Joint Propulsion Conferences 10.2514/6.

2013-3970
July 14 - 17, 2013, San Jose, CA
49th AIAA/ASME/SAE/ASEE Joint Propulsion Conference

Combustion of Boron and Fluorocarbon Solid Fuels in a

Hybrid Rocket
Terrence L. Connell, Jr.1, Grant A. Risha2, Richard A. Yetter3
The Pennsylvania State University

Colin W. Roberts4, Gregory Young5

Naval Surface Warfare Center-Indian Head Division, Indian Head, Maryland, USA

A composition comprised of 80% polytetrafluoroethylene and 20% boron (by weight) is

considered as a potential high-density solid fuel mixture for mixed hybrid rocket propulsive
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applications. Constant pressure strand burner experiments were conducted over a pressure
range from approximately 1.46 to 10.6 MPa (198 to 1,538 psia) under nearly constant
pressure in nitrogen environment to determine the low-pressure self-deflagration limit and
measure burning rates as a function of pressure in an optically accessible chamber. A
burning rate correlation rb[cm/s] = 0.042(P[MPa])0.531 was determined for the given
formulation. A low-pressure self deflagration limit of approximately 2.2 MPa (319 psia) was
obtained. Pressurized counterflow burner experiments conducted using pure oxygen
revealed formation of surface char which prevented measurement of solid regression rates
below 2MPa indicating an additional resistance for heat and mass transfer. Static-fired
rocket motor experiments were conducted to determine the pressure and flow dependencies
of the system by variation of oxidizer flow rates and nozzle throat areas, and to evaluate
propulsive performance parameters. Characteristic exhaust velocity efficiency (C*efficiency),
which provides a measure of combustion efficiency, ranged from approximately 86 to 96%
depending on motor operating conditions. While classical hybrids do not have a strong
dependence of fuel regression rate on pressure, a pressure dependence was observed in this
system below the self deflagration limit due to the pressure dependence of the decomposition
and fluorination kinetics of the solid fuel mixture. Below the self-deflagration limit, the
motor operated at a constant pressure, typical of a classical hybrid, while above the limit, a
progressive burn was observed characteristic of a composite propellant. Systematic oxidizer
dilution with nitrogen revealed a decrease in pressurization rate with decreasing oxygen
content and an ignition limit was achieved for this system when the oxygen mass fraction
was reduced from 0.65 to 0.6. C*efficiencies were not noticeably affected by oxidizer
dilution with nitrogen over the range considered.

I. Introduction

F OR many years metallic particles have been included in reactive formulations for various types of chemical
propulsion systems as a way to increase performance through increased energy density, higher reaction
temperatures, and tailored burning rates [1-3]. Particles may be added to a binder and oxidizer and stored as a
composite solid propellant, suspended in a liquid fuel, combined with a binder and stored as an inert solid fuel, or
combined with an oxidizer into a fuel rich mixture and stored as a pyrolant. Pyrolant compositions have
applications as igniters/initiators [4-6], flares [4, 6], thermal decoys [6], base-bleed applications to reduce projectile
drag [6, 7], propellant for solid propulsion [6], fuel for air breathing systems [6, 8], and may have applications in

1
Research Assistant, Department of Mechanical and Nuclear Engineering
2
Associate Professor, Division of Business and Engineering, Altoona College
3
Professor, Department of Mechanical and Nuclear Engineering
4
Research Scientist, RDT&E Department
5
Research Scientist, RDT&E Department

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Copyright © 2013 by Terrence L.
Connell Jr., Richard A. Yetter, Grant A. Risha, Gregory Young. Published by the American Institute of Aeronautics and Astronautics, Inc., with permission.
 hybrid propulsion as well, provided an adequate oxidizer supply is stored within the system [9, 10]. Of the possible
metallic particles for consideration as a fuel, boron is always considered because of its high volumetric energy
density. However, difficulties in its ignition characteristics and combustion efficiencies have prevented it from
being widely used.
The overall performance of a propulsion systems benefits from increasing reactant density, increased energy
content, and reduced storage volume/structural mass, and therefore solid propellants and fuels employing high
density binders and containing metallic or other high density fuels are of interest. In the present study, a solid fuel
comprised of polytetrafluoroethylene (Teflon®, PTFE, C2F4) and boron (B) was considered for hybrid rocket
applications, due to high material densities, and high heat of reaction of boron with both oxygen and fluorine on
both a gravimetric and volumetric scale. In such a system, the oxidizer requirement may be significantly reduced, as
fluorine produced by decomposition of PTFE reacts with boron to form boron trifluoride (BF3). Gaseous oxygen
was introduced as the oxidizer, although other potential oxidizers could be considered [9]. The presence of fluorine
was expected to enhance the removal rate of the passivating boron oxide layer, thus potentially solving the boron
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ignition problem while the absence of hydrogen eliminates the formation of metaboric acid (HOBO) and other boron
hydrides, which could adversely affect the combustion efficiency. In this paper, one formulation containing 80%
PTFE with 20% boron (by weight) was considered for use in a mixed hybrid propulsion application. Strand burning
experiments were conducted to determine the low-pressure self-deflagration limit and mixture burning rates as a
function of pressure. Pressurized counterflow burner studies were conducted to develop an understanding of the
mixture burning process under a continuous flow of gaseous oxygen. Small-scale static-fired rocket motor
experiments were performed to determine the pressure and flow dependencies of the propulsion system and overall
performance.

II. Background
Classically, the hybrid propulsive system is comprised of an inert solid fuel grain stored within a combustion
chamber and burned with separately contained liquid, gaseous, or gelled oxidizer which is injected through porting
within the grain. During combustion, heat feedback from the diffusion flame pyrolyzes the solid fuel causing the
grain web to regress [11]. Unlike composite propellants, the combustion process is virtually independent of pressure,
and the fuel regression rate is controlled by the total mass flux of the system. Researchers have considered many
options to increase regression rates and reaction temperatures and decrease product molecular weights thereby
increasing thrust through increased exhaust mass flow and higher exit velocities. Some of these include multi-port
grain geometries which present greater surface area within a given volume [12, 13], addition of metallic particles
[14-16], introduction of hydrogen containing metal hydrides [17-21] and high-nitrogen containing compounds [22],
non-polymeric fuels such as paraffin wax which burn by shedding droplets from the molten surface [23, 24], and
even doping the inert fuel with small amounts of oxidizer to tailor a pressure dependence [25].
Pyrolant compositions are also of interest as potential fuels for hybrid propulsion systems as high mixture
density, high reaction temperature, and reduced oxidizer requirement may benefit the overall propulsive
performance of the system through greater density-specific impulse, and reduced oxidizer storage volume [9].
Considerable research has been conducted on formulations containing magnesium (Mg) and Teflon® (PTFE) [4-8,
26-29], although other metals, including aluminum (Al) [30, 31], silicon (Si) [31], titanium (Ti) [26, 30, 32], and
boron (B) [7, 9, 10, 26, 30], have been combined with PTFE and studied as well. However, in a propulsion system,
high molecular weight (MW) products and two-phase flow reduce performance, therefore minimizing condensed
phase products and lowering product MW is critical. From the perspective of energy release, in both oxygen and
fluorine containing systems, boron theoretically yields greater volumetric and gravimetric heats of combustion than
Mg, Al, and Si. Furthermore boron trifluoride exhibits a boiling temperature of 172K (1atm) [33], while boron
oxide (B2O3) vaporizes at much higher temperature (2338K at 1atm [34]). In the past, boron has been considered as
a potential energetic ingredient/additive to solid propellants [1] and fuels (liquid [35] or solid [15, 36]) to enhance a
systems propulsive performance, although realizing the performance benefits is another matter, as high conversion
efficiencies can be difficult to achieve [37].
The combustion process of boron in oxygen containing environments has been described by many researchers
as a two stage process comprised of an ignition stage in which the boron oxide coating the neat boron particle is
melted and vaporized exposing boron directly to the oxidizing environment, and a combustion stage where no oxide
remains on the surface and the neat boron is consumed [38-42]. Glassman et al. describe the first stage of boron
combustion in oxygen containing environments as a diffusion controlled oxidation of an oxide-coated boron particle
until increasing temperatures eventually lead to oxide vaporization and exposure of the neat boron to the oxidizing
atmosphere [39]. Dreizin et al. suggest phase change may be the initiating factor in the first stage of boron
combustion [43]. Unlike an aluminum particle which may burn in the vapor phase provided the pressure of the

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 oxidizing environment does not increase the vaporization temperature above the flame temperature, the boron
particle will burn heterogeneously, due to the high vaporization temperature of boron [2, 44].
Early experimental works from Macek and Semple combusted micron sized boron particles in various oxidizing
environments under atmospheric [42] and pressurized conditions [38]. They measured the ignition delay and burning
times for the particles which show trends of increasing ignition delay and reduced burning times with increasing
pressure for air and oxygen diluted with argon [38]. Under pure oxygen, the ignition delay and burn times were
shown to be significantly reduced under atmospheric conditions; however experiments were not conducted at
elevated pressures [38, 42]. Li and Williams present data which reveal a transition from diffusion to kinetically
controlled combustion as the boron particle size is reduced to tens of microns in diameter [40]. A further study by
Macek [45] considered the effect of particle size under similar experimental conditions and included an analysis of
boron combustion under atmospheric and pressurized conditions in oxygen-free environments containing nitrogen
fluoride (NF3). A comparison of NF3 and O2 diluted with argon under atmospheric conditions indicated that micron-
sized boron particles burning in the NF3 environment exhibited no ignition delay and longer burn times compared to
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similar particles combusted in the O2 environment [45]. A similar study conducted by Ulas et al. combusted both
amorphous and crystalline micron-sized boron particles in the products of a methane fueled flame, through which
NF3 was also flowed [46]. In agreement with Macek, the authors report the presence of fluorine renders the first
stage (ignition stage) of the combustion process virtually indistinguishable. The substitution of fluorine for oxygen
was shown theoretically to accelerate the gasification rate of boron oxide with increasing fluorine concentration by
Yetter et al. [47], and Zhou et al. [48] suggest that particle burning rates may increase for small boron particles
burning under kinetically controlled conditions in oxidizing environments containing high concentrations of fluorine.
Reduced particle ignition delays and increased burning rates benefit systems where short residence times may result
in the ejection of partially reacted ingredients and thus manifest poor combustion efficiencies. Krier et al. employed
a shock tube to generate high-pressure/temperature environments in which ignition and combustion of boron
particles under various oxidizing environments, pressures, and temperatures, were systematically studied [49, 50].
Introducing sulfur hexafluoride (SF6) as a source of fluorine, they show for a low concentration of SF6 in O2, both
the ignition delay time at a given temperature was reduced and ignition was achievable at reduced temperatures
when the pressure was increased from 8.5 to 34atm [49]. Furthermore, at a given pressure, both increasing the
fluorine concentration and reducing the boron particle size reduced the ignition delay time, while burn times for a
given particle size reportedly decreased with increasing fluorine concentration [50].
In addition to ignition difficulties, the formation of metaboric acid (HOBO) occurs when hydrogen containing
species are present in the reactive mixture as opposed to formation of liquid boron oxide (B2O3) which provides
additional heat release as gas-phase B2O3 is condensed in the nozzle of the propulsive device [47]. However, in
systems where the nozzle exit temperature is higher than the B2O3 condensation temperature, this additional energy
release will never be realized. Perhaps more importantly is the effect of hydrogen fluoride (HF) on boron
combustion. Krier et al. report that at a given pressure under oxidizing environments containing gaseous oxygen
(O2) and an O2/HF mixture, the boron particle ignition delay times were similar, although particles combusted in the
O2/HF environment exhibited an increased ignition temperature limit [49]. Foelsche et al. went on to show, under
higher pressure conditions the presence of 5% HF in oxidizing gases (containing O2, H2O, and HF) did not
significantly enhance the boron particle burning time, while ignition delays at a given pressure were shown to be
increased by nearly a factor of two over the baseline oxygen/water/nitrogen oxidizing gas mixture [51]. In a further
study, the ignition and burn times are shown to decrease and eventually plateau, under fixed pressure conditions,
with increasing fluorine concentration [52]. From all of these published results, the benefits of fluorine presence
with respect to both the ignition and combustion of boron is evident, and therefore in systems which consider boron
as an energetic ingredient to the reactive formulations, including a source of fluorine should be considered as well.
Only a small amount of fluorine introduced to an oxygenated system is necessary to considerably reduce both
particle ignition delays and burn times [50, 52]. However, if the mixture contains both hydrogenated and fluorinated
compounds, formation of HF may be detrimental to the boron combustion process, as HF has been shown to be
relatively unreactive with both boron and boron oxide [53]. Although the removal of hydrogen containing species
from the reactive mixture may result in higher MW products, the benefits may be manifested in reduced ignition
delays (as shown experimentally using HF [51]) and therefore permit additional time to completely burn the particle
within residence time of the motor and ultimately result in greater combustion efficiencies.
Kubota and Serizawa conducted experiments in the late 80’s in which mixtures of PTFE, Mg and Viton (3%,
binder) were pressed and burned under pressurized nitrogen environment, using fuse wires to capture the
propagation rate [4]. In these experiments variables included pressure, mixture ratio, and particle size. Their results
show that burning rate increased with pressure, reduction in particle size, and increasing Mg particle loading, even
when the loading far exceeded the stoichiometric ratio and despite decreasing flame temperatures. Ignition

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 experiments conducted in air by Fetherholf et al. showed ignition delay time was reduced by introducing and
increasing the fraction of boron in the Mg/PTFE formulations, with the shortest delay times recorded for B/PTFE
mixtures containing no magnesium [7]. They also claim the overall combustion of these mixtures was benefited by
the inclusion of boron as a reactive ingredient in the formulations, although no burning images, descriptions, or burn
rate data were provided for boron containing compositions.
Shidlovskii and Gorbunov pressed several PTFE/B formulations in plastic tubes and combusted the samples in a
pressurized nitrogen environment [26]. Their results showed that burning rates increased with both boron loading
and pressure, over a pressure range from approximately 2 to 10 MPa. Boskovic and Negoicic also reported faster
burning rates with increasing boron loading [30]. More recently Young et al. studied a range of PTFE/B
formulations to be considered for propulsion applications [9, 10]. They manufactured PTFE/B compositions in
which two types of PTFE were considered with a boron loading ranging from 10 to 40% of the mixture weight,
combusting pellets manufactured of pressed PTFE and boron with gaseous oxygen under atmospheric conditions in
a counterflow burner to characterize the effects of flame strain rate (by variation of oxidizer velocity), heating
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samples under an inert environment while simultaneously measuring weight loss and endothermic/exothermic heat
flow using a thermogravimetric and differential scanning calorimetry, and rapidly heating samples and analyzing the
products using an FTIR [10].
Furthering the work presented by Young et al. [9, 10], thermochemical analyses were conducted for the given
PTFE/B and a comparable HTPB/B system having the same boron loading fraction to determine the benefits and
detriments exhibited by the C/O/F/B and C/O/H/B systems using NASA’s Computer Program for Calculation of
Complex Chemical Equilibrium Compositions and Applications (CEA) program [54, 55]. The conditions include
oxidizer to fuel ratios optimized for maximum specific impulse (0.45 and 1.9 for 80%PTFE/20%B and
80%HTPB/20%B, respectively), a combustion chamber pressure of 3.4 MPa (500psia), and ideal expansion to
atmospheric pressure. To observe the effect of HOBO formation versus B2O3 on performance, an additional
calculation was performed with HOBO, H3B3O3, H3B3O6, and H3BO3 removed from the product database to force
B2O3 production. The PTFE/B composition specific impulse was reduced by nearly 12% and density-specific
impulse was increased by approximately 37% compared to the HTPB/B formulation. Furthermore the oxidizer mass
requirement was reduced by a factor of four, which, as suggested by Young et al. [9], equates to reduced oxidizer
volume, necessary insulation and structural mass. The exhaust product composition which is primarily comprised of
BF3, OBF, and CO with virtually no B2O3 shifts to primarily H2, H2O, HOBO, and CO when the binder/fuel is
changed from PTFE to HTPB. Interestingly, when formation of HOBO is prevented, specific impulse for the
HTPB/B composition is reduced by several seconds. The exhaust temperature, which is hotter than the B2O3
vaporization temperature, prevents condensation and thus the additional energy released during phase change is not
achievable. The combustion and exhaust temperatures for the PTFE/B composition are nearly 20 and 37% hotter,
respectively, than the HTPB/B case. In future considerations, the possibility of temperature reduction in favor of
reduced product molecular weight through addition of high-density energetic fillers/additives to the formulation
could be explored.

III. Solid Fuel Manufacture and Characterization

PTFE/B samples (pellets, strands, and center-perforated motor grains) were manufactured from 800 nm SB95
(SB Boron Corporation) boron and granular 7C (DuPont Corporation) polytetrafluoroethylene. Young et al.
determined an active boron content of 87.2 wt% with an additional 3.4 wt% of the sample being comprised of
magnesium [10]. Images of both the boron particles and PTFE material, obtained via scanning electron microscope,
are also presented in reference [10]. The particles were agitated under high shear to break up agglomerates, then
combined and mixed using a V-blender to produce a uniform composition which was then stored overnight under
vacuum to remove moisture. Pellet and strand samples of the given formulation were then pressed at 7 tons for 60
seconds using a 10 mm die and center-perforated grains were pressed at 12.5 tons for 60 seconds using a special die,
which simultaneously compressed the mixture and formed the port. Average pellet, strand, and grain dimensions,
mass, and density determined from recorded measurements are presented in Table 1 with one standard deviation (σ)
variation.

Table 1. Average Pellet, Strand, and Center-Perforated Grain Dimensions and Density.
Inner Diameter [cm] Outer Diameter [cm] Length [cm] Density [g/cc]
Pellets - 0.982±0.008 0.963±0.020 2.083±0.020
Strands - 0.977±0.001 4.080±0.027 2.100±0.009
CP Grains 0.952±0.010 2.154±0.005 6.520±0.120 2.105±0.025

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 Once formed, the PTFE/boron samples were sintered following the patented process developed by Joshi [56].
The sintering process may be supplemented for the addition of a binder such as Viton® (DuPont™), which may be
dissolved and deposited via forced precipitation on to the particles suspended in solution [57, 58]. This method of
coating, referred to as the “shock-gel” process [58], has been used successfully by researchers prior to pressing their
compositions [31]. However, inclusion of Viton® (chemical formula: C10F13H7) into the reactive mixture is
disadvantageous energetically, as the largely negative enthalpy of formation (-2784 kJ/mol [34]) results in a reduced
heat of reaction with increasing binder fraction. Introducing hydrogen within the composition provides the potential
for formation of hydrogen fluoride (HF) which is both toxic and corrosive, and the presence of which has been
shown to increase particle ignition time [51]. Furthermore, PTFE (which contains 76% fluorine by weight) has a
fluorine-to-carbon ratio (F/C) of 2 while Viton® (which contains 66% fluorine by weight) yields an F/C ratio of 1.3;
hence, as more binder is introduced to the mixture the fraction of carbon produced during metal/fluorine reaction is
increased, which would require additional oxidizer. Alternatively, researchers have pressed metal/PTFE mixtures
without any binder or post-processing (i.e., sintering) and report that a fragile structure is produced with a potential
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for void space formation [31]. Yarrington et al. report fragmentation of binderless samples during combustion
studies conducted in a pressurized environment, and suggest flame propagation into voids within the sample were
the cause [31]. Young et al. studied the mechanical properties of sintered and unsintered PTFE/B samples having
the solids loading varied up to 30% (by weight), and report virtually no mechanical strength for unsintered samples,
while tensile tests conducted on sintered samples showed variation of Young’s modulus was a function of boron
loading [9]. They show that a boron loading of 30% (by weight) exhibited low ductility, stretching only 9% and
resulting in a corresponding increase in Young’s modulus by a factor of 4 over the baseline (pure PTFE) sample,
while reducing the boron loading to 20% (by weight) resulted in 93% sample elongation and a reduction in Young’s
modulus of 25% compared to the sample containing 30% (by weight) boron [9]. For these reasons the sintering
process, rather than inclusion of a fluoroelastomeric binder or merely pressing pellets without binder, was applied to
the PTFE/boron composition considered for this work. The boron particle loading fraction was chosen based on a
compromise between good mechanical properties and theoretical performance.

IV. Experiments
A. Strand Burner
Pressurized combustion studies on the self-deflagration rate of the 80%PTFE/20%B composition were
conducted using a windowed pressure vessel. More detail may be found in references [59, 60]. Strands were
suspended within the chamber volume and aligned such that observation and recording of the combustion process
was permitted via one of the optical viewing ports. Both uncoated and nail polish coated samples were combusted,
yielding uniquely different results. Samples were backlit through an optical diffuser using a 35 Watt high-intensity
discharge (HID) xenon lamp, and a blue/violet filter was placed between the optical port and video camera to wash
out the flame and aid in viewing the regressing surface. A standard Sony video camera, recording at 29.97 frames
per second, was used to monitor and record the combustion process. Ignition of the samples was achieved using
resistively heated 28 gauge nichrome wire (12 vdc igniter voltage) threaded through a sliver of NOSOL 363 double
base gun propellant placed directly on the surface of the strand. The chamber was pressurized by filling with inert
nitrogen (N2) gas to a specified pressure via a remote operated regulator, following which an electro-pneumatically
actuated exhaust valve was opened, metering flow through the chamber via a choked orifice, creating a quasi-steady
nearly constant pressure condition under which the sample combustion process was observed. Igniting the strand
under these conditions minimizes the pressure rise due to the evolution of combustion products while
simultaneously flushing the chamber and improving optical clarity. A particle filter placed upstream of the exhaust
orifice prevents exhausting the condensed phase material, and potentially clogging the orifice. A schematic of the
system showing both the strand and counterflow burner assemblies and how they interface with the pressure vessel
is provided in Figure 1.

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 Pellet and
pellet co-flow
housing
Counterflow burner
Strand burner assembly
assembly

Concentric oxidizer and

oxidizer co-flow tubes
Igniter posts
Leak-test valves

Strand
Check valves
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Pressure Pressure
transducers Orifices transducer

PT
Oxidizer
Optical port
Oxidizer
PT
co-flow

Pellet co- Exhaust

PT
flow
Motorized
Chamber regulator
pressurant M. R.
Pressure
vessel
Figure 1. Pressure vessel and flow system schematic for both strand burner and pressurized opposed flow
systems.

Chamber pressure was monitored using a calibrated SETRA pressure transducer located at one of the many
available ports in the chamber wall, and pressure data were recorded at 1000 Hz using a Nicolet Genesis data
acquisition system. Experiment operation was controlled through a custom-built LabVIEW interface and external
relays. Burn rate data were reduced from recorded video using commercially available software to review and track
frame-by-frame footage of the regressing strand surface, which was then scaled based on the known (measured)
strand diameter and timed to the frame rate of the camera. From these values a trajectory plot (distance vs. time plot)
was generated, the slope of which corresponds to the sample burning rate at the measured pressure. For each
burning rate, the corresponding recorded chamber pressure, averaged over the total run duration was used. To
prevent inclusion of any non-steady ignition transient in the reduced burning rate, data were not immediately taken
upon sample ignition, rather, the combustion front was permitted to propagate a short distance before distance data
were recorded (as shown in Figure 2). Several images of one uninhibited 80%PTFE/20%B (wt%) strand burning in
a pressurized nitrogen environment (at an average pressure of 10.58 ± 0.11 MPa) are provided in sequential order in
Figure 2 to indicate the steady, flat, self-propagating nature of the composition, and several trajectory plots with
corresponding average chamber pressures plus and minus one standard deviation are provided in Figure 3.

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Downloaded by "Indian Institute of Technology, Bombay" on March 31, 2025 | http://arc.aiaa.org | DOI: 10.2514/6.2013-3970

Figure 2. Images of an 80%PTFE/20%B (wt%) strand burning in pressurized nitrogen environment obtained
from recorded video used to determine strand burning rates.

3
r = 0.1475 cm/s
b
P = 10.58 +/- 0.11 MPa
avg
2
2.5 R = 0.998

r = 0.1115 cm/s
b
2 P
avg
= 7.02 +/- 0.09 MPa
Distance [cm]

2
R = 0.995

1.5
Decreasing
Pressure

1
r = 0.0923 cm/s
b
P = 4.22 +/- 0.06 MPa
avg
0.5 2
R = 0.999

0
0 4 8 12 16 20 24 28 32
Time [s]
Figure 3. Burning rate trajectory plots developed by reducing recorded video footage of 80%PTFE/20%
(wt%) strands burning in a pressurized nitrogen environment.

B. Pressurized Counterflow Burner

Pressurized counterflow burner experiments (PCBE) were attempted to determine the effect of flame strain rate
on the burning rates of pellets containing 80%PTFE/20%B by weight. This system, well described in a previous
publication [61], uses the same optical pressure vessel used for the strand burner experiments. The sample pellet is
retained within a holder, which is extended into the chamber volume and aligned with the optical viewing ports.
Electrical isolation of the two halves of the pellet holder permit the hold-down wire to also act as the igniter when
required, and a linear variable displacement transducer (LVDT) is employed to fix the location of the pellet surface
while simultaneously measuring the pellet decomposition rate. Axially aligned, opposed flow tubes are extended
into the chamber a fixed distance from the pellet surface (5 mm). Both the pellet and oxidizer flow tube are
surrounded by a co-flow gas (pressurant gas) which reduces shear induced mixing of the oxidizer and evolving
pellet decomposition products. The combustion process is visualized and recorded using a standard Sony video
camera.

C. Rocket Motor
Small-scale motor experiments were conducted to determine pressure and flow rate effects on system operation
and propulsive performance. Center-perforated PTFE/B motor grains were press-fit into paper phenolic tubes to
provide protection and facilitate cartridge loading into a well-described [62] sled-mounted combustion chamber.
Graphite liners position the grain within the chamber while forming open volumes between the head-end injection

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 system (pre-chamber) and the inlet to the grain, and between the exit of the grain and nozzle converging section
(post-chamber). The latter volume provides additional mixing and reaction time prior to exhausting the combustion
products through the nozzle. Nozzles, machined from high density graphite, exhibit a fifteen degree diverging half-
angle which was expanded to maintain a targeted exit to throat area ratio of 10. The throat lengths were maintained
at approximately 0.318 cm (0.125 in) while the converging angle is varied to maintain a fixed overall nozzle length.
Motor diagnostics include SETRA pressure transducers located at ports in both the pre and post-combustion
chambers which provide measurement and recording of instantaneous chamber pressures during motor operation, as
well as a force transducer to measure thrust. Motor operation was controlled using a custom LabVIEW sequencing
program coupled with external relays. Data were recorded at 1000 Hz using a Nicolet Genesis data acquisition
system. Schematics of the motor, flow control, and system diagnostics are provided in Figure 4 and Figure 5.

P.T. Pressure transducers P.T.

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Center-perforated Post-combustion
grain chamber
Pre-chamber Graphite nozzle

Oxidizer inlet
Sled

Force transducer
Linear guide bearings
Figure 4. Hybrid rocket motor schematic diagram.

Video
Inert valve Check camera
valve
Inert
Orifice Inert pressure
transducer
Safety
High-pressure Upstream Igniter head Exhaust
inert gas oxidizer pressure leads system
Force
transducer
PT

Oxidizer transducer Sled

valve GOX
PT

High-pressure
gaseous oxygen Check Orifice
valve Chamber
Flex Pre-Chamber PT PT
Post-Chamber
line Pressure Transducer Pressure Transducer
Figure 5. Hybrid rocket motor experiment flow system layout.

The firing sequence is separated into time-controlled segments including a pre-fire time where the oxidizer flow
system pressurizes and reaches steady-state, and the chamber is purged continuously with oxidizer, ignition and pre-

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 determined firing duration, and a post-firing inert gas purge cycle. Ignition was achieved using an electric match
placed at the inlet of the grain port. Use of an ignition aid was necessary, despite the presence of oxygen, as ignition
via electric match alone was not successful. A light coating of NC/NG lacquer was applied to the grain port prior to
loading to aid ignition and enhance flame spreading across the surface. A standard Sony video camera provided
remote visualization and video recording of each firing. An image of a motor plume is provided in Figure 6, and
pressure and thrust profiles from a motor firing are presented in Figure 7.
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Figure 6. Plume image from a typical motor firing.

10 Pressure area = 1.52MPa*s 40

I = 189.3N*s O valve closed
total 2

d = 0.422cm (0.166in)
t,i
35
O line pressure
8 2
upstream of orifice 30
Pressure [MPa]

t
burn
25
Thrust [N]

20

4 Thrust
Igniter 15
Trigger Pre and post-chamber
pressures
10
2
Ignition 5
O valve open N purge valve open
0 2 2
0
-4 0 4 8 12
Time [s]
Figure 7. Pressure and thrust profiles from a motor firing with firing sequence noted in the plot.

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American Institute of Aeronautics and Astronautics
 Measured chamber pressure and thrust data coupled with recorded pre and post fired grain and nozzle data and
theoretical performance values obtained using NASA’s Computer Program for Calculation of Complex Chemical
Equilibrium Compositions and Applications (CEA) program [54, 55] permit calculation of motor performance
parameters including the characteristic exhaust velocity efficiency, which provides a measure of combustion
efficiency. During the motor firing the nozzle throat may be eroded or be reduced due to slag accumulation. For the
motor firing provided in Figure 7, the initial throat diameter was reduced from 0.422cm (0.166in) to approximately
0.399cm (0.157in) resulting in an overall increase in expansion ratio (Ae/At). Under these conditions, an average
value was estimated for theoretical calculations. The average oxidizer to fuel ratio (O/F) was determined using the
oxidizer mass flow rate (calculated using isentropic choked flow, recorded upstream pressure, known gas properties,
and measured orifice discharge coefficient) and mass burning rate of the grain. The grain mass burning rate was
determined using the grain mass consumed and burn time (tb), which was estimated from the chamber pressure
profile. Experimental C*avg values were calculated using the average pressure (Pavg), oxidizer and fuel mass flow
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.
rates ( m avg), and nozzle throat area (At,avg). The average expansion ratio, O/F ratio, chamber pressure, and reactants
are input into CEA to determine the theoretical characteristic velocity (C*theo). The C* efficiency (ηC*avg) was then
estimated by taking the ratios of experimental and theoretical values. Although specific impulse efficiencies (ηIsp)
were calculated as well, nozzles were not optimized for this system; rather, an area expansion ratio of 10 was
maintained for all tests.

V. Results and Discussion

A. Strand Burning Rate
Strand burning experiments were conducted over a pressure range from approximately 1.46 to 10.6 MPa (198 to
1,538 psia). Visualization of the grain during combustion was difficult, due to production of condensed phase
material, however, backlighting and filtering out the flame permitted increased camera exposure which aided
visualization and tracking of the regressing surface. The lowest pressure strand test, conducted at an average
pressure of 1.46 MPa (198 psia) was observed to ignite, propagate a short distance through the strand and then
extinguish. When the chamber pressure was increased to approximately 2.2 MPa (319 psia), the strand was
observed to ignite and the entire grain was consumed, although the burning process could only be observed for the
first third of the grain as evolution of condensed phase material eventually clouded the optical port making surface
tracking impossible. A comparison study conducted between uncoated strands and strands having coating applied to
the surface (to inhibit flame spreading) revealed that the coating (inhibitor) was both unnecessary and actually
produced faster linear burning rates than the uncoated strands. No evidence of side burning was observed for
uncoated strands. Three strand batches were tested to promote confidence in batch to batch manufacture and
repeatability, including several strands from the batch manufactured and tested by Young et al. [9]. Linear burning
rate results for uncoated strands, provided in Figure 8, were fit using the Saint Roberts Law correlation where the
burning rate (rb) is equal to the measured pressure raised to an exponent (n) and multiplied by the pressure
coefficient (A), as shown in Eq.1 [63].
n
rb [cm/s]=A(P[MPa]) (1)

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American Institute of Aeronautics and Astronautics
 0.531
r = 0.042(P[MPa])

Linear Burning Rate [cm/s]

b

0.1

Linear Burning Rate

Young et al. Data

0.1
Previous Batch
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[cm/s]
(Young et al.)
Batch 1
Batch 2 0.531
r = 0.042(P[MPa])
b
Low-pressure regime
data (Young et al.) 0.01
1atm Counterflow 0.1 1 10
data (Young et al.) Pressure [MPa]
0.01
2 3 4 5 6 7 8 910
Pressure [MPa]
Figure 8. Linear burning rates for PFTE/B strands combusted under a pressurized nitrogen environment.

The low-pressure limit determined is in agreement with data presented by Shidlovskii and Gorbunov [26] for
pressed PTFE/B compositions using 3 µm amorphous boron particles, although they do not discuss whether attempts
were made to ignite samples at lower pressure conditions. Further conclusions cannot be drawn by comparison of
results as boron loading fractions, particle sizes, and method of manufacture differ. In general, their data begins at
approximately 20atm (2 MPa), and for the composition containing 19.5 wt% boron, the pressure exponent is very
similar to current results with the corresponding coefficient increased by nearly a factor of two.

B. Motor Operational Characteristics and Performance

Motor firing experiments were conducted by allowing the grains to burn to completion, permitting overall grain
burn time to be determined by analysis of the recorded pressure profiles. Systematically reducing the nozzle throat
area (and thus increasing chamber pressure) transitions the system from a nearly constant pressure to progressive
burn profile as shown in Figure 9. A magnified pressure and thrust profile exhibiting this transition is provided in
Figure 10. The experiment times are zeroed to ignition for comparison, and shown in the figures only to the end of
the burning of the grain.

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American Institute of Aeronautics and Astronautics
 6
d = 0.366cm (0.144in)
t,nozzle,i
d = 0.366cm (0.144in)
t,nozzle,i
80 m O = 15.4 g/s
2
m O = 15.4 g/s
Chamber Pressure [MPa]

5 2
d = 0.391cm (0.154in)
t,nozzle,i
m O = 15.4 g/s
2

4 d = 0.391cm (0.154in)
t,nozzle,i 60

Thrust [N]
m O = 15.4 g/s
2 d = 0.422cm (0.166in)
t,nozzle,i
m O = 15.3 g/s
3 2

d = 0.422cm (0.166in) 40 d = 0.48cm (0.189in)

t,nozzle,i t,nozzle,i
m O = 15.3 g/s m O = 15.4 g/s
2 2 2

20
1
d = 0.48cm (0.189in)
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t,nozzle,i
m O = 15.4 g/s
0 2
0
0 2 4 6 8 10 12 0 2 4 6 8 10 12
Time [s] Time [s]
Figure 9. Pressure and thrust profiles for a series of motor firings having a nearly constant oxidizer mass flow
rate and varied nozzle throat area. The time is zeroed to ignition to align the profiles for comparison.

120
d = 0.366cm (0.144in)
5 t,nozzle,i
Chamber Pressure [MPa]

m O = 15.4 g/s
2
100
4
Grain ignition, 80

Thrust [N]
flame spreading, Nearly constant
3 combustor fill time pressure burning
60

2
40

1 Progressive
self-deflagrating 20
burning

0 0
0 0.5 1 1.5 2 2.5
Time [s]
Figure 10. Expanded pressure and thrust profile exhibiting the nearly constant pressure to progressive
burning transition of a center-perforated PTFE-B propellant grain combusted with gaseous oxygen. The
time is zeroed to ignition to align the profiles for comparison.

This transition occurs near the self-deflagration limit (approximately 2MPa) determined by strand test
experiments and suggests once the deflagration limit is achieved, the diffusion flame which forms at the
oxidizer/fuel interface and sustains combustion via heat feedback to the grain port surface becomes significantly less
important in sustaining the combustion process, as the grain should continue to burn without the presence of the
oxidizer provided the necessary pressure is maintained. The pressure profile provided in Figure 10 suggests three
zones may exist during the grain combustion process. The first zone is considered to include ignition, flame
spreading, and combustor fill time, where the NC/NG, with the aid of gaseous oxygen flowing through the grain port
spreads the flame outward from the region ignited by the electric match. Burn-surface area increases as the
combustion front propagates down the port increasing the chamber pressure both through mass addition and
increasing bulk gas temperature. The observed pressure rise time for this system is longer than startup times
exhibited with HTPB as the fuel for this motor, however, HTPB produces nearly 3.3 times more moles of gas per
kilogram of fuel (approximately 11.8 times more moles of gas per mole of fuel) than the given PTFE/B mixture,
under stoichiometric proportions. The HTPB grain lengths were also considerably longer than the current grains.
Furthermore, strand tests, which were conducted uncoated, show that flame spreading does not exceed the linear

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 burning rate and therefore the ignition process is controlled by the ignition aid, the convective flow through the grain
port, and increasing mass addition from the ignited surface. The second zone exhibits a nearly constant pressure
profile, until the self-deflagration limit is reached. Motor experiments which reach operating pressures above the
self-deflagration limit transition to a progressive burning mode which exhibits increasing pressure with burn surface
area. Motors that do not attain the transition pressure operate at nearly constant pressure.
Motor grains considered for this study were manufactured in two batches, and therefore a repeatability firing
was conducted to compare batch to batch variation and promote confidence in system repeatability (Figure 11). The
times are zeroed to time of ignition to align the profiles for comparison. The average pressures for these tests were
1.61±0.01MPa, and burn times repeated within approximately 200 ms, based on the pressure profiles.
2
Batch 2
P = 1.60MPa
avg
Chamber Pressure [MPa]
m O = 15.2g/s
2
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t = 9.23s
1.5 b

Batch 1
P = 1.62MPa
avg
m O = 15.3g/s
2
t = 9.44s
1 b

0.5

d = 0.422cm (0.166in)
t,nozzle

0
-4 -2 0 2 4 6 8 10
Time [s]
Figure 11. Repeatability and batch-to-batch fuel grain comparison. The time is zeroed to ignition to align the
profiles for comparison.

Oxidizer mass flow rates were varied, fixing the nozzle throat dimension to permit a throttling effect on the
system. The results are presented in Figure 12. Under these conditions two parameters are simultaneously varied,
as the variation of flow rate alters the initial motor pressure.
4 80
d = 0.422cm (0.166in) d = 0.422cm (0.166in)
t,nozzle t,nozzle

3.5 70
Chamber Pressure [MPa]

m O = 21.6 g/s m O = 21.6 g/s

3 2
60 2
Thrust [N]

2.5 50
m O = 15.3 g/s m O = 15.3 g/s
2 2
40 2

m O = 8.9 g/s
1.5 30 2

1 20

0.5 m O = 8.9 g/s

10
2

0 0
0 5 10 0 5 10
Time [s] Time [s]
Figure 12. Pressure and thrust profiles from a series of motor firings with varied oxidizer mass flow rate and
fixed nozzle throat area. The time is zeroed to ignition to align the profiles for comparison.

Pressure effects on burning propellants and solid fuels can be determined by combusting strands within a
pressurized and optically accessible chamber. Johansson et al. demonstrated flame strain rate effects on the burning

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American Institute of Aeronautics and Astronautics
 rate may be obtained using a counterflow burner designed to operate in a pressurized environment [61]. Due to
difficulties in obtaining burning rate data with this system because of char formation, motor studies were conducted
to determine the flow effects as well. If pressure were maintained constant under varied oxidizer mass flow rates
between motor tests, the variation in burn time deduced from the recorded pressure profiles would provide insight
into burning rate variation as a function of flow rate. However, this required iterative nozzle throat area variation to
attain the targeted pressure. To minimize the number of tests in the matrix, nozzle dimensions were estimated to
bracket the desired operating pressure and the burn time was determined by interpolation. A target pressure for
comparison (1.61 MPa) was determined by the average of the chamber pressures shown in Figure 11. The results,
presented in Table 2, show no significant burn time trends with respect to flow rate and therefore suggest burning
rates are nearly independent of oxidizer flow rate over the range of conditions tested. This is in contrast to HTPB
solid fuel, where the burning rates are correlated as a function of oxidizer (or total) mass flux and not as a function
of pressure. An early study conducted with this motor showed that when the average oxidizer mass flux was
increased by nearly 27%, the average HTPB regression rate increased by approximately 20% [62]. The motor
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results complimented regression rate results reported by Risha [36], who conducted hybrid motor experiments using
a slightly larger-scale motor over a larger oxidizer mass flux range.

Table 2. Estimated burning times for PTFE/B grains under varied oxidizer flow rates at a pressure of 1.61
MPa.

Oxidizer Mass Flow Rate

[g/s] Burning Time [s]
8.9 8.9
15.3 9.3
21.7 9.5

The relative independence of oxidizer mass flux (oxidizer mass flow rate divided by grain port area) on the
grain burning rate may be coupled to both the gas-phase combustion process and combustion characteristics of the
solid fuel. In the classical hybrid system pyrolyzing solid fuel and injected oxidizer diffuse together within the
boundary layer forming a diffusion flame, the location of which was shown by Marxman and Gilbert to be a
function of both fuel and oxidizer mass fluxes, oxidizer to fuel ratio, and properties of the reactants [11]. They
suggest the flame is located at the mixture ratio which yields the maximum flame temperature, which is typically a
fuel rich mixture, and developed an equation to approximate the location of the flame with respect to the boundary
layer thickness [11]. Employing Marxman and Gilbert’s equation, the flame location relative to the boundary layer
thickness for both pure HTPB and the 80%PTFE/20%B mixture reacted with oxygen was estimated using the O/F
ratio which theoretically produced the maximum temperature. The calculations suggest the HTPB/O2 diffusion
flame exists approximately 2.5 times further from the fuel surface than the flame developed during PTFE/B
combustion. Calculations performed using simple diffusion flame theory [64] provide a similar result. Increasing
the oxidizer mass flux would then shift the diffusion flame deeper into the boundary layer. Because its flame is
already much closer to the surface, the increase in oxidizer mass flux does not appear to have as much affect on the
fuel regression rate as with polymeric fuels such as HTPB. Although PTFE reportedly transitions to a gel-like state
at a temperature of 600K [65], a “melt” layer was not observed. Pyrolysis and counterflow experiments both show
the PTFE/B samples form a char layer on the surface, differing significantly from HTPB which does form a melt
layer. This char layer may provide another resistance to both heat and mass transfer, in addition to the resistance of
the gas phase boundary layer, further reducing the oxidizer flow effect.
The pressure dependence in the non self-deflagrating mode, may be explained by the combustion chemistry,
hybrid combustion theory, and results from previous studies. X-ray diffraction (XRD) analysis of post-self-
deflagration products collected from a PTFE/B sample indicated the condensed phase material was comprised of
boron carbide (B4C) and carbon (C) [10]. Equilibrium calculations performed using CEA [54, 55] suggest without
the presence of any oxidizer, the reaction products should include BF3(g), B4C(s), and C(s). Simultaneous
thermogravimetric (TG) and differential scanning calorimetry (DSC) analysis results of PTFE exhibited an
endotherm with no mass loss at approximately 601K (which corresponds to the PTFE gel temperature [65]), and the
onset of decomposition was shown to occur around 823K, followed by virtually 100% mass loss [10]. However,
when boron was combined with the PTFE, an exothermic peak was shown during PTFE decomposition. A pyrolysis
study suggests the primary PTFE decomposition product may be gas phase C2F4 [66], although considerable

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American Institute of Aeronautics and Astronautics
 production of C3F6 has been reported as well [67]. Considering these findings and the results from equilibrium
calculations, two possible reaction pathways are shown to illustrate the extremes of the combustion process:

→ 1C2F4(g) + 2.31B(s), ∆HR = +151.04 kJ

1C2F4(s) + 2.31B(s)  R.1.1

→ 1.33BF3(g) + 0.49B2O3(s) + 2CO2(g), ∆HR = -2267.45 kJ

1C2F4(g) + 2.31B(s) + 2.73O2(g)  R.1.2

→ 1.33BF3 + 0.24B4C(s) + 1.76C(s), ∆HR = -721.75 kJ

1C2F4(s) + 2.31B(s)  R.2.1
→ 1.33BF3(g) + 0.49B2O3(s) + 2CO2(g), ∆HR = -1394.66 kJ
1.33BF3 + 0.24B4C(s) + 1.76C(s) + 2.73O2(g)  R.2.2

While the overall reaction is shown to be highly exothermic, exhibiting an overall heat of combustion of
638.84MJ/kmolfuel (16.9 MJ/kgfuel), in the first set of reactions (R.1.1 to R.1.2), the PTFE is assumed to decompose
to C2F4(g), which then reacts with boron and oxidizer in the diffusion flame, while the second set of reactions (R.2.1
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to R.2.2) assume the PTFE and boron react at the grain surface and the equilibrium products of that reaction are then
combusted with oxygen in the diffusion flame.
In the first reaction pathway, step 1 (R.1.1) shows the decomposition of PTFE to C2F4(g) is endothermic. To
maintain the pyrolysis process, heat feedback from the diffusion flame would be necessary to decompose the PTFE
material and sustain the combustion process. As pressure is increased the reaction shifts toward the second pathway,
which shows PTFE and boron may react to form B4C(s), and C(s), along with BF3(g) in the gas phase. This reaction
pathway yields an exothermic first step, contributing to approximately 34% of the total energy release. Under these
conditions, the presence of the diffusion flame may no longer be critical, as the heat generated in the first global step
(R.2.1) may self-sustain the decomposition/combustion process. Below the self-deflagration limit, the reaction
presented in R.2.1 is not fully achieved, however, reactions occurring in the gas phase between the fuel surface and
diffusion flame may be pressure dependent, as reaction rates can scale with pressure [44]. With increasing pressure,
heat is released closer to the fuel surface and contributes to the burning rate dependence on pressure below the self-
deflagration limit. The diffusion flame, while necessary to sustain the overall reaction below the self-deflagration
pressure, shifts away from the surface throughout the run, as the oxidizer mass flux is continually reduced due to
increasing port area while the fuel mass flux remains constant with pressure. The near-constant pressure operation
below the self-deflagration limit is then a result of pressure dependent reactions occurring between the grain surface
and the diffusion flame, and the overall combustion process is sustained by heat feed-back from the diffusion flame
and coupled to the overall system operating pressure.
This may also explain the burning rate dependence on flame strain rate shown by Young et al. under
atmospheric conditions [9]. Under low pressure conditions, pressure dependent reactions occur slower and further
from the surface, hence the decomposition process is more sensitive to the presence of the diffusion flame.
Counterflow burner studies conducted by Johansson et al. show the pressure dependent decomposition and burning
rate of ammonium perchlorate became virtually insensitive to the presence of the diffusion flame when the pressure
was increased from atmospheric pressure to approximately 1.5 MPa (218 psia) [61]. They explain that under low
pressure conditions straining the diffusion flame affects the surface temperature gradient and therefore alters the
burning rate. Increasing the pressure serves to increase chemical reaction rates occurring between the decomposing
surface and the diffusion flame, while the diffusion flame remains unaffected by pressure, and eventually the heat
released by reactions occurring near the surface prevents the diffusion flame from significantly affecting the surface
temperature gradient [61].
The oxygen concentration of the injected gas was systematically reduced to determine both the effect on
performance and the lower ignition limit. Motor results, presented in Figure 13 show minimal effect of oxygen
concentration on motor operating pressure, however an ignition limit was achieved when the oxidizer mass fraction
was reduced to 65%.

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American Institute of Aeronautics and Astronautics
 Varied Oxidizer Concentration
2 30
100% O 65% O
2 2
100% O
35% N 2 76% O
1.8 2 2
Chamber Pressure [MPa]

24% N
25 2

1.6

1.4 76% O 20

Thrust [N]
2
24% N
2
1.2 65% O
2
15 35% N
2
1

0.8 10

0.6 d = 0.422cm (0.166in) d = 0.422cm (0.166in)

t,nozzle
t,nozzle
m O + m N = 15.2 ± 0.1 g/s 5
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2 2 m O + m N = 15.2 ± 0.1 g/s

2 2
0.4
0 2 4 6 8 10 0 2 4 6 8 10
Time [s] Time [s]
Figure 13. Motor studies conducted with the oxidizer mass fractions reduced by mixing with nitrogen. The
time is zeroed to ignition to align the profiles for comparison.

Further reducing the oxidizer mass fraction to approximately 60% resulted in a delayed and brief ignition, and
upon removal of the grain, a small region within the port (presumably where the electric match contacted the grain
surface) was burned. This suggests, when chamber pressures are below the self-deflagration limit, the presence of
oxygen in the near-surface region of the grain port is critical in achieving ignition. It is hypothesized that upon
ignition, the oxygen present in the boundary layer was rapidly consumed in the area of ignition, creating a nitrogen
and product-rich region through which additional O2 molecules must diffuse to maintain combustion at the port
surface. During ignition, the heat feed-back from its gas is too low to maintain combustion.
Measured, calculated, and theoretical performance parameters from the two repeat firings (shown in Figure 11)
and the oxygen dilution study (Figure 13) are presented in Table 3. The theoretical results were obtained as
previously described, using CEA [54, 55], recorded motor pressure data, the boron purity data provided by Young et
al. [10], and given oxidizer mass fractions. The repeat study show calculated C*efficiency (ηC*avg), which equate to
combustion efficiency, are nearly 89%. Similar efficiencies were achieved with this system for ammonium
perchlorate (AP)/HTPB composite [68] and such efficiencies are within the range calculated for HTPB/O2 with this
system as well [62]. The dilution of pure oxygen with nitrogen exhibited virtually no effect on the C* efficiency. A
comparison of burn rates are provided in both Table 3 and Table 4 for tests exhibiting nearly constant pressure
profiles. The estimated burning rate (rb,estimated) is calculated using the deduced burning time and known web
thickness (as the grains were burned to completion) and compared to burning rates calculated using the given St.
Roberts Law correlation and average chamber pressure. As shown in both tables, the estimated and calculated
burning rates (rb,percent difference) generally agree within approximately 20% (although differences as low as 4.5% and as
high as 28% were calculated).

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 Table 3. Tabulated results for the repeat runs shown in Figure 11 and diluted oxidizer experiments provided
in Figure 13.
dt,nozzle,i [cm] 0.422 0.422 0.422 0.422
Pavg [Mpa] 1.62 1.60 1.39 1.78
tburn,grain [s] 9.435 9.228 11.635 9.234
rb,estimated [cm/s] 0.063 0.065 0.053 0.066
n
rb=A(Pavg) 0.054 0.054 0.050 0.057
rb,percent difference [%] 16.8 20.9 6.7 15.1
∆mfuel/tburn [g/s] 4.3 4.3 3.5 4.4
O2 mass flow rate [g/s] 15.3 15.2 11.5 10.0
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N2 mass flow rate [g/s] 0.0 0.0 3.6 5.3

O/Favg 3.56 3.53 4.37 3.53
C*avg [m/s] 1090.2 1092.6 985.5 1124.8
C*theoretical [m/s] 1228.4 1231.0 1169.3 1239.8
ηC*avg [%] 88.8 88.8 84.3 90.7

The results provided in Table 4 summarize tests which exhibit a relatively constant pressure profile and
therefore C* efficiencies were estimated. As discussed in the experimental section, average pressures, nozzle throat
areas, and O/F ratios are calculated in an effort to determine these efficiencies. As the grains exhibit increasing
burning surface area (Aburn = π*Dport*Lgrain), assuming a constant rate of web consumption and no end-burning at the
average pressure, the mass evolution from the grain port increases with time. Therefore the fuel mass burning rate
could increase by as much as a factor of ~ 2.27 over the duration of the burn. Additionally, in many cases, upon
removal of the nozzle, a slag coating was observed which reduced the nozzle throat diameter. This reduction in
throat area was taken into account for C*efficiency estimation, based on the assumption that the nozzle throat was
reduced throughout the run. All three of these parameters directly influence the calculated characteristic velocity.
Calculated C*efficiencies ranged from 74.7 to 96%, however, the two low efficiencies shown in Table 4 both
exhibited significantly reduced nozzle throat areas in comparison to the other firings. Overall, reduction in nozzle
throat areas varied from 0 to 24%, although the range is decreased to 12% if the two low efficency cases are not
considered. In addition, the recorded pressure profiles for these two firings exhibited more pressure variation
throughout the run, and therefore the average pressure would be expected to yield greater uncertainty in the
calculated results. Based on these measurements and observations, it is believed that C*efficiencies ranging from 86
to 96% are more representative of typical combustion efficiencies for this system, and agree well with previously
published results for HTPB/O2 in an identical motor [62].

Table 4. Tabulated results for motor experiments having varied oxidizer mass flow rates and pressures, all
within the plateau burning region, below the self deflagration limit.
dt,nozzle,i Pavg ∆mfuel/tburn
[cm] [MPa] rb,percent difference [%] [g/s] O2 mass flow rate [g/s] ηC* [%]
0.422 0.96 10.4 2.9 8.9 86.9
0.345 1.71 28.0 4.3 9.0 76.4
0.373 1.29 16.7 3.7 8.9 74.7
0.422 1.62 16.8 4.3 15.3 88.8
0.480 1.10 16.0 3.4 15.4 85.5
0.422 1.60 20.9 4.3 15.2 88.8
0.480 1.49 20.3 4.2 21.6 94.5
0.462 1.71 14.6 4.3 21.8 96.0

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 VI. Conclusions
Strand, counterflow burner, and static fired motor experiments were conducted using a fuel composition
comprised of 80% polytetrafluoroethylene and 20% boron (by weight). The formulation was considered as a
potential high-density solid fuel mixture for mixed hybrid rocket propulsive applications. Constant pressure strand
burner tests were conducted over a pressure range from approximately 1.46 to 10.6 MPa (198 to 1,538 psia) under
nearly constant pressure in a nitrogen environment to determine the low-pressure self-deflagration limit and measure
burning rates as a function of pressure in an optically accessible chamber. A burning rate (cm/s) correlation having
a pressure (MPa) coefficient of 0.042 and exponent of 0.531 was developed. One strand test, conducted at an
average pressure of 1.46 MPa (198 psia) was observed to ignite, propagate a short distance through the strand and
then extinguish, while a second strand was observed to ignite and the entire grain was consumed when the pressure
was increased to approximately 2.2 MPa (319 psia), suggesting a self deflagration limit within this pressure range.
Pressurized opposed flow experiments were attempted as well to aid in determination of flame strain rate on mixture
burning rates under varied pressure conditions. However, the formation of surface char made quantitative
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measurements difficult. Static-fired rocket motor experiments were conducted to determine the pressure and flow
dependencies of the system by variation of oxidizer flow rates and nozzle throat areas. The system was observed to
operate nearly independent of oxidizer flow conditions at a given pressure although the presence of the oxidizer was
shown to be critical both during ignition, and when operating the motor under the self-deflagration pressure limit.
Typical estimation of C*efficiencies for this system ranged from approximately 86 to 96%. Systematic oxidizer
dilution with nitrogen revealed an ignition limit in the current system when the oxygen mass fraction was reduced
from 0.65 to 0.6, as ignition was achieved but delayed for the lower mass fraction, and fuel burning was quickly
extinguished. Combustion efficiencies were not noticeably affected by oxidizer dilution with nitrogen over the
range considered. Although a limit of 60% O2 was determined during the present study, this limit appears to result
from poor ignition and not combustion. Thus at motor operating pressures, nitrous oxide (N2O) and air may also be
plausible oxidizers. Furthermore additives may be developed which tailor the critical self-deflagration pressure and
therefore permit manufacture of compositions which specifically meet a desired range of operating conditions, and
may be throttled between the two modes of combustion.

Acknowledgements
The authors would like to acknowledge the Air Force Office of Scientific Research for sponsoring this work
under contract numbers FA9550-07-1-0582 and FA9550-13-1-0004. The support of NASA through the
Nanoenergetics Propulsion Project is gratefully acknowledged. Also, the efforts of Mr. Larry Horner and his
assistance with several motor firings are greatly appreciated.

18
American Institute of Aeronautics and Astronautics
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