruster experienced steady-state operation, tremendously high differential pressure during the startup phase.
roughly from 0.8 s to 3.6 s. Fig. 10 provides the variation of the The pressure perturbation may be caused by the impact of hyper-
mass flow rates of the propellants over time. The fuel was injected golic ignition, accompanied with the oversupply of fuel. The aver-
into the chamber slightly earlier than the oxidizer because of the age mass flow rate of the oxidizer and the fuel during steady-state
two main factors; the difference in the response times of the con- operation was approximately 129.9 g/s and 23.2 g/s, respectively,
trol valves and the existence of the cavitating venturi. Although the which was very close to the design values.
fuel was oversupplied before the chamber pressure was fully built The rising time and combustion instability, which are essen-
up, the mass flow rate of the oxidizer was consistent. The result in- tial factors for control, were estimated for the design validation. At
214 H. Kang et al. / Aerospace Science and Technology 49 (2016) 209–214
Table 4
Performance data of 500 N scale non-toxic hypergolic bipropellant
thruster ground model.
Parameters Experimental data
Mass flow rate of fuel 23.2 g/s
Mass flow rate of oxidizer 129.9 g/s
C ∗ efficiency 88.3 (±2.1%)
Rising time (t rising ) 158 ms
Pressure instability (P ins ) ±7.69%
this point, the rising time (t rising ) was defined by Eq. (1), where
t 10% and t 95% are the times when the pressure first approaches
10% and 95% of the average chamber pressure, respectively. The
combustion instability was measured in terms of pressure oscilla-
tion ( P ins ) inside of the chamber, defined in Eq. (2), where P max
and P min are the maximum and minimum pressures, respectively;
P ave is the average chamber pressure during steady-state opera-
tion. C ∗ efficiency (ηc ∗ ) is also a crucial factor to evaluate how the
propellants are effectively combusted. The C ∗ efficiency was esti-
mated by Eq. (3) where C ideal∗ can be obtained from the NASA CEA
code, and C exp ∗ is calculated by using the nozzle throat ( A ), the
th
average chamber pressure and the total mass flow rate of the pro-
pellants (ṁtot ).
t rising = t 95% − t 10%
P max − P min
P ins (%) = × 100
P ave
∗ pellant propulsion concepts for space transportation and technology develop-
C exp ∗ P ave × A th
ηc∗ (%) = × 100, C exp =
C∗
ideal
ṁtot
Table 4 gives the performance data of the 500 N scale non-
toxic hypergolic bipropellant thruster. Typically, for technical rea-
sons, the pressure fluctuation is not recommended to be allowed
to exceed approximately ±5% during steady-state operation [19].
The experimental fluctuation was slightly higher than this stan-
dard. The calculated C ∗ efficiency was also slightly lower than
those of commercial thrusters, which are higher than 90%. Al-
though the performance of the thruster seems unsatisfactory
compared to commercial standards, various areas of improve-
ment remain, which achieved better performance, considering
that the thruster was designed as a ground test model. The ris-
ing time and combustion instability in the startup phase can
be improved by introducing a new design of injector and con-
trolling the injection sequences of the propellants. Consequently,
this work demonstrated the successful operation of an engineer-
ing model of 500 N scale bipropellant thruster using the novel
non-toxic hypergolic propellant combination, which represents
the feasibility of this novel concept engine for future space mis-
sions.
4. Conclusions
This research was devoted to finding a novel combination of
non-toxic hypergolic bipropellants and evaluating the performance
of 500 N scale non-toxic hypergolic bipropellant thruster. The pro-
pellant combination of energetic reactive fuel (Stock 2) and 90 wt.%
H2 O2 was selected for the static firing test. This work success-
fully demonstrated the steady-state operation of the thruster for
3.5 s, which implies that the concept of the green hypergolic
bipropellant thruster is feasible. However, to increase the perfor-
mance of the thruster, future work must be conducted to find
more energetic non-toxic hypergolic propellants and to develop a
thruster with a more sophisticated design. The work represented
in this study has profound implications for future studies in the
green space technology fields and may contribute to solving the
problems caused by existing toxic propellants.
Conflict of interest statement
There is no conflict of interest statement.
Acknowledgement
This research was supported by Basic Science Research Pro-
gram through the National Research Foundation of Korea (NRF),
funded by the Ministry of Science, ICT and Future Planning
(NRF-2014M1A3A3A02034777).
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