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Expandable graphite effect on solid fuel and propellant combustion

Article in FirePhysChem · December 2021

DOI: 10.1016/j.fpc.2021.12.001

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FirePhysChem
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Expandable graphite effect on solid fuel and propellant combustion

Gabriele T. Muller1, Alon Gany2,∗
Faculty of Aerospace Engineering, Technion - Israel Institute of Technology, Haifa 32000, Israel

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

Keywords: This paper presents an investigation on a novel method for manipulating and enhancing the burning of solid fuels
Expandable graphite and propellants by expandable graphite additive. Expandable graphite (EG) is a form of intercalated graphite.
Solid fuel combustion At elevated temperature it undergoes an increase in volume, forming elongated strings/fibers many folds longer
Hybrid combustion
than the original particles/flakes. It was found experimentally that the addition of 1-5% of expandable graphite
Burning rate enhancement
(original particle size 100-150 micrometer, onset of expansion at 200-230°C) to a polymeric fuel matrix (polyester)
Combustion visualization
in hybrid combustion, increased the fuel regression rate by 2 fold and more. It was hypothesized that the EG
strings forming near the burning surface protrude into the hot gas environment increasing heat transfer into the
fuel via conduction. Furthermore, the swelling effect at the surface layer might increase the effective surface area,
hence further increasing the burning rate. High-speed photography of a surface subjected to flame in oxidizing
atmosphere showed EG fibers protruding and growing on the surface, supporting the increased heat transfer
hypothesis. On the other hand, the addition of the same EG to an ammonium perchlorate-based propellant showed
a tendency to reduce burning rate and even extinguish the flame at EG fractions higher than about 3-5%. It is
concluded that in the case of hybrid or solid fuel ramjet combustion, EG can serve as a novel and effective burning
rate enhancer while employing polymeric fuels of good mechanical properties in contrast to paraffin fuels which
have inferior mechanical properties. The influence of EG on the combustion of solid propellants needs further
investigation, looking for combinations of EG and propellant types that may exhibit a similar effect.

1. Introduction
The objective of this research was to investigate the effect of ex-
pandable graphite (EG) additive on the burning rate of solid fuels (with
relation to hybrid combustion or solid fuel ramjets) and solid propel-
lants.
Expandable graphite is a form of intercalated graphite, where guest
ingredients (typically, small molecular fractions of sulphur or nitrogen-
based compounds) are introduced among its crystalline layers. It ap-
pears as particles/flakes of a typical size of 100-500 micrometer. At el-
evated temperatures (typically between 140 and 300°C, depending on
the preparation method), it starts to swell and elongate, forming worm-
like fibers or strings several folds longer than the size of the original
particles [1].
Expandable graphite is a heat transfer promoter [2] used in phase
change materials (PCMs) to increase their thermal conductivity. Other
specific properties of expandable graphite besides high thermal con-
ductivity are corrosion resistance, softness, and compression resilience.
Studies [3–5] revealed properties of mixtures of paraffin or polymers
with expandable graphite such as flammability, thermal conductivity,
∗
Corresponding author.
E-mail addresses: gabriele.thamires@gmail.com (G.T. Muller), gany@tx.technion.ac.il (A. Gany).
1
Intern student from Universidade Federal da Integração Latino-Americana (UNILA), Foz do Iguaçu, Brazil
2
Professor Emeritus
and stability. It was noted that occasionally EG may act as a flame retar-
dant, possibly due to swelling or accumulation over the burning surface.
Nevertheless, combustion rate enhancement has been reported as
well: Elanjickal and Gany [6] investigated the influence of small mass
fractions (1%-5%) of EG particles in the solid fuels of hybrid motors,
demonstrating some 2-fold increase in burning rate for polymeric ma-
terials (particularly polyester) and up to 50% increase for paraffin wax.
Their theoretical model (in good agreement with the experiments) as-
sumed an increase in heat transfer into the bulk fuel due to conduction
through EG fibers forming at the surface layer and protruding into the
hot gas environment. Muller and Gany [7] conducted high-speed pho-
tography of a polymeric fuel (polyester) subjected to flame in oxidizing
atmosphere (air) at atmospheric pressure. They showed the penetration
and growth of expandable graphite fibers during combustion within a
characteristic time of a few tens of milliseconds, supporting the hy-
pothesis of enhanced heat transfer to the fuel via conduction. Hahma
[8] showed substatial burning rate enhancement in firing tests of ener-
getic charges consisting of pressed pyrotechnic powders containing 1%
EG (and occasionally a higher percentage). He assumed that the reason
was mainly crumbling of the burning surface layer due to swelling and
enlargement of the EG flakes near the surface.

https://doi.org/10.1016/j.fpc.2021.12.001
Received 9 November 2021; Received in revised form 24 November 2021; Accepted 1 December 2021
Available online 7 December 2021
2667-1344/© 2021 Xi’an Modern Chemistry Research Institute. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)
G.T. Muller and A. Gany
Fig. 1. SEM photograph of original expandable graphite flakes, Type ES 100
C10, nominal size 100-150 micrometer, of Graphit Kropfmühl GmbH, Germany
[1]. Picture size 150 × 150 micrometer.
The effect of EG on the combustion of solid fuels and propellants
received only little attention in the literature, while according to our
research it may be very promising. This article presents further experi-
mental investigation on this subject.
2. Material and methods
The research has been mainly experimental, consisting of several se-
tups and procedures. The first set of experiments showed the effect of EG
additive on the fuel regression rate in hybrid propulsion. It was derived
from static firing tests of a lab-scale hybrid motor employing polyester
fuel in the form of a hollow cylinder, 190 mm length, 20 mm initial
port diameter, with gaseous oxygen (oxidizer) flowing through the port.
Firing tests at a range of oxygen mass flux from about 10 to 80 kg/(s
m2 ) were conducted without and with 5% of expandable graphite ad-
ditive. Test chamber pressure was within a typical range of 8-12 bar,
but no effect of the pressure on the fuel regression rate was observed.
The EG flakes used were Type ES 100 C10, nominal size 100-150 mi-
crometer, of Graphit Kropfmühl GmbH, Germany [1], characterized by
temperature of onset of expansion of 200-230°C. See SEM photograph in
Fig. 1. The polyester elemental composition, as determined by a Thermo-
ScientificTM Flash 2000 CHNS analyzer, was C42 H41 O10 (approximately
CHO0.25 ).
The second test procedure was exposure of a slab of polyester fuel
containing different mass fractions of EG (up to 5% of the overall fuel
amount) to a burner flame in atmospheric environment and observ-
ing the behavior of the EG fibers growing on the surface. The aim was
mainly qualitative. Some quantitative data such as characteristic length
and time of the growing fibers, were presented in a previous publication
by these authors [7].
The third set of tests comprised the burning of strands of solid pro-
pellants at atmospheric pressure. The propellants used consisted of 75%
ammonium perchlorate (AP) oxidizer of 200 micrometer mean particle
size and 25% polyester as the fuel binder with different mass fractions
(from 0.5% to 5%) of expandable graphite, added in place of part of the
polyester.
3. Results and discussion
3.1. Solid fuels in hybrid motors
Figure 2 presents a comparison of data of firing test results of fuel re-
gression rate in a hybrid motor for plain polyester and for polyester with
5% of expandable graphite. The accuracy of the experimental points is
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FirePhysChem 2 (2022) 72–75
Fig. 2. Comparison between the fuel regression rate in a polyester / oxygen
hybrid motor vs oxygen mass flux without and with 5% EG additive.
Fig. 3. SEM image of an expanded EG fiber (1-1.2 mm long) as observed on the
fuel surface after combustion (after [6]).
±5%. The Enhancement of regression rate due to the EG additive is sub-
stantial, some 2-fold and more, over a range of oxidizer (oxygen) mass
fluxes. Similar results were obtained in earlier research in our group [6].
Elaboration on the energetic performance (also included in [6]) showed
practically no theoretical or experimental effect of the EG inclusion on
the specific impulse or characteristic velocity. That research analyzed
paraffin wax fuel as well, revealing a similar, but less pronounced, re-
gression rate enhancement effect. It also developed a model attributing
the EG effect to additional heat transfer mechanism due to conduction
through the EG fibers, exhibiting good agreement with the experimental
results. A picture of an expanded EG fiber observed on the fuel surface
after combustion is presented in Fig. 3 (after [6]).
3.2. High-speed photography of the burning fuel surface
High-speed (1000 frames per second) video movies of the burning
surface of polyester fuel slabs subjected to a burner flame in open air
surrounding, revealed very interesting details about the behavior of EG
strings. One could observe the strings penetrating through the surface
layer into the surrounding hot gas environment, glowing due to the
flame, and growing to a final length (typically about 1 mm) within 20-60
ms. Measurement and distribution of the characteristic time and length
of the expanded fibers were reported by these authors [7]. Figure 4
presents a series of snapshots taken from a high-speed video movie of
a fuel containing 3% EG. The aim of the figure is to demonstrate the
dynamics of processes occurring on the burning surface, implied by the
variation of the EG strings position, shape, and glowing.
3.3. Solid propellants
Figure 5 presents a series of pictures taken during atmospheric pres-
sure combustion of solid propellant strands consisting of 75% AP / 25%
polyester with different mass fractions of expandable graphite additive.
G.T. Muller and A. Gany FirePhysChem 2 (2022) 72–75

Fig. 5. Qualitative pictures from high-speed (1000 frames per second) video
movies of atmospheric pressure burning of 75% AP / 25% polyester propellant
strands containing different fractions of EG type ES 100 C10. Strand width 8
mm. The pictures are not to exact scale.

Fig. 4. Processes occuring on the surface of a polyester fuel containing 3% EG,

during flame. Field of view width about 12 mm. Time from ignition is indicated.

One can see that this type of EG (ES 100 C10 of Graphit Kropfmühl
GmbH) in combination with the AP / polyester propellant had somewhat re-
tarding effect on the propellant combustion. The flame was the largest and
the most luminous for the plain propellant, getting less extensive with the in-
crease in EG mass fraction. The difference was not large up to about 2% EG.
However, at 3% EG the flame became unstable, and when ignited it would
occasionally extinguish after a short burn time. At 5% EG it was almost im-
possible to sustain the flame after ignition. Figure 6 summarizes quantitatively
the propellant burning rate at atmospheric pressure vs the EG mass fraction,
showing the decrease in burning rate with increasing EG mass fraction, as in-
dicated by the flame behavior in Fig. 5. The burning rate data revealed spread
and possible error within ±10%. Apparently, the accumulation of EG fibers
on the burning surface disturbed the diffusive interactions of the reactants Fig. 6. Burning rate at atmospheric pressure vs mass fraction of expandable
graphite for a 75% AP / 25% polyester solid propellant.
as well as the heat feedback from the flame to the gasifying surface. This
effect should be studied further. Possibly, with different types of expandable
graphite (different size, expansion characteristics, and temperature of onset
Combustion experiments with the addition of 5% EG to a solid polyester
of expansion), different propellant compositions, and higher pressures, the in-
fuel in a hybrid motor resulted in a 2-fold enhancement of the fuel
fluence would be different, and combustion enhancement might be observed.
regression rate. Furthermore, high-speed video pictures showed pene-
One should refer to Hahma [8], who reported substantial increase in regres-
tration and growing of EG fibers on the burning surface. On the other
sion rate when adding EG to energetic charges made of pressed pyrotechnic
hand, combustion experiments of solid propellant strands consisting of
ingredients.
75% AP and 25% polyester, revealed a decrease of burning rate when
adding 0.5%-3% of EG, and difficulty to sustain combustion for larger
Conclusions EG fractions. The main practical conclusion is, that in the case of hy-
brid combustion of polymeric fuels, expandable graphite additive can
Expandable graphite (EG) was studied for its effect on combustion be used as an effective regression rate enhancer. Further conclusion is
of solid fuels and solid propellants. The peculiar property of expand- that the increase in regression rate is likely to be due to conductive heat
able graphite is its swelling and elongation at elevated temperatures, transfer to the fuel through the EG fibers. As regards solid propellants,
e.g., from 100-150 micrometer particles to a millimeter and more string. further research is required to find out the effect of different types of EG

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G.T. Muller and A. Gany FirePhysChem 2 (2022) 72–75

on various propellants, looking for combinations of EG and propellant
types that may lead to enhancement of the burning rate.
Declaration of Competing Interest
There are no conflicts to declare.
Acknowledgments
This research was supported by PMRI – Peter Munk Research Insti-
tute, Technion.
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