Fuel 255 (2019) 115729

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Ignition of boron-based green hypergolic fuels with hydrogen peroxide T

Vikas K. Bhosale, Junyeong Jeong, Sejin Kwon
⁎

Department of Aerospace Engineering, Korea Advanced Institute of Science and Technology, KAIST, 291 Daehak-ro, Yuseong-gu, Daejeon 34141, Republic of Korea

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: Exploring novel green hypergolic fuels ignited with hydrogen peroxide (H2O2) offers a number of opportunities
Ionic liquid in space propulsion with regard to replacing conventional toxic propellant combinations. The green hypergolic
Hypergolic fuel fuels, BeH bond-rich zwitterions and ionic liquids (ILs) were synthesized; their hypergolic reactivity was in-
Combustion vestigated with 95% H2O2. Remarkably, ammonia borane (AB) and 1-ethyl-3-methyl imidazolium borohydride
Hybrid propellant
([EMIM][BH4]) exhibited the lowest ignition delay times of 8.1 and 18.5 ms, respectively. For a comprehensive
Bipropellant
application, the reactivity of liquid and hybrid fuel blends were studied. A liquid fuel blend, [EMIM][BH4] and
methyl imidazolium borane (MIMB) (1:1, w/w) exhibited the ignition delay time of about 35 ms. Further, a solid
hybrid fuel blend consisting of 40% AB-paraffin revealed a hypergolic ignition delay time of 9.2 ms.
Additionally, the gas phase heat of formation and specific impulse were calculated using G09 and NASA-CEC-71
programs, respectively. The specific impulse of AB was 273 s, which is higher than the stated hypergolic zwit-
terions. Hence, the BeH bond-rich zwitterions and ILs are promising choices for new generation green hy-
pergolic liquid and hybrid rocket propulsion.

1. Introduction
Hypergolic fuels have a remarkable significance in rocket applica-
tions. They have a propensity for auto-ignition with storable oxidizers
viz., HNO3, N2O4, and H2O2. These fuels can help eliminate an external
ignition source and provide simplicity for the “start” and “restart” cap-
ability of the rocket engine [1]. Therefore, hypergolic fuels have com-
prehensive applications in space vehicles, space stations, manned
landers, altitude control and stabilization, orbit modifications, etc [2–5].
Hypergolic fuels are classified into (i) solid and (ii) liquid hypergolic
fuels. Solid hypergolic fuels are typically used as a fuel grain in hybrid
propellants [6–8]. Solid hypergolic fuel grain includes hydrazones,
thiocarbohydrazones, monocyclohexanoethiocarbohydrazone (CHTCH),
tagaform (polybutadiene with an aromatic amine), metal hydrides, etc.
which are commonly used in hybrid rocket propulsion. Liquid hypergolic
fuels, Hydrazine-based derivatives (monomethyl hydrazine, MMH;

⁎
Corresponding author.
E-mail address: trumpet@kaist.ac.kr (S. Kwon).

https://doi.org/10.1016/j.fuel.2019.115729
Received 11 February 2019; Received in revised form 24 June 2019; Accepted 26 June 2019
Available online 03 July 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
V.K. Bhosale, et al.
unsymmetrical dimethyl hydrazine, UDMH) have considerable im-
portance in bipropellant applications [1]. Because, these fuels have high
performance in combination with oxidants such as HNO3 and N2O4.
However, these liquid propellant combinations are highly toxic to hu-
mans and with regard to the surrounding environment. Notably, the
amine and hydrazine-based derivatives are carcinogenic and have high
vapor toxicity [9]. The oxidizers, HNO3 is corrosive and N2O4 generates
toxic vapors under ambient conditions [10]. Hence, it is essential to find
the green hypergolic combinations, which are environmentally friendly
without compromising their performance.
Rocket-grade hydrogen peroxide (RGHP, > 90%) has been widely
used as a green oxidizer with various hypergolic fuels [11,12]. Because,
hydrogen peroxide is of low toxicity, has low vapor pressure and exo-
thermally decomposed into environmentally-benign byproducts. Re-
searchers have studied hypergolic combinations of RGHP with various
reactive fuels such as lower aliphatic alcohols, hydrocarbons, polyalk-
ylene polyamines, glycol ethers (diglyme, triglyme and tetraglyme),
and dimethylformamide [11]; in addition, the promoters sodium bor-
ohydride, lithium hydride, and lithium aluminum borohydride have
been used to help lower the ignition delay time of the fuel. Nonetheless,
the metal borohydrides are moisture sensitive and precipitate in time
due to their poor stability in fuel. Apart from the borohydrides, active
metal catalysts such as Cu(I), Cu(II), Co(II), Fe(II), Fe(III), Ru(II), Ru
(III), Mn(II), Sm(III) and V(II) have been reported to date to lower the
ignition delay of hypergolic fuels [13]. However, the high molecular
weight of the metal catalyst can lower the specific impulse due to the
high molecular weight of exhaust products. Hence, it is essential to find
the green hypergolic fuel having a low ignition delay with RGHP.
Recently, ionic liquids (ILs) and zwitterions have been investigated
as components in green hypergolic fuel for rocket propulsion [14–21].
ILs are salts of an organic cation and organic or inorganic anions that
melt below 100 °C [22]. They have negligible vapor pressure, com-
parable viscosity and density, better thermal stability, and are hy-
pergolic with storable oxidizers [23]. Furthermore, zwitterions have
low vapor pressure, low viscosity, comparable thermal stability and are
reactive with HNO3 and N2O4 [16,24–26]. However, few studies on ILs
hypergolic with RGHP are available and there are a limited number of
investigations on hypergolic ignition of pure zwitterions with RGHP. In
2011, Stefan et al. investigated aluminum borohydride-based hypergolic
ILs with 98% RGHP, ignition delay < 30 ms [10]. Later, Gozin et al.
developed closo-icosahedral peridoborane and iodocuprate-based pro-
moters to help lower the ignition delay of ILs and zwitterions with
RGHP [27,28]. Nevertheless, combustion of high molecular weight
promoters can lead to the production of high molecular weight exhaust
products which apparently lower the specific impulse. Simultaneously
maintaining the high performance and lowering the toxicity of pro-
pellant is extremely difficult. Hence, the ultrafast igniting environment-
friendly fuel with RGHP is the challenge of current research.
In this article, green hypergolic fuels based on ILs and zwitterions
were synthesized and hypergolic performance was investigated with
95% RGHP. The hydrogen-rich BeH bond encased in ILs and zwitter-
ions impart the hypergolic ignition with RGHP [16,25,29]. Interest-
ingly, all fuels exhibited hypergolic reactivity with RGHP, except
N,N,N′,N′ tetramethyl ethylene diaminebisborane (TMDABB).
2. Experimental section
The zwitterion fuels (Fig. 1) include ethylenediamine bisborane
(EDABB), N,N,N′,N′-tetramethyl-ethylene-diamine bisborane
(TMDABB), methyl imidazolium borane (MIMB) and 1,3-dimethyl
imidazolium borane (DMIMB), were synthesized using reported method
[14]. Furthermore, the ILs fuels (Fig. 1), 1-ethyl-3-methyl imidazolium
borohydride ([EMIM][BH4]), 1-ethyl-3-methyl imidazolium cyanobor-
ohydride ([EMIM][BH3CN]) and 1-allyl-3-ethyl imidazolium cyano-
borohydride ([AEIM][BH3CN]) were synthesized using a reported
method [30]. Additionally, a liquid fuel blend of IL, [EMIM][BH4] and
2
Fuel 255 (2019) 115729
MIMB (1:1, w/w) was prepared. Further, hybrid fuels containing 25 and
40% of ammonia borane (AB) grain with paraffin blends were prepared
using a pressed method. The detail synthesis method and structural
analysis of zwitterions, ILs and blends are described in the Supporting
Information (SI-A & B).
Ignition delay of the fuels was measured with RGHP (95% H2O2)
using a hypergolic drop test setup (Fig. 2). The sequence of images
containing 1000 frame per second (fps) footage was recorded using a
high-speed charge-coupled device (CCD) camera (X-StreamTM XS
model with 1000 fps capability). A 1000 µl syringe was used to dispense
10 µl of liquid fuel into the pool of cylindrical glass beaker containing
1000 µl of oxidizer RGHP and a 1000 µl syringe was used to drop 10 µl
of RGHP into the petri dish containing a measured quantity of solid
fuel. The distance between the syringe point (where fuel or oxidizer is
dispensed from) and the top surface of the oxidizer or fuel was main-
tained 110 mm during the ignition test. The average size of the oxidizer
drop was measured and determined to be 3.0 mm. The time lapse be-
tween the initial contact of the fuel with the oxidizer and the emergence
of a flame was measured.
The heat of formation (ΔHf) values of EDABB, TMDABB, MIMB,
[EMIM][BH3CN], [AEIM][BH3CN] and [EMIM][BH4] were calculated
by employing the isodesmic reactions. A G09 suite program was used to
simulate data [31]. The computational details are provided in the
Supporting Information (SI-D). The specific impulse of hypergolic fuels
was also obtained by using NASA-CEC-71 software [32]. The para-
meters such as the chamber pressure (Pc, 2.4 × 106 Pa), exit pressure
(Pe, 9.8 × 104 Pa), nozzle area expansion ratio of the nozzle exit area to
the nozzle throat area (Ae/At, 4.0) and various oxidizer to fuel ratios
(O/F, 0.5–5.5) were considered during the simulation.
3. Result and discussion
3.1. Synthesis
The BeH bond-rich moieties are known to be hypergolic with HNO3
[30]. Hence, the BeH bond containing zwitterions and ILs were syn-
thesized in the laboratory, except AB borane, which was purchased
from Sigma Aldrich. The dry solvent THF was used for the experiment,
because metal borohydrides are moisture sensitive and the presence of
H2O causes various side reactions. White crystalline solids of EDABB,
TMDABB, and DMIMB were obtained; MIMB was a liquid at room
temperature. The TMDABB was water insoluble, and DMIMB was re-
crystallized from water. Further, ILs, [EMIM][BH3CN], [AEIM][BH3CN]
and [EMIM][BH4] were synthesized by simple metathesis reactions
involving halide salt and metal borohydride in the selective solvent
(CH2Cl2 or MeCN) at room temperature. ILs, [EMIM][BH3CN] and
[AEIM][BH3CN] were liquid, and [EMIM][BH4] was solid at room
temperature. IL, [EMIM][BH4] was used to prepare a blend with zwit-
terion MIMB.
Consequently, hypergolic reactivity of liquid blend 50:50 (w/w)
was investigated. AB grains are hydrolytically stable [8]; hence, 25 and
40% AB blends were prepared with solid paraffin (Fig. 3) to find the
application of fuel grains in hybrid propellants. The cast method was
used to make a pellet; its hypergolic reactivity was then studied. The
physicochemical properties and performance evaluation of the zwit-
terions and ILs are summarised in Table 1. They exhibited higher
density and thermal stability than the toxic hydrazine-based fuels.
3.2. Hypergolic ignition
An auto ignition of fuel when it comes in contact with an oxidant is
the characteristic property of a hypergolic fuel. This property is mea-
sured practically in terms of an ‘ignition delay (ID)’ [1]. It is the time
lapse between the initial contact of fuel with an oxidizer and first flame
develops. A short ignition delay of fuel is required to use fuel reliably in
rocket propulsion. An “open cup drop test” was conducted to measure
V.K. Bhosale, et al. Fuel 255 (2019) 115729

Fig. 1. Structures of hypergolic fuels.

Fig. 2. Hypergolic drop test setup of ignition delay measurement.

the precise ignition delay of fuels at atmospheric pressure; a detailed
procedure is described in Section 2. The ignition test of each molecule
was performed in triplicates; the average reading was noted (Table 1).
Figs. 4–6 depicts the series of hypergolic images of fuels; a bright green
flame that was observed confirms the hypergolic initiation by early
combustion of the boron-containing species. According to the chemical
nature of the zwitterions and ILs, ignition delay varies with RGHP. AB
exhibited the shortest ignition delay of about 8.1 ms; a smooth com-
bustion was noted without occurrence a columbic explosion. However,
the ignition occurs with a swelling of the AB surface at 5.3 ms. Other
zwitterions such as EDABB, MIMB and DMIMB exhibited the ignition
delays of 30.7, 258 and 59.2 ms, respectively. Among these, TMEDBB
was not ignited with RGHP, even though it has a borane-rich moiety.
This may be due to TMEDBB having alkyl substituents which lead to
non-hypergolic behaviour [34].
ILs, [EMIM][BH3CN] and [AEIM][BH3CN] have shorter ignition
delay values with WFNA as 1.5 and 3.1 ms, respectively [30,35], and
exhibit longer ignition delays (> 1000 ms) with RGHP in both fuel-rich
and oxidizer-rich conditions. This may be due to the weak acidic nature
of RGHP than WFNA. As expected, IL [EMIM][BH4] exhibited the
lowest ignition delay of 18.5 ms (Table 1) and which is shorter than
aluminium borhydride based ILs (ignition delay, 30 ms) [10]. The
[BH4] anion is more reactive than [BH3CN] anion with RGHP under the
conditions observed. However, IL, [EMIM][BH4] is very difficult to use

3
V.K. Bhosale, et al. Fuel 255 (2019) 115729

investigate the BeH bond based RGHP reactive green hypergolic fuels.

3.3. Thermal stability

The thermal behavior of zwitterions, ILs and a 40% blend of AB

25% AB-Paraffin 40% AB-Paraffin
Fig. 3. Images of 25 and 40% AB-paraffin blends.
in liquid bipropellant applications, because it is a solid at room tem-
perature. Therefore, a liquid fuel blend of MIMB and [EMIM][BH4]
(1:1, w/w) was prepared to find the hypergolic reactivity with RGHP. A
shorter smooth ignition occurs at about 35 ms in fuel-rich conditions
and 46.1 ms under oxidizer-rich conditions (Figs. 5b and 6), which is
within the acceptable limit of hypergolic liquid fuel (ignition delay time
of 50 ms) [1]. Interestingly, the ignition delay of liquid fuels in fuel-rich
conditions was found considerably lower than the oxidizer-rich system.
This may be due to the high latent heat of hydrogen peroxide (1260 kJ/
kg) [36]. Ignition of fuel occurs when sufficient amount of heat is
generated during the pre-ignition reaction. The amount of heat energy
generated during the pre-ignition reaction in oxidizer pool may be
immediately absorbed by unreacted hydrogen peroxide and therefore
longer the ignition delay of fuel. However, in fuel-rich systems, the total
heat energy generated during pre-ignition reaction of fuel and oxidizer
may be used for an ignition process and exhibits shorter ignition delays.
Moreover, the solid hypergolic fuel grain could help prepare a green
hypergolic hybrid fuel for rocket application. Therefore, we tested 25
and 40% AB-paraffin hybrid fuel blends with RGHP. The ignition delay
times of 25 and 40% AB paraffin blends were found to be 17 and 9.7 ms,
respectively. Interestingly, the ignition delay time of 40% AB-paraffin
was quite similar to the pure AB ignition delay time.
In conclusion, BeH bond-rich hypergolic solid fuel components in
granular form as well as related liquid fuels serve as better alternatives
for the conventional hypergolic rocket fuel system when taking into
consideration the toxicity of such fuels. This study therefore serves to
paraffin were measured by using a simultaneous thermal gravimetric
analyzer (TGA) and differential scanning calorimeter (DSC) analyzer
(SI-C). The DSC curves obtained for AB, DMIMB and [EMIM][BH4]
showed an endothermic peak corresponding to melting temperatures
120, 135 and 50 °C, respectively. The TGA results also confirm that the
observed an endotherm belongs to the physical process of melting and
not to the chemical process of thermal decomposition. However,
EDABB does not exhibit the endotherm, and it starts to decompose at
92 °C with a decomposition temperature of 128 °C. The decomposition
temperature of AB, EDABB, MIMB, DMIMB and [EMIM][BH4] were
found to be at 127, 128, 260, 234 and 130 °C, with weight losses of 22,
27, 52, 72 and 76%, respectively, from 25 to 400 °C (Table 1). A
somewhat higher thermo-stability of MIMB was determined due to its
more stable molecular structure.
Fig. 7 reveals that AB exhibits poor thermal stability (Td: 127 °C)
and exhibits a two-stage thermal decomposition. However, a 40% AB
paraffin blend exhibited a melting temperature of 124 °C; it was in-
creased by 4 °C in comparison with AB (Fig. 8) rationalized by the van
der Waals interaction between AB and paraffin that helps to enhance the
thermal stability. ILs, [EMIM][BH3CN] and [AEIM][BH3CN] are ther-
mally stable up to 247 and 265 °C, respectively (Table 1). However, IL
[EMIM][BH4] underwent decomposition at 130 °C. This clearly in-
dicated the importance of an anionic moiety component in the thermo-
stability of the compounds rather than the structure of the cation (See
Fig. 9).
3.4. The heat of formation and specific impulse
The foregoing considerations prompted us to investigate the heat of
formation of zwitterions and ILs; to our delight, positive and sig-
nificantly higher values of ΔHf ranging from −124 kJ/mol to 225 kJ/
mol were obtained for all trials (Table 1). Interestingly, the imidazo-
lium-based zwitterions and ILs exhibited a positive heat of formation
with higher amount of IL, [AEIM][BH3CN], 225 kJ/mol. The compound
EDABB has the lowest heat of formation, −124 kJ/mol. However, Δ Hfs

Table 1
Physicochemical properties and performance of hypergolic fuels.
Hypergolic fuels Tma (°C) Tdb (°C) ϱc (g/cm3) ηd (mPa∙s) ΔHfe (kJ/mol) ID (ms)f

Fuel richness Oxidizer richness

AB 120 127 0.780 – −38.07 8.1 ( ± 0.8) –

EDABB – 128 – −92.32 30.7 ( ± 1.8) –
TMEDBB – – – – −124.75 No ignition –
MIMB −7g 260 0.930 5 149.30 258.0 ( ± 5.2) 249 ( ± 4.9)
DMIMB 135 234 1.050 – 61.61h 59.2 ( ± 2.3) –
[EMIM][BH4] 50 130 0.920 – 132.20 18.5 ( ± 1.5) –
[EMIM][BH3CN] −71i 247 0.980 19 136.06 > 1000 > 1000
[AEIM][BH3CN] < −50i 265 0.953 17 225.23 > 1000 > 1000
MMHj −52 88k 0.874 0.775 55.00 – –
UDMHj −57 62k 0.786 0.492 52.00 – –

a
Tm: melting temperature.
b
Td: decomposition temperature.
c
ϱ: density.
d
η: viscosity.
e
ΔHf: gas phase heat of formation.
f
ID: ignition delay of fuel measured with RGHP (95%, H2O2) in fuel rich and oxidizer rich condition.
g
Ref. [24].
h
Ref. [25].
i
Ref. [33].
j
Ref. [18].
k
Boiling point.

4
V.K. Bhosale, et al. Fuel 255 (2019) 115729

Fig. 4. High-speed camera ignition sequence images of (a) AB, (b) DMIMB, (c) [EMIM][BH4] and (d) 40% AB-paraffin blend.

Fig. 5. High-speed camera ignition sequence images of liquid fuel under oxidizer-rich conditions of (a) MIMB and (b) [EMIM][BH4] & MIMB (1:1, w/w) blend.

values of the aromatic zwitterions and ILs are higher than UDMH and
MMH [24].
Specific impulse (Isp) is the total impulse produced per unit of
propellant expended; it define the efficiency of rocket engines. The
theoretical specific impulse of AB, EDABB, TMDABB, MIMB, DMIMB,
[EMIM][BH3CN], [AEIM][BH3CN], [EMIM][BH4], MMH and UDMH
was calculated with 95% H2O2 using NASA-CEC-71 software. The gas
phase heat of formations were considered for the simulation of the
specific impulse. The parameters used during the evaluation consist of
infinite-area combustion (IAC) model and frozen flow conditions. The
specific impulse was evaluated at certain set values of chamber pressure
(Pc, 2.4 × 106 Pa), exit pressure (Pe, 9.8 × 104 Pa), nozzle area expan-
sion ratio of the nozzle exit area to the nozzle throat area (Ae/At, 4.0)
and considering the various oxidizer to fuel ratios (O/F, 0.5–5.5).
AB exhibited the highest specific impulse of 273 s at optimum O/F,
2.5; ILs, [EMIM][BH3CN] and [AEIM][BH3CN] show the lowest specific

5
V.K. Bhosale, et al. Fuel 255 (2019) 115729

Fig. 6. High speed camera ignition sequence images of liquid fuel under fuel-rich conditions of [EMIM][BH4] & MIMB (1:1, w/w) blend.

105 20
Td: 127 oC TGA
DSC
100
Td: 166 oC 15

Weight loss: 9.96%

95
Heat flow (W/g)

10
Weight (%)

90

5
85
Weight loss: 12.55%
0
80

Tm: 120 oC
75 -5
50 100 150 200 250 300 350 400

Temperature (OC)

Fig. 7. DSC-TGA of pure ammonia borane (AB).

Td: 339.0 oC
TGA
DSC 14 Fig. 9. Graph of specific impulse (Isp) vs oxidizer-to-fuel (O/F) ratio of zwit-
100
Weight loss: 2.7% terions and ILs.
Weight loss: 3.9% 12
90 10
MMH and UDMH at optimum O/F (Table 2). These studies can be ef-
Heat flow (W/g)

8 ficient to boost the influential role of AB hypergolic propellant for green

Weight (%)

80 Td: 124.8 oC
Td: 163.5 oC 6
space propulsion.
Weight loss: 42%
70 4
4. Conclusions
2
60 In this work, BeH bond-rich zwitterions and ILs were synthesized,
0
comprehensively characterized and their hypergolic performance stu-
50 Tm: 60.99 oC
-2 died with 95% H2O2. For the first time, we are reporting hypergolic
Tm: 124.8 oC
-4 reactivity of AB with RGHP with a short ignition delay of about 8.1 ms.
50 100 150 200 250 300 350 400 The zwitterions and ILs show a smooth deflagration and participation of
Temperature (OC) boron upon the initial combustion. Hence, 25 and 40% AB-paraffin
blends were prepared in the pursuit of applications for AB fuel grain in
Fig. 8. DSC-TGA of 40% AB-paraffin blend.
hybrid propulsion. The 40% AB-paraffin blend exhibited a similar ig-
nition delay (9.7 ms) as found for AB. Specific impulse of AB was also
impulse of 253 s at O/F, 3.5 (Fig. 7). This may occur due to the low demonstrated higher (Isp, 273 s) than the MMH and UDMH.
molecular weight of exhaust products of AB. Overall, all molecules IL, [EMIM][BH4] exhibited the lowest ignition delay of 18.5 ms than
show the specific impulse > 253 s. Interestingly, AB and EDABB ex- the ILs, [EMIM][BH3CN] and [AEIM][BH3CN] (ignition delay >
hibited the higher specific impulse than conventional hypergolic fuels, 1000 ms) with 95% H2O2. Interestingly, a hypergolic liquid fuel blend

6
V.K. Bhosale, et al.
Table 2
Specific impulse (Isp) of hypergolic fuels at optimum O/F ratio.
Hypergo-lic fuels AB EDABB TMEDBB MIMB DMIMB
l
O/F 2.5 3.0 4.0 3.0 3.5
Ispm (s) 273 262 259 256 254
l
optimum oxidizer-to-fuel ratio; mspecific impulse calculated using NASA-CEC-71 program.
of [EMIM][BH4] and MIMB (1:1, w/w) exhibited ignition delay of
about 35 ms and which is in the acceptable limit of liquid hypergolic
fuels. In particular, RGHP reactive environment-friendly BeH bond-rich
green hypergolic zwitterions and ILs fuels can be better alternatives
when considering the conventional toxic propellant combinations.
Acknowledgments
We gratefully acknowledge the financial support from Defense
Acquisition Program Administration and Agency for Defense
Development, South Korea under the contract UD180046. The authors
would also like to thank Professor David G. Churchill for his continuous
support for research guidance.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuel.2019.115729.
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