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Proceedings of the Combustion Institute 39 (2023) 5677–5686

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Understanding the pyroelectric combustion behaviour

of metallized electrically controlled solid propellants
Kanagaraj Gnanaprakash, Jack J. Yoh∗
Department of Aerospace Engineering, Seoul National University, Seoul 08826, Republic of Korea

Received 4 January 2022; accepted 4 July 2022

Available online 19 August 2022

Abstract

Solid rocket propellants that demonstrate variable burning rates are highly desirable in various propulsion
applications. Electrically controlled solid propellants (ECSPs) are one such kind that ignite and combust only
when external electric power is applied, which enables to adjust/control their combustion rates. However, the
knowledge on their combustion mechanisms is scant in the limited literature. In this study, pyroelectric com-
bustion behaviour of metallized ECSPs, based on lithium perchlorate (LP) and poly vinyl alcohol (PVA),
containing 5%, 10%, and 15% tungsten (W) are investigated, in comparison to the non-metallized baseline
propellant. Theoretical performance parameters, heat release and mass loss from decomposition process, and
combustion rates are obtained. Pyroelectric combustion of ECSPs involves electrolytic decomposition of LP
producing oxidizer species, which react with fuel species from PVA and/or W in thermochemical reactions, to
generate heat and products including LiCl, HCl, LiOH, WO3 , etc. Results indicate that addition of W reduces
the theoretical adiabatic combustion temperature and overall heat release from exothermic decomposition
by 19% and 36% respectively, in ECSP-M15 containing 15% W, compared to the baseline case. However,
relatively low voltage response time for metallized ECSPs implies that their ionic conductivity is higher than
the baseline ECSP. More importantly, combustion rates of all ECSPs increase exponentially with increase in
applied initial voltage in the 100–500 V range. Inclusion of W enhances the combustion rates significantly by
4.9 times at 100 V and by 1.7 times at 500 V for ECSP-M15 relative to the baseline propellant. This signifies
that electrochemical mechanisms become the rate controlling step at high electric power, in governing the
pyroelectric combustion behaviour of ECSPs. Further, these propellants were successfully tested for multi-
ple burn/no-burn conditions under the application/removal of the external electric power, which is highly
desirable for various propulsion systems.
© 2022 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Keywords: Electrically controlled solid propellants; Tungsten; Pyroelectric combustion rates; Electrolytic decomposition;
Thermochemical reactions

1. Introduction

Solid rocket propellants have been utilized in

∗ Corresponding author. various propulsion systems due to their simple de-
E-mail address: jjyoh@snu.ac.kr (J.J. Yoh). sign, high energy density, high reliability, good per-

https://doi.org/10.1016/j.proci.2022.07.036
1540-7489 © 2022 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
5678 K. Gnanaprakash and J.J. Yoh / Proceedings of the Combustion Institute 39 (2023) 5677–5686
formance characteristics, etc. In recent times, there
is a growing interest in solid propellants that can ex-
hibit multiple cycles of start/stop capabilities and
variable thrust during in-flight operations. Elec-
trically controlled solid propellants (ECSPs) are
one special class that demonstrate such character-
istics. These propellants ignite and combust only
when external electric power is applied at suffi-
cient levels, known as pyroelectric combustion be-
haviour [1,2]. This process is highly exothermic and
the combustion rate of these propellants can be
controlled/adjusted by varying the applied external
power [3]. In addition, ECSPs exhibit high stabil-
ity, and are not susceptible to accidental ignition by
spark, impact or even open flame [1,2].
Several studies on ECSPs based on hydroxyl
ammonium nitrate (HAN) oxidizer have been re-
ported in the past [4–7]. Typically, HAN was of-
ten stabilized with chemical agents and blended
with poly vinyl alcohol (PVA) binder, which exhib-
ited the unique pyroelectric behaviour. He et al.
[4] have studied thermal characteristics of differ-
ent HAN/PVA based ECSPs and showed their de-
composition temperature in the range of 112–238
◦
C. Glascock et al. [5] have investigated the uti-
lization of high performance electric propellants
(HAN/PVA based), in an ablative pulsed plasma
thruster, and compared their impulse and perfor-
mance measurements with traditional polytetraflu-
oroethylene propellant.
Recently, Baird and Frederick [6] have reported
the thermochemistry of combustion in above EC-
SPs and discussed their electrochemical mecha-
nisms. In another study, the effect of aluminium
(Al) as metal additive on ignition and combus-
tion characteristics of ECSPs was investigated by
Bao et al. [7]. They have considered different par-
ticle sizes and contents of Al, and proposed pos-
sible mechanisms of enhanced combustion in alu-
minized propellants. However, these ECSPs exhib-
ited self-sustaining combustion at 1 MPa, which
could deprive from their multiple start/stop capa-
bilities. In addition, HAN is highly hygroscopic
which results in significant melting during combus-
tion and poor thermal stability with these ECSPs
[8,9], and limit their applications.
Therefore, lithium perchlorate (LP) has been
considered recently in ECSPs instead of HAN, to
improve their thermal stability. He et al. [8] have in-
vestigated thermal and combustion characteristics
of LP/PVA-based aluminized ECSPs, and showed
that their burning rates increased with increasing
the electrical voltage and ambient pressure. Fur-
ther, it was shown that their thermal stability and
hygroscopicity was better than HAN-based ones.
Similarly, Wang et al. [9] have studied the ther-
mal reactivity, decomposition and combustion per-
formance of polyethylene oxide-polyacrylonitrile
based ion conductive energetic composites, as a re-
placement for HAN-based ECSPs. It was demon-
strated that burning rates of these composites were
strongly dependant on their ionic conductivity. In a
different study, tungsten (W) was considered as an
alternate metal additive, since it can improve ther-
mal decomposition and performance characteris-
tics of ECSPs [10]. Also, the volumetric energy den-
sity (∼85 kJ/cm3 ) of W is similar to Al [11], and the
thermal conductivity is comparable between these
two metal additives.
In most previous studies, HAN-based ECSPs
were considered and their governing reaction mech-
anisms were elucidated. However, there are only
limited studies on LP-based ECSPs that were at-
tempted to investigate factors influencing their de-
composition and combustion characteristics. Such
mechanisms are still not yet completely understood
due to their complex physicochemical processes,
electrochemistry coupled with thermochemical re-
actions, multiphase heat and mass transfer, etc. On
the other hand, these studies have considered only
Al as metallic fuel in their propellant compositions,
which was not favourable at increased pressures.
In the present study, pyroelectric combustion
behaviour of baseline and metallized ECSPs based
on LP/PVA containing tungsten as metal additive
is investigated. W is considered in these ECSPs
mainly to examine their multiple burn/no-burn ca-
pabilities at atmospheric conditions as well as ele-
vated pressures (>1 MPa), which was not observed
with aluminized ECSPs because they exhibit self-
sustaining combustion at such high pressures, as
reported by other previous studies [8,9]. Experi-
ments are performed to investigate the propellant
morphology, thermal decomposition, and combus-
tion characteristics at atmospheric conditions. Fur-
ther, theoretical performance parameters and com-
bustion rates are compared amongst different EC-
SPs. Subsequently, important electrolytic decom-
position and thermochemical mechanisms involved
in their pyroelectric combustion are presented.
2. Experimental
2.1. Propellant samples
ECSPs consist of LP as oxidizer, PVA as binder
and fuel, tungsten (particle size of 1 μm) as metal
fuel additive, boric acid (H3 BO3 ) as cross-linking
agent, and glycerine as plasticizer (to improve con-
ductivity and electrochemical properties of PVA
[12]). Initial propellant formulations considered in
this study are shown in Table 1. For all samples, the
original weight ratio of LP and water was main-
tained as 1:1.85, for complete solubility. To inves-
tigate the influence of W addition in metallized
ECSPs, weight percent of other ingredients and
LP/water ratio were retained the same as baseline
ECSP, except for the metal content.
The procedure for propellant preparation was
explained in detail in our previous work [13].
A planetary centrifugal mixer (Thinky ARE-310,
 K. Gnanaprakash and J.J. Yoh / Proceedings of the Combustion Institute 39 (2023) 5677–5686
Table 1
Compositions of different ECSPs, and their theoretical performance results.
Samples LP (%) H2 O (%) PVA
(%)
ECSP (φ = 0.97) 29.47 54.53 10
ECSP-M5 (φ = 1.04) 27.72 51.28 10
ECSP-M10 (φ = 1.14) 25.96 48.04 10
ECSP-M15 (φ = 1.19) 24.21 44.79 10
φ – Equivalence ratio; Tad – adiabatic combustion temperature; Isp – specific impulse; Cprod – total concentration of
products.
Japan) was utilized for mixing ingredients. Homo-
geneous transparent propellant slurry was obtained
without any voids after mixing, which cured into
rubbery solid material in a hot air oven at 35 ◦ C
for 7–10 days. During curing, some water evapo-
rated from ECSPs, so the final water content was
different from initial formulations. Cured samples
were cut and utilized for thermal, morphological
and combustion studies.
2.2. Techniques
Differential scanning calorimetry (DSC 3+,
Mettler Toledo) and thermogravimetric analysis
(TGA 2, Mettler Toledo) were performed to in-
vestigate thermal decomposition characteristics of
ECSPs. Experimental procedure followed for these
tests was similar to our previous study [13], and
based on the International Confederation for Ther-
mal Analysis and Calorimetry Kinetics Commit-
tee [14]. Heating rate of 20 °C/min was selected for
both DSC and TGA tests in the temperature of 30
to 600 °C. In addition, heat release, decomposition
temperature, and mass loss from different exother-
mic reactions were evaluated using a built-in Ad-
vanced Kinetics and Technology Solution software
(AKTS) [15].
To obtain surface morphological features of
ECSPs, a field emission scanning electron micro-
scope (FE-SEM) (JSM-7800F Prime, Jeol Ltd.,
Japan) with a resolution of 1.0 nm (15 kV) was em-
ployed. This was coupled with an energy dispersive
spectroscopy (EDS) for identifying the elemental
composition. Around 2 mg of actual ECSPs and
their residues from combustion tests were examined
in SEM and EDS.
Combustion tests were conducted by utilizing
a combustion test stand and regulated DC power
supply (1 kV and 1 A), as shown in Fig. 1. The
applied input power was recorded through voltage
and current probes, using a two-channel digital os-
cilloscope (Tektronix, TBS1052B-EDU, 50 MHz
bandwidth, sampling rate of 1 GS/s). The voltage
probe was from Hantek (T3100, 100 MHz band-
width, attenuation of 100:1), and the current probe
was from Tektronix (A622, 100 kHz bandwidth,
output scale of 100 mV/A). The combustion test
stand consists of a set of electrodes made up of
molybdenum (10 mm × 20 mm × 5 mm), support
5679
h3 bo3 glycerine W (%) Tad Isp (s) Cprod
(%) (%) (°C) (mol/kg)
2 4 – 1830 177.3 34.1
2 4 5 1784 169.6 31.5
2 4 10 1603 157.0 30.2
2 4 15 1479 145.4 29.6
stands, and connections for input power. The pro-
pellant and electrodes were positioned in a vertical
burning configuration such that top electrode was
positive, bottom electrode was negative, and pro-
pellant was placed in between these electrodes.
The above vertical configuration was utilized to
obtain pyroelectric combustion rates of ECSPs at
different initial voltages, under ambient conditions,
using combustion photography. The initial voltage
was varied in the range of 100–500 V, at an incre-
ment of 100 V. ECSPs were cut into samples with
a cross section of ∼5 mm × 5 mm and length of
6–8 mm. Combustion was captured using a high-
speed camera (Phantom V711, with resolution of
800 × 600 pixels2 ) fitted with a 105 mm Nikkor
macro lens [16], at a framing rate of 100 fps and
exposure time from 500 to 3000 μs depending on
propellant formulations. A custom MATLAB code
was utilized to obtain the combustion rates.
In this study with flat plate electrode configura-
tion, the propellant must always be in contact with
the electrodes and pyroelectric combustion occurs
preferentially at the positive electrode, when the ex-
ternal power was applied. Due to burn away of the
propellant surface, the top electrode is displaced
vertically downwards by gravity at the same rate
as propellant regression, which is the typical sce-
nario with ECSPs burning in this electrode configu-
ration. Because of high radiation intensity from the
flame/combustion zone, pixels near the actual pro-
pellant burning surface were saturated in combus-
tion images and it was highly challenging to locate
the exact burning surface. Therefore, locus points
of displacement of the moving top electrode were
considered and plotted against the time to get com-
bustion rates, instead of tracking the actual regress-
ing propellant surface. This rate of displacement of
the top electrode was presumed to be exactly the
same as propellant regression rates.
All combustion rate data points at each initial
voltage were repeated at least once and an uncer-
tainty of ±3% was calculated for this measurement.
It was found out that the deviation in combustion
rates at 100 V was more than the accepted range
of 10% after the first set of repetitions. Therefore,
multiple repetitions were conducted for all voltage
conditions to ensure that the deviation was within
this range. In some tests, it was hard to deduce com-
bustion rates for ECSPs under certain conditions
5680 K. Gnanaprakash and J.J. Yoh / Proceedings of the Combustion Institute 39 (2023) 5677–5686

Fig. 1. Schematic of the experimental setup. (Insets: Magnified view of the test stand and image of ECSP-M5).

due to poor combustion images. In such cases, more

repetitions were required to obtain the data for that
initial condition.

3. Results and discussion

3.1. Theoretical calculations

The theoretical performance parameters namely

specific impulse (Isp ), adiabatic combustion tem-
perature (Tad ), and total concentration of prod-
ucts (Cprod ) of various ECSPs were obtained us-
ing a thermochemical equilibrium code (Cheetah
[17]), by solving rocket problem at typical condi-
tions of 7.0 MPa chamber pressure, 0.1 MPa exit
pressure, and 25 °C ambient temperature. The en-
thalpy of formation for PVA from [8] was consid-
ered for these calculations. Results obtained from
this analysis are presented in Table 1 for all pro-
pellants. Note that propellant compositions con-
sidered for this theoretical calculation were differ-
ent from initial formulations, because they were
recalculated after assuming only 20% water to Fig. 2. Theoretical performance of ECSPs with increas-
be present in them (confirmed later with TGA ing W content; (a) adiabatic combustion temperature and
mass loss results in Section 3.3). It is seen from specific impulse, (b) major and minor products concen-
Fig. 2a that theoretical Tad and Isp values decreased tration.
monotonously when tungsten is added and its con-
tent was increased further. For ECSP-M15 with
15% W content, theoretical Tad and Isp values re- ECSPs with increasing W content. However, there
duced by 19.2% and 17.9% respectively, relative to is an interesting result with respect to oxidizer-rich
the baseline ECSP. A similar trend in total products or fuel-rich stoichiometry amongst various ECSPs,
concentration is noticed with the increase in W con- similar to that reported in our previous study [13].
tent (Table 1), in which M15 exhibited a decrement Note that O2 is present only in the baseline case,
of 13.2% in Cprod compared to ECSP. whereas H2 and CO are seen with metallized EC-
The combustion products from this analysis SPs. This implies that the former is an oxidizer-
shown in Fig. 2b consists of H2 O, CO2 , and LiCl rich formulation close to the stoichiometric ratio,
(l) as major products, and H2 , CO, O2 , LiCl (g), since maximum Tad possible with LP/PVA mixture
and WO3 (s) as minor products. It is apparent that is ∼2000 °C. On the other hand, metallized EC-
WO3 (s) is increasingly present only in metallized SPs are fuel-rich formulations, which tend to be
 K. Gnanaprakash and J.J. Yoh / Proceedings of the Combustion Institute 39 (2023) 5677–5686 5681

further fuel-rich with more W (M15). In addition,

concentration of major products also decreased
with increase in W content, suggesting more incom-
plete combustion with ECSP-M15. Thus, inclu-
sion of W to ECSPs decreases their energy content
and performance parameters because of increas-
ing fuel-rich stoichiometry with metallized for-
mulations and increasing energy dissipation from
other reactions to initiate metal oxidation, al-
though W participates actively in thermochemical
reactions.
Furthermore, these results imply that the oxida-
tion of W is increasingly limited due to the con-
densed phase reaction of W particles and high
molecular weight of W combustion products, as
metal content is increased. In contrast, combustion
rates with these ECSPs increased significantly with
increase in W content especially at low initial volt-
ages, as shown later. This is due to significant elec-
trochemical decomposition of LP in ECSPs gen-
erating substantial oxidizer species, which are not
considered in theoretical calculations. This signifies
that inclusion of W to ECSPs induces favourable
impact on their pyroelectric combustion behaviour
for utilization in various propulsion systems.

3.2. Surface morphology of ECSPs

Surface features of the baseline ECSP and met-

allized ECSP-M15 were observed in SEM and their
EDS mappings were obtained over multiple areas
to examine the distribution of various ingredients.
Morphology of both ECSPs resemble more like
heterogeneous propellant rather than completely
miscible ingredients (Fig. S1 in the supplementary),
since both LP and PVA dissolved in water at the
mixing stage. EDS mapping results show that C
(∼20%) is noticed in smooth regions on the baseline
ECSP surface, signifying the presence of binder.
Waves are clearly evident on smooth regions of
binder (Fig. S2a), suggesting that there was possi-
ble displacement of binder to some extent in the
curing stage. Other regions indicate both O and Cl
elements, representing the presence of LP oxidizer.
Interestingly, numerous needle-like and
pyramid-like structures (dimension of 20–50
μm) of LP are observed on the surface, due to
its recrystallization during curing, although plas-
ticizer can possibly reduce this process. These
structures are regular but formed into various
shapes. More voids are noticed on the surface,
indicating that water molecules evaporated while
curing, thus leaving empty spaces between oxidizer
structures. With ECSP-M15, W is sporadically
distributed in binder regions and also clustered
at some regions in the mixture (Figs. S1b & S2b).
Needle-like oxidizer structures are more prominent
than pyramid structures in M15, and EDS results
indicate ∼10% of W in this sample. In general, it
is hard to quantify recrystallization and the effect
of crystal tendency on the pyroelectric combus-
Fig. 3. Comparison of thermal behaviour of the baseline
case with metallized ECSPs; (a) DSC and (b) TGA curves.
tion behaviour of these ECSPs, and need to be
considered in a separate study.
3.3. Thermal decomposition behaviour
DSC and TGA results obtained for different
ECSPs at 20 °C/min are presented in Fig. 3. The
trends noticed with these curves that correspond to
various reactions are exactly similar to that of those
reported in our previous study [13], which focused
primarily on the thermal decomposition behaviour
of ECSPs. There is a slight variation in the heat
release from the third exothermic peak (slightly
larger) of the baseline ECSP at 458 °C between the
current and previous studies. This implies that more
unreacted LP decomposition and secondary reac-
tions occurred in the third exotherm, contribut-
ing to additional heat release and less residues at
600 °C, specifically with this set of ECSPs. Further,
major primary reactions under second exothermic
peak occurred at 347 °C. The total combined heat
release from all exotherms is obtained as 3729 J/g
for the baseline case.
This overall heat release decreased with increas-
ing content of W in metallized ECSPs (Fig. 3a),
which is similar to theoretical Tad presented in
Section 3.1. The heat release for ECSP-M15 was re-
5682 K. Gnanaprakash and J.J. Yoh / Proceedings of the Combustion Institute 39 (2023) 5677–5686
duced by 36.4% in comparison to ECSP-M5. In ad-
dition, the decomposition temperature of the ma-
jor exothermic peak decreased to lower values as
W content was increased. This indicates the cat-
alytic behaviour of W in ECSPs that initiated reac-
tions at lower temperatures [13]. TGA results show
that there was mass loss of ∼20% below 150 °C
(Fig. 3b), corresponding to the evaporation of
water in all ECSPs. The compositions recalcu-
lated for theoretical estimations shown before in
Section3.1 were based on this water content in pro-
pellants. The major decomposition reaction started
at ∼250 °C and ended at ∼500 °C for all cases, but
with different mass losses over this stage depend-
ing upon their W content. The trend in mass loss
from TGA is similar to the heat release trend from
DSC, for various ECSPs. Note that the content of
residue increased with W content in ECSPs. This
indicates that large amount of sample was unburnt
(more unreacted W) at 600 °C after the test, which
correspondingly reduced the heat of reaction, as
observed from DSC data. On the other hand, el-
emental composition results obtained from energy
dispersive analysis (EDS) were inconclusive and it
was difficult to deduce possible content and compo-
sition of residues from XRD analysis as well, since
those results were inconsistent [13].
3.4. Pyroelectric combustion behaviour
Combustion tests were conducted for all EC-
SPs in the voltage range of 100 to 500 V and con-
stant current of 1 A. The minimum electrical en-
ergy required for ignition of these ECSPs was not
obtained in this study. Instantaneous snapshots of
pyroelectric combustion of ECSPs are shown in
Fig. 4, at different time instances. Here, the first
part in each image represents the first occurrence of
ignition (t0 ). Samples are marked in red boxes, and
the top face of positive electrode and the bottom
face of negative electrode are marked with green
lines.
When the external power source (100 V and 1
A) was turned on, the baseline ECSP started to
conduct current from the top positive electrode to
the bottom negative electrode. This initiated V and
A values to increase progressively, as seen in digi-
tal oscilloscope. At this stage, liquid bubbles were
observed near the interface between the top elec-
trode and propellant surface, caused by the evap-
oration of water still present in ECSP. Once V
and A reached their maximum values, ignition was
achieved and pyroelectric combustion occurred at
the top electrode-propellant interface. Combustion
gases from the burning surface were forced out at
the top electrode. Since these propellants burn con-
siderably fast enough, the heat transfer from the top
electrode or the flame to unburnt propellant surface
was not significant enough to affect their combus-
tion rates. Moreover, there was no variation in com-
bustion rate of propellants within each test (start
or end). Hence, it was assumed that steady burning
was achieved and burning rates were unaffected for
each case.
Since the top electrode was merely placed on
the flat propellant top surface and allowed to move
freely in the vertical direction, it displaced (due to
gravity) at exactly the same rate as propellant burn-
ing. Therefore, the rate of displacement of the top
electrode was presumed as the pyroelectric com-
bustion rate of ECSPs. This also ensured continu-
ous contact between the top electrode and the pro-
pellant surface, for uninterrupted combustion. This
process ended once the propellant was burnt out or
the contact was lost. At high voltages (500 V), the
bubbling period decreased and pyroelectric com-
bustion of ECSP occurred at faster rates. This im-
plies that high input power improved combustion
rates due to enhanced electrochemical mechanisms.
Similar aspects were noticed with metallized for-
mulations, all of which displayed faster burning
than the baseline ECSP, at each initial voltage.
However, the combustion zone of metallized EC-
SPs appeared much brighter than the baseline case
near the top electrode-propellant interface. This
is attributed to the high energy release from in-
tense luminous combustion of W particles in metal-
lized propellants, which were observed to be emerg-
ing out of the propellant burning surface. Further-
more, molten W droplets coalescing together to
form large agglomerates were evident at the front
face near the propellant burning surface, promi-
nently with M10 and M15 in tests conducted at
100 V (Fig. S3 in the supplementary). Note that the
baseline ECSP appeared more luminous within it-
self compared to metallized ECSPs because the for-
mer was translucent, which allowed for transmis-
sion of the light radiation from the flame through
the propellant (Fig. 4a).
The change in voltage and current signals,
corresponding to actual combustion images in
Fig. 4, recorded for different ECSPs are shown in
Fig. S4 of the supplementary. All propellants fol-
lowed similar trend throughout their combustion.
Voltage started to rise gradually and attained a
maximum value causing ignition, while current var-
ied from 1 A to 0.5 A before reaching its maximum.
During combustion, voltage decreased from its
maximum to 300 V and current fluctuated around 1
A. Once contact between propellant and electrodes
was lost, voltage dropped down to minimum and
the process completed.
The time taken to attain maximum voltage from
the onset of voltage rise is termed as the voltage
response time in this study. The overall combus-
tion time is the interval between maximum and
minimum voltages, subsequent to ignition. Note
that the combustion time depends on sample length
and cannot be compared directly amongst differ-
ent cases since this length was not maintained the
same in all tests. Figure S4 illustrates that the volt-
age response time for the baseline ECSP (0.54 s)
 K. Gnanaprakash and J.J. Yoh / Proceedings of the Combustion Institute 39 (2023) 5677–5686
Fig. 4. Instantaneous snapshots of pyroelectric combustion of ECSPs at 400 V and 1 A. (a) Baseline, (b) M5, (c) M10.
is noticeably higher than that of metallized ECSPs
(0.40 s), in general. This implies that the ionic con-
ductivity of the latter is higher than the former,
due to the presence of W particles that typically
have high electrical conductivity. A previous study
has reported that higher ionic conductivity for en-
ergetic materials indicate lower impedance, which
results in reduced response time when voltage is ap-
plied [9]. Low voltage response time of metallized
propellants is similar to the reduced decomposi-
tion temperatures noticed before (Fig. 3a). In ad-
dition, overall combustion time of metallized EC-
SPs is marginally less than the baseline case, at high
initial voltages.
Pyroelectric combustion of ECSPs involves
electrochemical mechanisms coupled with thermo-
chemical reactions. During initial electrolytic de-
composition of LP, the applied electric power to
ECSP causes positive ions (Li+ ) to be electrostati-
cally attracted toward the negative electrode and si-
multaneously negative ions (ClO− 4 ) toward the pos-
itive electrode. Bubbling period observed in com-
bustion images (Fig. 4) would assist this movement
of ions within the bubbly layer and not through the
closely packed solid phase of ECSPs. Accumula-
tion of ions would occur near the top electrode in
this bubbling layer on the propellant burning sur-
face. However, the ions that accumulate near the
top electrode would be mostly negative ions from
the electrolytic decomposition of LP. Further pro-
cesses between these ions and those from water elec-
trolysis would generate new oxidizer species. Now,
these oxidizer species would react with fuel species
5683
from PVA and/or W, to produce products along
with a corresponding heat release through thermo-
chemical reactions. Moreover, the flow of electrons
across the propellant generates heat or thermal en-
ergy through Joule heating [3], which also initiates
some reactions between oxidizer and fuel.
The pyroelectric combustion mechanism for
LP/PVA-ECSPs proposed here is based on previ-
ous studies on HAN/PVA propellants [3,6,18]. First
the electrochemical decomposition of LP/water
mixture needs to be realized before considering
thermochemical reactions of the mixture involv-
ing PVA. Initially, water electrolysis generates O2 ,
H+ proton, and electrons at the anode, while H2 and
OH− radical are produced at the cathode. Since LP
electrolyzes into Li+ and ClO− 4 ions in the mixture,
the proton reacts with negative ions at the anode
to produce HCl, and OH− radical reacts with posi-
tive ions at the cathode to produce LiOH Eqs. (1) &
((2)). Since LP/water mixture is an ionic liquid, it
supports the movement of ions to their respective
electrodes. This decomposition at anode may in-
clude an intermediate step as well that generates
perchloric acid (HClO− 4 ). Thus, the electrochemical
decomposition of LP/water mixture produces HCl,
LiOH, H2 and O2 (Eq. (3)).
When PVA is included in the mixture, the elec-
trolytic decomposition process is slightly modified
resulting in generation of additional species (CO2
and H2 O), which would also include some thermo-
chemical reactions. Note that the decomposition
reaction of LP/PVA/water mixture includes exces-
sive hydrogen in products (Eq. (6)). In general, the
5684 K. Gnanaprakash and J.J. Yoh / Proceedings of the Combustion Institute 39 (2023) 5677–5686

water content in ECSPs is very low and may be

ignored in their global combustion reaction. With
metallized ECSPs, W reacts with oxidizer to
LP/water electrochemical decomposition,
Anode:
H2 O → ½O2 + 2H+ + 2e−
(Li+ )(ClO4− ) + H+ → HClO− 4 + Li
+

→ HCl + 2O2 + Li+

Cathode:
2H2 O + 2e− → H2 + 2OH−
(Li+ )(ClO4− ) + OH− → LiOH + ClO− 4

Overall reaction at the anode :

 
4(Li+ ) ClO− 4 + 2H2 O Fig. 5. Pyroelectric combustion rates vs. applied initial
→ 4HCl + 9O2 + 4Li+ + 4e− (1) voltage of metallized ECSPs relative to the baseline case.

Overall reaction at the cathode :

  presented in Eqs. (7) & (8). Notice LiCl is consid-
4(Li+ ) ClO− 4 + 4H2 O + 4e
−
ered in these reactions since pure thermal decom-
→ 4LiOH + 2H2 + 4ClO−
4 (2) position of LP involves LiCl generation as well.
More importantly, the baseline ECSP has oxidizer-
Global electrolytic process of LP/water decom- rich stoichiometry, while metallized ECSPs have
position fuel-rich stoichiometry, consistent with Section 3.1.
4LiClO4 +6H2 O → 4LiOH + 4HCl + 2H2 +9O2 Other parameters such as electric power, species
concentration and quantity, pressure, preferen-
(3) tial electrode for combustion, etc. may also have
LP/PVA/water electrolytic decomposition, their influence on pyroelectric combustion of
ECSPs.
Reaction at anode : Combustion images were utilized to obtain py-
  roelectric combustion rates of different ECSPs,
4 ClO−4 + 2H2 O + 2C2 H4 O
which are shown in Fig. 5 as a function of the ap-
→ 4HCl + 4CO2 + 4H2 O + 4O2 + 4e− (4) plied initial voltage. Combustion rate of ∼0.3 mm/s
was noticed for the baseline ECSP at 100 V, which
Reaction at cathode : increased to ∼3.0 mm/s at 500 V. In this range,
combustion rates have increased exponentially by
4(Li+ ) + 8H2 O + C2 H4 O + 4e−
10 times, with a correlation of 82%. High electric
→ 4LiOH + 2CO2 + H2 O + 7H2 (5) power enhances electrolytic decomposition of ionic
LP oxidizer, which in turn improves the overall
Global electrolytic decomposition of combustion behaviour and thus combustion rates,
LP/PVA/water with applied electric potential relative to these processes at low voltage. With
4LiClO4 +10H2 O + 3C2 H4 O metallized formulations, combustion rates were in-
creased by 6.3 times, 4.2 times, and 3.4 times in the
→ 4LiOH + 4HCl + 6CO2 +5H2 O + 4O2 +7H2 100–500 V range, for M5, M10, and M15, respec-
(6) tively. Overall, the trend for all ECSPs remained
the same with respect to electrical power, irrespec-
Pyroelectric combustion reactions of baseline tive of their formulations. This suggests that these
and metallized ECSPs propellants can be potentially utilized for variable
throttle control applications. Further, this trend is
4LiClO4 + 2[−C2 H4 O−]n → 4CO2 + 3H2 O similar to results of linear burning rates vs. volt-
+ 3O2 + 3LiCl + HCl + LiOH (7) age reported by He et al. [8], for aluminized EC-
SPs (LiClO4 /PVA/Al/H2 O propellants) in the range
of 80–400 V. More importantly, combustion rates
for W-based ECSPs are considerably higher than Al
4LiClO4 + 3[−C2 H4 O−]n + W → 6CO2 cases at similar electric power, regardless of slight
+ 3H2 O + WO3 + 2H2 + 3LiCl + HCl + LiOH compositional variations.
(8) Addition of W to ECSPs enhanced their
combustion rates substantially at low voltages
generate tungsten oxide (WO3 ) besides other prod- (<200 V), whereas this effect was marginal at high
ucts. Based on these, overall pyroelectric combus- voltages (>400 V). Combustion rates increased by
tion reactions of baseline and metallized ECSPs are 4.9 times at 100 V and by 1.7 times at 500 V for
 K. Gnanaprakash and J.J. Yoh / Proceedings of the Combustion Institute 39 (2023) 5677–5686
ECSP-M15 relative to the baseline ECSP. A con-
verging trend in combustion rates was observed
at high voltages. At low power, high heat release
from W combustion was significant in enhancing
combustion rates. However, at high electric power,
electrochemical mechanisms become more domi-
nant than such thermochemical reactions and the
rate controlling step in governing pyroelectric com-
bustion of ECSPs, regardless of the presence of
metal additives. Besides, combustion mechanism of
ECSPs involves combination of multiple processes
that also includes Joule heating and electrochemical
reactions, all of which merge together to result ul-
timately in thermochemical reactions causing heat
release. But, this enhancement in combustion rates
at high power was predominantly due to improved
electrochemical reactions.
SEM images and EDS mapping results of
residues from combustion tests of baseline, M5,
and M15 ECSPs are shown in Fig. S5 of the sup-
plementary. Combustion residue of the baseline
ECSP displays porous and frothy surface. EDS
mapping indicates presence of elemental C in un-
burnt smooth regions of binder, in addition to
O and Cl from products. Metallized ECSPs show
presence of elemental W in EDS, corresponding
to WO3 from their residues. Furthermore, spherical
metal oxide particles of diameter less than 1 μm are
observed prominently with ECSP-M15 (Fig. S5c).
This implies that significant combustion of parent
W particles has occurred to decrease their metal ox-
ide particle sizes.
Recall that, inclusion of W decreased the net
heat release from thermal decomposition reaction
of ECSPs (Fig. 3a). Further, theoretical Tad and
Isp also showed similar trend with increase in the
W content (Fig. 2a). In contrast, combustion rates
increased with increase in W content in these pro-
pellants. This is because of significant W oxida-
tion at actual burning conditions and high tem-
perature that enhances the combustion rates of
ECSPs, whereas such oxidation may not occur
at low temperatures considered in thermal analy-
sis, thus resulting in reduced net heat release. On
the other hand, high ionic conductivity of met-
allized ECSPs improve electrochemical decompo-
sition mechanisms and subsequently their com-
bustion rates, whereas such mechanisms are not
considered for theoretical calculations. Thus, it is
evident from the present study that addition of
W alters global reaction mechanisms and signif-
icantly enhances the pyroelectric combustion of
ECSPs.
Note that all ECSPs considered in the present
study ignited and burnt in the initial voltage range
of 100–500 V and 1 A current under atmospheric
conditions, regardless of their formulations. More
importantly, these propellants were successfully
tested for multiple burn/no-burn conditions under
application/removal of the external electric power.
This specific pyroelectric combustion behaviour is
5685
highly desirable in most propulsion systems. How-
ever, there are many challenges associated with
these propellants such as maintaining constant
contact between the propellant and electrodes, en-
suring numerous start/stop operations under dif-
ferent burning conditions without interruption, at-
taining visco-elastic nature, etc. Furthermore, it
is essential to correlate attributes of electric volt-
age and current signals with the actual pyroelectric
combustion behaviour of ECSPs to completely un-
derstand their governing mechanisms. This creates
opportunities for future studies to focus on such ar-
eas of research in order to further improve the per-
formance characteristics of ECSPs for their utiliza-
tion in various applications.
4. Conclusions
Pyroelectric combustion behaviour of metal-
lized ECSPs based on LP/PVA/W was investigated,
relative to the non-metallized baseline ECSP. To
study the influence of tungsten (W), three differ-
ent contents (5%, 10%, 15%) were considered in
their formulations. Theoretical performance cal-
culations indicated that addition of W in ECSPs
decreased their adiabatic combustion temperature
and resulted in more incomplete combustion. Re-
sults from thermal analysis showed that the base-
line ECSP exhibited the highest heat release from
exothermic decomposition amongst all cases. How-
ever, the catalytic behaviour of W reduced the de-
composition temperature in metallized ECSPs, rel-
ative to the baseline case. Pyroelectric combus-
tion of ECSPs involved liquid bubbling, ignition at
maximum voltage and current, followed by electro-
chemical decomposition of LP and thermochemi-
cal reactions.
Electrolytic decomposition of LP/PVA/water
mixture produced LiOH, HCl through perchloric
acid, CO2 , H2 O as products. Presence of W in EC-
SPs produced WO3 as well, which altered this re-
action mechanism. However, the voltage response
time for metallized ECSPs was relatively lower than
the baseline case, implying that the presence of W
increased the ionic conductivity of the former. For
all ECSPs, combustion rates increased exponen-
tially by 3–10 times with applied initial voltage in
the range of 100–500 V. More importantly, inclu-
sion of W to ECSPs enhanced their combustion
rates considerably at low voltages (<200 V), due
to significant burning of W particles at high tem-
peratures. These results signify that electrochemical
mechanisms become more dominant and the rate
controlling step at high electric power, in govern-
ing combustion mechanisms of ECSPs. Although,
the above interpretation could have been expected
to some extent, the actual quantitative increment
in combustion rates with respect to the applied ini-
tial voltage would not have been realized without
this present work. Furthermore, the predominance
5686 K. Gnanaprakash and J.J. Yoh / Proceedings of the Combustion Institute 39 (2023) 5677–5686
of electrochemical decomposition even in the pres-
ence of W as metal additive in ECSPs is observed
only for the first time in this work.
Declaration of competing interest
The authors declare that they have no known
competing financial interests or personal relation-
ships that could have appeared to influence the
work reported in this paper.
Acknowledgements
This work was funded by the National Research
Foundation of Korea (Project Grant No. NRF-
2020R1I1A1A01065097) contracted through
IAAT and IOER at Seoul National University.
Supplementary materials
Supplementary material associated with this ar-
ticle can be found, in the online version, at doi:10.
1016/j.proci.2022.07.036.
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