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AIAA 2004-3821

40th AIAA/ASME/SAE/ASEE Joint Propulsion Conference and Exhibit


11-14 July 2004, Fort Lauderdale, Florida

Characterization of Nano-Sized Energetic Particle


Enhancement of Solid-Fuel Burning Rates in an X-Ray
Transparent Hybrid Rocket Engine
Brian Evans*, Nicholas A. Favorito, Eric Boyer, Grant A. Risha, Robert B. Wehrman, and Kenneth K. Kuo**
The Pennsylvania State University
University Park, PA 16802

Conventional polymeric fuels for hybrid rocket propulsion have relatively low regression
rates. Two possible solutions were examined: utilization of energetic nano-sized particles,
and adoption of non-polymeric paraffin fuel. Addition of 13 wt.% of nano-sized tungsten
powder to HTPB-based fuel resulted in an increase of 38% in fuel regression rate compared
to the pure HTPB fuel. The use of nano-sized tungsten powders in solid fuels for volume
limited propulsion systems is greatly beneficial due to its high density, high heat of oxidation,
and low oxidation temperature. SEM/EDS micrographs of the newly processed energetic
paraffin-based solid fuels have shown that the nano-sized Silberline aluminum flakes are
homogenously mixed in the fuel matrix. Paraffin-based solid fuels containing aluminum
flakes showed a significant increase in regression rate over the non-aluminized paraffin fuel.
A real-time X-ray radiography system enables the measurement of the instantaneous radius
of the solid fuel grain. The radial increment of the regressing fuel surface can be correlated
with time in a power-law form. An implicit relationship showing the dependency of
instantaneous fuel regression rate on the total mass flux was obtained. The functional
relationships for aluminized HTPB and paraffin fuels were obtained in graphical forms.
Results show that the conventional power-law relationship between the average regression
rate and average oxidizer mass flux cannot be applied to the instantaneous regression rates
of solid fuel burning in hybrid rocket motor conditions.

I.

Introduction

Hybrid rocket motors (employing a solid fuel and a gaseous, liquid, or gel oxidizer) posses many advantages
over conventional solid-propellant rocket motors including on/off capability, thrust tailoring operability, minimal
environmental impact, and also an inherent safety.1,2,3 With the ever growing concern of safety and reliability in the
space-propulsion industry, the hybrid rocket can fill a void due to the inherent safety stemming from the physical
separation of the fuel and oxidizer and the ability to control the combustion event by regulating the oxidizer flow
rate as a function of time. In hybrid rocket combustors, the regression rate of solid polymeric fuels is dictated by the
total mass flux in the port region. This mass flux is the local sum of the burned products and the unconsumed
oxidizer in the flow stream. Since the oxidizer and fuel-pyrolysis products are not initially premixed in the hybrid
rocket engine, the rate of the combustion is diffusion-limited. In other words, the combustion processes of the
reactants in hybrid rockets are dominated by the mixing and reaction rates of the pyrolyzed fuel species with the
turbulent oxidizer stream flowing through either the center port or multiple ports of the solid-fuel grain.4,56,7 For the
case of paraffin fuels (e.g., C32H66), the combustion process is still diffusion limited; however, the fuel droplets are
shed from the surface waves of the molten fuel layer generated during the combustion process. The mixing of the
fuel components and the oxidizer involves the evaporation of fuel droplets and oxidizer gas in the two-phase flow

M.S. Student, AIAA Student Member.


M.S. Student

Ph.D. Candidate, AIAA Student Member

Ph.D. Research Associate, AIAA Member


**
Distinguished Professor of Mechanical Engineering, AIAA Fellow

Copyright 2004 by Brian Evans , Nicholas A. Favorito , Eric


Boyer , Grant
A. Rishaof
, Robert
B. Wehrman,
Kenneth K. Kuo. Published by the American Institute of Aeronautics and Astron
American
Institute
Aeronautics
andand
Astronautics

field. In addition, the mixing of the oxidizer species with those generated from surface pyrolysis/evaporation of the
molten fuel also controls the combustion rate.
Due to the relatively low mass-burning rate of polymer-based solid fuels, such as hydroxyl-terminated
polybutadiene (HTPB) and hydroxyl-terminated polyether (HTPE) compared to solid propellants, a large fuel
burning surface area is required to attain a given thrust level. The utilization of various energetic nano-sized powder
additives in the fuel formulation is one way to alleviate this problem by increasing the fuel regression rate. Previous
studies conducted by Risha, et al.8,9,10,11 have evaluated 19 different HTPB-based fuel formulations using a LongGrain Center-Perforated (LGCP) hybrid rocket motor. In addition to the 19 fuel formulations previously tested,
nano-sized tungsten powders and nano-sized rod shaped aluminum have been acquired and tested as performance
enhancing additives in HTPB-based solid fuels.
Another means of increasing the mass-burning rate of solid fuels is by the use of paraffin wax-based solid fuels,
which have shown to increase regression rates to 3 times that of traditional polymeric fuels such as HTPB.12 The
combination of paraffin-based solid fuels and nano-sized energetic particles drastically increases the regression rates
of solid fuel formulations. The large increase in fuel regression rate that is attained helps to alleviate the need for
complex port geometries required with current polymer-based fuel formulations.
A. Objective of Research
Existing solid propellant missiles have relatively low specific impulses, but high density impulses. In addition,
the burning rates of the current solid propellant grains in the existing systems are limited due to the less efficient
burning-rate modifiers that have been utilized in the conventional solid propellants. Several other undesirable
features of the solid-propellant rocket systems are: 1) not being capable of thrust modulation; 2) the propellant grain
cannot be extinguished once the grain is ignited; 3) their susceptibility to mechanical damage and subsequent flame
spreading into the damaged regions and potential catastrophic motor failure; and 4) solid fuel mechanical properties
are sacrificed because of relatively low loading densities. As mentioned, the major disadvantage of the existing
solid-fuel grain formulations is the relatively low mass-burning rate of the fuel, requiring a relatively large fuel
surface area for a desired thrust level. Low burning rates of solid fuels have been shown to be enhanced by the
addition of energetic metal powders. In addition the use of non-polymeric fuels such as paraffin wax increase the
burning rate of solid fuels by many hundred percent.
The objective of this research is to find means of further enhancement of the mass-burning rate of solid fuel
formulations for use in hybrid rocket motor propulsion systems. To accomplish this goal there have been two main
methods of fuel burning rate enhancement:
1)
Nano-sized particle addition for increasing the heat that is released near the surface of the fuel. This
will increase the linear regression rate of the fuel and thus the mass flow-rate of propellant.
2)
Paraffin-based solid fuel formulations have an inherently high mass-burning rate due to the
hydrodynamically unstable liquid layer that is formed on the surface of the fuel during combustion.13,14
Evaluation of various fuel formulations with either and/or both of these mass-burning rate enhancement
techniques has led to the development of novel solid fuel formulations with greatly enhance mass-burning rates.
With the X-ray Translucent Casing (XTC) hybrid rocket motor the surface of the fuel is imaged throughout the
duration of the combustion test. This allows for the instantaneous regression rate to be determined as a function of
time. The regression rate can than be correlated to the instantaneous oxidizer mass flux.

II.

Method of Approach

B. Hybrid Rocket Motor Casting Procedures


1. HTPB-Based Solid Fuel Processing
The XTC hybrid rocket motor was used to burn two baseline solid fuel formulations, one of which is the cured
HTPB. The HTPB was formulated using R45-M resin with either Isonate 143L methylene diphenyl isocyanate
(MDI) or isophorone diisocyanate (IPDI) curing agent with T-12 catalyst. It is advantageous to use IPDI curing
agent in casting fuel grains that contained particles with a high specific surface area, such as the nano-sized
tungsten, because of the ability to vary the working time of the solid fuel. The casting process for solid-fuel
formulations for the XTC motor grain is similar to the LGCP motor.15 The solid fuel was mixed following the same
procedure for introducing particles into the resin and degassing. Also the grains were cast utilizing a previously
developed novel low-melting point wax mandrel process, in order to create a center-perforated grain. Grains were
cast in paper phenolic tubes that have an outer diameter of 114.3 mm (4.5 inches) and an inner diameter of 63.5 mm
(2.5 inches) in lengths up to 457.2 mm (18 inches). Typical test durations for the XTC ranged from 5 to 7 seconds
depending on the fuel formulation and the injected oxidizer mass flux.

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American Institute of Aeronautics and Astronautics

2. Paraffin-Based Solid Fuel Casting


The casting procedure for paraffin-based solid fuels differs from that of HTPB-based solid fuels significantly. To
cast paraffin-based fuels a centrifugal casting procedure is used. This will cause the wax to be pressed outward on to
the paper phenolic grain tube as it cools. This is necessary because of the nature of paraffin wax to shrink as it cools
which results in gap formation between the inner surface of the phenolic tube and the outer surface of the fuel. To
prevent in-depth radiation absorption, small percentages of opaque particles were added to the solid fuel. These
particles can either be carbon black or aluminum powders. In addition to this radiation absorption blockage effect,
nano-sized aluminum has been shown by the authors to increase the burning rates of solid fuels by significant
amounts.
Two slightly different procedures were implemented for casting solid-fuel grains for the LGCP and the XTC
hybrid rocket motors. To achieve the smooth bore in the center port of the LGCP fuel grain, the casting is completed
in two steps to overcome the significant shrinking effect. First, the tube was only filled partly with the liquid paraffin
and then spun on a lathe until the grain cooled (~1 hour) to create a large center port. Then, this partially loaded
grain was again filled with liquid paraffin and spun until it was cooled. The final internal surface was machined to a
very smooth port of desired dimension.
Casting of paraffin-based (C32H66) solid-fuel grains for the XTC hybrid rocket motor varies slightly from the
casting procedure for the LGCP motor. A horizontal casting procedure like the one described above has been used
for casting XTC grains. For the XTC motor with much larger diameter fuel grains, the important factor in
controlling the fuel quality was found to be the restriction of the particle movement during the cooling/solidification
process. A multiple step casting and solidification process was used for both the baseline paraffin fuel formulation
(paraffin wax with 3% carbon black by weight) and fuel grains containing significant percentages of nano-sized
aluminum flakes. The speed of the lathe was selected to limit the centripetal forces applied to the particles, while
still maintaining good adhesion between the interfaces. In order to help with the adhesion of the fuel to the phenolic
grain tube or to previously cast fuel layers two hydrocarbon-based additives have been acquired whose physical
properties aid in this. Both materials are completely soluble in paraffin wax and have good compatibility
characteristics with paraffin. One of these additives also is very strong and will impart its strength onto the solid fuel
through the physical structure of the material.
Energy Dispersion X-ray Spectroscopy (EDS) was utilized to check the homogeneity of the cast fuel samples.
EDS enables various elements to be detected and gives a qualitative analysis of the homogeneity of the fuel. To
check for particle migration, samples were taken at the inner and outer surface of a fuel layer. Figures 1 and 2 show
the sample characterization micrographs for the inner and outer regions of a cast fuel, respectively. Figure 1a is a
scanning electron microscope (SEM) of the sample taken from the inner radius region of the paraffin solid fuel
containing 13% Silberline aluminum flakes by weight. Figures 1b and 1c show the distribution of carbon and
aluminum atoms in the fuel matrix, respectively. The size of these three micrographs are identical with 250 m in
both vertical and horizontal directions (at 500x magnification). These EDS micrographs indicate the highly uniform
nature of the dispersion of the aluminum particles. Figure 2 shows the SEM and EDS micrographs of the fuel
sample taken from the outer radius region of the fuel grain. Again the uniformity of the aluminum particle
distribution is verified through the EDS micrographs. The similarity between Figures 2c and 1c indicates the radial
distribution of the aluminum concentration is very uniform. The thickness of the Silberline nano-sized aluminum
flakes is approximately 100 nm. However the width and height of the flake are approximately 27 and 10 m,
respectively. These flakes are relatively large particles in the width and height dimensions. Using the presently
developed method for fuel cooling/solidification, the distribution of aluminum particles is already very uniform.
Applying the same method to solid fuels containing smaller aluminum particles such as Alex one can be sure that
the particle distribution will be very uniform.

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American Institute of Aeronautics and Astronautics

C. Hybrid Rocket Motor


Experimental Setup
A
variable-throat
venturi
with
upstream
pressure and temperature
measurements
was
employed in the gaseous
oxygen feed system in
Figure 1. Micrographs of unburned inner surface of paraffin fuel layer a)SEM order to attain the desired
micrograph, b) carbon elemental map, c) aluminum elemental map. All constant mass flow rates.
micrographs are 250 mm in height and width and are at 500x magnification
From previous experiments
using the LGCP motor, the
a
b
c
range of oxidizer mass flux
was determined and scaled
accordingly so that the
larger scale XTC motor
(see Fig. 3) had similar
initial operating conditions.
Flow rates of up to 0.42
Figure 2. Micrographs of unburned outer surface of paraffin fuel layer a)SEM kg/s can be obtained
micrograph, b) carbon elemental map, c) aluminum elemental map. All through the use of this
micrographs are 250 mm in height and width and are at 500x magnification
venturi, which is sufficient
for the desired oxidizer
mass
fluxes.
Oxidizer
mass fluxes ranging from
Blast Shield
X-ray
Image
60-290 kg/m2-s have been tested in the XTC
Source
Intensifier
hybrid rocket motor to obtain a range of data for a
given fuel formulation.
The dominating parameter that dictates the
mass-burning rate in a hybrid rocket motor is the
oxidizer mass flux. Since there is no discernable
pressure effect, the steady-state chamber pressure
of the XTC can be similar to or much greater then
that of the LGCP while still maintaining
approximately the same linear regression rate.
Because of this, the chamber pressure has been
selected to range from approximately 2.17 to 4.24
MPa (300 to 600 psig), which is similar to the
Figure 3. X-ray imaging setup used with XTC hybrid range used for the LGCP and will allow for
comparison in performance.
rocket motor
a

D. Fuel Formulation Consideration and Thermochemical Calculations of Paraffin-Based Fuels with


Silberline and Nano-Sized Tungsten Particles
For examining the burning rate enhancement by a new type of particle, the smaller quantity of nano-sized
particles required for a series of evaluation test firings in the LGCP hybrid rocket motor is highly beneficial. For this
reason, 20 types of nano-sized particles have been evaluated using the LGCP motor. 18 fuel formulations were
evaluated previously and a complete list of the particle type, percent by weight added to the solid fuel, and
performance enhancement can be found in References 8 and 9. In addition, two new types of nano-sized tungsten
particles have been evaluated as well: one is a neat tungsten particle with no oxide coating and the other with a 5%
oxide coating by weight. A comparison of the effectiveness of these two types of particles and their burning
characteristics is included below. These particles were obtained from Nano-Mat, Inc. for evaluation using the LGCP
hybrid rocket motor. The solid-fuel regression results of the HTPB-based fuels with these two new particles can be
compared to our previous data to determine the benefit on combustion performance using tungsten particles.
To further enhance the burning rate of new fuel formulations, the use of a non-polymeric fuel formulation has
also been implemented. Paraffin-based solid fuels have been shown to increase the burning rate several times over
that of traditional polymeric fuels such as HTPB. Testing and analysis of paraffin-based fuel formulations have been

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American Institute of Aeronautics and Astronautics

Density Impulse [g-s/cm ]

Density Impulse [g-s/cm ]

considered in both the LGCP and XTC hybrid rocket motors. A wide range of average oxidizer mass fluxes (60-290
kg/m2-s) have been evaluated for comparison to results obtained in the LGCP hybrid rocket motor for particle
addition to HTPB-based solid fuels and to
further extend the range of data.
340
The addition of Silberline aluminum
particles has shown to increase the linear
regression rate of HTPB-based solid fuel
320
formulations by approximately 30% over
the baseline pure HTPB fuel. Burning rate
enhancement is also expected for paraffin300
based solid fuel formulations containing
different amounts of aluminum particles.
280
Besides the increase in the regression rate
of the solid fuel, the density impulse of the
PF w/ 20% SILBAL
metallized fuel is also higher than the
PF w/ 17% SILBAL
260
PF w/ 13% SILBAL
baseline case. Figure 4 shows a comparison
PF w/ 10% SILBAL
of density impulses for varying percentages
PF w/ 7% SILBAL
of Silberline aluminum nano-sized flakes.
PF
w/
4%
SILBAL
240
Pure Paraffin Fuel
All data presented is for liquid oxygen as
the oxidizer and a chamber pressure of
1000 psia. As can be seen the addition of
220
1
1.5
2
2.5
3
3.5
4
4.5
5
aluminum to paraffin based fuels can
O/F
indeed be highly beneficial in volume
limited systems as the density impulse
Figure 4. Thermochemical calculations of density Isp of varying increases very significantly (8%) with a
percentages of Silberline aluminum nano-particles added to 20% aluminum addition by weight.
Figure 5 shows a comparison of density
paraffin
Isp of pure Paraffin to various weight
percentages of nano-sized tungsten particles.
The number of particles in a 13% by weight
340
tungsten addition is much lower than that of
a 13% by weight aluminum addition due to
the significantly higher molecular weight of
320
tungsten. The large increase in density Isp
that is observed, even over comparable
300
weight
percentages
of
Silberline
aluminum, is also very advantageous in
volume-limited systems.
280
PF w/ 20% W addition
PF w/ 13% W addition
PF w/ 17% W addition
PF w/ 10% W addition
PF w/ 7% W addition
PF w/ 4% W addition
Pure Paraffin Fuel

III.

Discussion of Results

The energetic powder additive to the


HTPB-based fuel that has shown the largest
increase in burning-rate enhancement in
previous series of tests is the Viton-A
240
coated Alex aluminum nano-sized powders
with an increase of 120% in mass-burning
rate and 123% increase in the average linear
220
1
1.5
2
2.5
3
3.5
4
4.5
5
regression rate at an oxidizer mass flux of
O/F
112 kg/m2-s. A number of other candidates
Figure 5. Thermochemical calculations of density Isp of varying also exhibited significant performance
percentages of tungsten nano-particles added to paraffin
increase compared to the baseline solid fuel
HTPB. For these candidates, which include
Silberline aluminum flakes, Viton-A coated Silberline aluminum flakes, Technanogies aluminum, an average
increase in linear regression rate of 60-70% was seen.8,9,11 The addition of Viton-A has proven to be beneficial in
increasing the average mass burning and linear regression rates.
260

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American Institute of Aeronautics and Astronautics

Average Regression Rate [mm/s]

E. Solid Fuels Containing Nano-Sized Tungsten Particles


The addition of nano-sized tungsten powder to solid-fuel formulations is beneficial due to the high volumetric
heat of oxidization (88.9kJ/cm3), which is approximately 6% higher than that of aluminum. For a volume limited
system this is extremely beneficial. The combustion of tungsten is also suitable for a rocket motor application due to
the strong heterogeneous reactions that begin at approximately 400-500 C and at higher temperatures, rapid
oxidation occurs, based upon information from reference 1616. If not for these strong heterogeneous reactions
occurring at relatively low temperatures, tungsten would be difficult to melt and vaporize due to its high melting
temperature (3,380 C) and extremely high boiling temperature (5,927 C).
As mentioned above, nano-sized tungsten powders were cast in an HTPB-based solid fuel formulation using an
IPDI curing agent with T-12 catalyst. To ensure that the IPDI curing agent did not alter the performance of the
baseline HTPB solid fuel formulation, a series of three baseline HTPB solid fuels were cast and tested using the
IPDI and T-12 in similar amounts as the tungsten nano-sized powder containing grains. This pure HTPB fuel
formulation is named SF20 and the data is contained in Fig. 6 and shows little variation in burning rate from SF1,
baseline HTPB fuel cast with MDI curing agent.
Comparison of the burning rate enhancement of the two newly developed fuels containing nano-sized tungsten
powders with the data of HTPB-based fuels containing other energetic powders is shown in Fig. 6. Even though the
HTPB with 13% tungsten powder showed only moderate increase in regression rate (about 38% at the average
oxidizer mass flux level of Gox~140 kg/m2-s) with respect to the pure HTPB, the 13% of tungsten by weight has
much fewer particles than 13% aluminum particles. At the equivalent amount of tungsten particles having the same
volume as the aluminum particles, one can expect a much higher burning rate enhancement. A fair comparison
should be based upon the equal molar percentage rather than equal weight percentage. The comparison of data in
Fig. 6 is still based upon the traditional weight
percentage consideration of fuel/propellant
3.5
formulation. It is noted that fuels containing the
tungsten particles with oxide coating showed a
3
slightly lower mass-burning rate than those with
the pure tungsten powder. Their slopes are quite
2.5
similar, though. This is expected since the active
tungsten content is less than that of the neat
2
particles, resulting in slightly lower energy
release.
The number of particles contained in a 13% by
weight tungsten fuel formulation is much less than
1.5
that of a 13% by weight aluminum or boron
because the molecular weight of tungsten is so
much higher. Comparing a 13% by weight
tungsten fuel formulation with an equimolar
1
concentration solid fuel formulation with
aluminum, the aluminum fuel would only contain
0.8
~2.14% by weight of aluminum. If an equimolar
60
80
100
120 140 160 180
concentration of tungsten were to be added to
equal the number of moles contained in a 13% by
Average Oxidizer Mass Flux [kg/m2-s]
weight aluminum fuel grain, a 50.4% by weight
13%C-ALEX (SF13)
Pure HTPB (SF1)
13%C-Boron (SF14)
13%ALEX (SF2)
tungsten fuel formulation would be needed. When
13%AVAL (SF15)
13%B C (SF3)
13%IHD-AR (SF16)
6.5%WARP-1 (SF4)
taking this factor into consideration, it is
13%NTECH80 (SF17)
6.5%B C+6.5%WARP-1 (SF5)
13%NTECH50 (SF18)
anticipated that the solid fuels with 50.4%
13%Boron (SF6)
5.65%Boron (SF19)
13%SILBAL (SF7)
tungsten particles by weight should show a
Pure HTPB/IPDI (SF20)
13%CLAL (SF8)
13%NMATWPure (SF21)
13%WARP-1 (SF9)
considerable increase in mass-burning rate, since
13%NMATW5 (SF22)
13%Cat-B C (SF10)
13%TECHAL (SF11)
Pure Paraffin w/ 2% Carbon Black (SF23)
equimolar basis is a more suitable means of
13%Al325 (SF12)
comparison. Higher percentage particle addition is Figure 6. Comparison of average linear regression rate
possible based upon test data obtained. The data for various solid-fuel formulations
observed plume jet did not show particle streaks,
which shows complete particle combustion within the rocket motor chamber. Combustion efficiency data shows
values from 77-87%, which falls in the upper half of previously reduced data. Since the surface temperature of
HTPB, which is approximately 660 C, is higher than the temperature for onset of oxidation of tungsten the particles
will start to under go heterogeneous combustion as soon as they are exposed to the oxidizing atmosphere of the
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American Institute of Aeronautics and Astronautics

motor combuster. Based upon this, complete combustion is anticipated even at much higher particle loadings
because of the means of ignition and heterogeneous combustion.

Average Linear Regression Rate [mm/s]

F. Paraffin-Based Solid Fuel


To evaluate the burning rate characteristics of paraffin-based solid fuels, both the LGCP and the XTC hybrid
rocket motors have been utilized. Initial baseline paraffin solid fuel testing, containing 2% carbon black by weight,
was conducted in the LGCP motor. The earlier tests of the paraffin fuels in this series exhibited certain amounts of
delamination of the fuel from the paper phenolic grain tube or between interfaces of consecutive casting layers.
Later on this delamination problem was solved by improvement of processing procedures. Further testing was
completed in the XTC hybrid rocket motor with paraffin-based fuel containing 13 wt. % of Silberline nano-sized
aluminum flakes. The measured chamber pressure and resultant burning rate data is given in Table 1. The resultant
linear regression rate data obtained from LGCP motor tests with the baseline paraffin solid fuel is also included in
Figure 6 for direct comparison with the HTPB-based solid fuels containing different types of nano-sized energetic
particles. It is quite obvious that the baseline paraffin solid fuels in the LGCP hybrid rocket motor demonstrated a
significantly higher regression rate than any of the HTPB-based fuel formulations containing nano-sized particles.
For clarity purpose, the data obtained from paraffin-based solid fuels containing Silberline aluminum flakes is not
included here, but is shown later in the text.
The testing of paraffin-based solid
Table 1. Paraffin-based solid fuel formulation test conditions and fuels in the XTC motor focused on
paraffin-based
fuel
formulations
resultant average regression rates
containing 13% by wt. Silberline
Average
Average
aluminum particle addition. Of the XTC
Gox,ave
Chamber
rb
Thrust
Test No.
2
rocket motor firings that were conducted,
[kg/m -s] [mm/s] Pressure
[N]
five of the tests produced useful results.
[MPa]
The five aluminized paraffin solid-fuel
NS-115-PFC2-100
72.4
2.05
3.11
131.1
tests firings exhibited very high regression
NS-116-PFC2-100
122.4
3.13
3.54
168.1
rates in comparison to baseline paraffin
NS-117-PFC2-100
108.9
2.79
2.09
162.1
solid fuels. Table 1 shows the average
oxidizer mass fluxes and linear regression
NS-121-PFC2-100
64.9
2.22
3.14
153.0
rates measured for these tests. The data
XTC-17-PF-SILBAL-13 190.0
4.84
2.34
1081.9
presented in Table 1 are plotted in Fig. 7
XTC-20-PF-SILBAL-13 148.4
4.56
1.69
806.9
against the data obtained for the baseline
XTC-21-PF-SILBAL-13 166.0
4.42
2.21
1041.6
paraffin-based solid fuel formulations. The
XTC-22-PF-SILBAL-13 290.3
7.16
3.10
1458.6
paraffin solid-fuel data of Karabeyoglu, et.
XTC-23-PF-SILBAL-13 217.4
6.58
3.31
1899.8
al.12 of the Stanford University are also
plotted on the same figure for comparison
purposes. The Stanford data curve fit has the
8
Paraffin Fuel w/ 2% Carbon Black (SF23)
same slope as the PSU data for nonaluminized
7
Paraffin Fuel w/ 13% Silberline Aluminum (SF24)
Stanford Paraffin Regression Rate Data
paraffin fuel; however, the regression rates of
6
PSUs data are higher due possibly to the
5
difference in processing techniques and the
slight difference in fuel formulations. The
4
difference in the amount and size of carbon
black powder of these two fuels could cause the
3
surface energy release amount to be different. It
2.5
is evident that there is a noticeable increase in
the linear regression rate of the solid-fuel
2

formulations containing Silberline nano-sized


aluminum flakes compared to the baseline
1.5
paraffin fuel formulations if the data were
60
80
100 125 150 175 200 250 300
extrapolated to a higher mass flux level. By
2
Average Oxidizer Mass Flux [kg/m -s]
extrapolating the curve fit obtained for the
Figure 7. Comparison of average linear regression rates of
baseline paraffin fuel formulation to the Gox,ave
baseline paraffin fuel, paraffin fuel containing 13% by wt.
value of 190 kg/m2-s, an increase of ~30% is

Silberline aluminum flakes, and Stanford paraffin burnseen for the formulations containing 13% by wt.
rate curve fit
Silberline particles. An increase of about 60%
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American Institute of Aeronautics and Astronautics

O2 flow

40 mm

Figure 8. Grain surface of a recovered paraffin-based solid fuel with 13% Silberline aluminum
showing wrinkled pattern (Test No. XTC-PF-10-SILBAL-13)
is seen for the difference between the aluminized paraffin and the Stanford curve fit results. Another observation
that can be made regarding the burning trends of the paraffin-based fuel formulations is the difference in slope of the
curve fits. This difference in slope is caused by the aluminum particles in the paraffin fuel combustion process. In
baseline paraffin fuel formulations, one of the governing parameters is the oxidizer flow velocity. This dictates the
size of the wave structure that occurs on the fuel surface (see Fig. 8) and also the size of the particles that are
stripped from the surface waves of the molten fuel layer and entrained into the combustion zone.
G. Instantaneous Regression Rate Determination
Analysis of the visual data obtained from four XTC test firings with HTPB-based and paraffin-based solid fuel
formulations containing 13% by wt. Silberline aluminum were analyzed in order to get a correlation of the
instantaneous fuel port radius near the aft end of the grain as a function of time. This was accomplished by
processing the video images from the real-time X-ray radiography system using a commercially available special
effects package that did not alter the actual fuel surface location. The special effect inverts the image density of the
original picture; this inversion greatly enhances the clarity of the fuel grain surface. Images are analyzed at ~0.25
second increments, which was chosen to be small enough to give sufficient resolution for the curve fit and large
enough to show the radial variation of the fuel surface. This time step is altered if an image is difficult to measure a
distinct fuel grain surface location. The deduced instantaneous radius is fit as a power law of time according to:

r (t ) r0 = a (t tign ) n

(1)

Tests XTC-05 and XTC-07 were conducted


with HTPB-based solid fuel grains containing
13% by weight Silberline aluminum flakes.
Figure 9 shows the deduced instantaneous port
8
radii (in terms of change of port radius) versus
time of these two tests. The difference between
6
the oxidizer flow rates of these two tests is
approximately 13% with Test XTC-05 being
higher. The power-law curve fit parameters a and
4
n for Tests XTC-05 and XTC-07 are presented in
Table 2. The exponent of the power law
correlation for the higher flow rate test is slightly
2
XTC-05 Instantaneous Change in Port Radius
greater than that for the lower flow rate test. The
XTC-07 Instantaneous Change in Port Radius
slopes of the two Silberline aluminum fuel grain
0
tests expressed by parameter a are quite similar. It
0
2
4
6
was noted that both curve fits have a high R2
Time from Ignition [sec]
value greater than 0.98 indicating a good match to
Figure 9. Deduced instantaneous port radii as functions of the data.
time for test firings XTC-05 and XTC-07
A similar plot for the two aluminized paraffin
Table 2. Power-law curve fit parameters for XTC fuel tests (Tests XTC-21 and XTC-22) is shown
motor tests with aluminized HTPB and paraffin fuels
in Fig. 10 using the same power law curve fit
Test No.
a
n
function. The fitting parameters a and n are also
shown in Table 2. Again it was found that the
XTC-05-SILBAL-13
1.758
0.9207
exponent n is higher for the higher oxidizer flow
XTC-07-SILBAL-13
1.793
0.8772
rate case. The flow rate of Test XTC-22 is about
XTC-21-PF-SILBAL-13
4.640
0.752
25% higher than that for Test XTC-21.
XTC-22-PF-SILBAL-13
7.762
0.9708
Change in Port Radius [mm]

10

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American Institute of Aeronautics and Astronautics

To determine a correlation of the regression


rate with respect to important operating
parameters (such as the instantaneous oxidizer
mass flux, port diameter, and total mass flux), a
data analysis procedure has been developed. Since
the instantaneous regression rate of the solid fuel
is governed by the local energy transfer rate and
mass diffusion processes occurring in the port of
the hybrid motor, it should depend strongly upon
the total mass flux at the given station. By
differentiating Eq. (1) with respect to time, we
have

Change in Port Radius [mm]

10

XTC-21 Instantaneous Change in Port Radius


XTC-22 Instantaneous Change in Port Radius

rb =

0
0.0

0.5

1.0

1.5

2.0

2.5

n 1
dr
n 1
= an ( t tign ) = an ( t *)
dt

Time from Ignition [sec]

(2)

Figure 10. Deduced instantaneous port radii as functions of where: t* t tign .


time for test firings XTC-21 and XTC-22
From this equation it can be seen that if the exponent n is less than unity, the regression rate decreases as time
increases. The total mass flux at an axial location is the total mass flow rate divided by the instantaneous port area,
hence

Gtotal =

m& total
n
ro + a ( t *)

(3)

where the total mass flow rate is the sum of the instantaneous oxidizer mass flow rate and the fuel flow rate from
surface pyrolysis, namely

m& total = m& ox + m& fuel , py = m& ox + p rb As


= m& ox + 2 L p an ( t *)

n 1

ro + a ( t *)n

(4)

Substituting Eq. (4) into Eq. (3) yields,

Gtotal (t*) =

m& ox + 2 L p an ( t *)

ro + a ( t *)n

n 2
ro + a ( t *)

n 1

(5)

Inverting Eq. (2) to express t* in terms of regression rate, we have


1

r (t*) n 1
t* = b
an

(6)

Eliminating t * from Eq. (5), we obtain the following relationship between rb (t*) and Gtotal (t*)

Gtotal (t*) =

m& ox

rb (t*)
an

ro + a

n
n 1

2 L p rb (t*)
n

rb (t*) n 1
+
r
a
o
an

(7)

This equation is in an implicit form of regression rate dependency on the total mass flux, oxidizer mass flux, initial
port radius, the axial distance and the power-law parameters. In order to express regression rate in terms of the total
mass flux, one has to make certain order-of-magnitude approximations of exponent n. Even though this expression
is much more complex than the conventional expression of regression rate in terms of power-law of oxidizer mass
flux, it is derived without major assumptions.

9
American Institute of Aeronautics and Astronautics

Using Eq. (7), the deduced instantaneous regression rates of the two aluminized HTPB-based fuel test runs
(XTC-05 and XTC-07) are plotted versus the instantaneous total mass flux in Fig. 11. Even though the slopes (a) of
the fuel radius change versus time are nearly identical (see Table 2 and Fig. 9), the functional relationships between
regression rate and total mass flux are quite different as indicated by the difference of curvature and location of these
two sets of data in Fig. 11. We have looked into the possibility for using instantaneous oxidizer mass flux to replace
the total mass flux; however, the results shown in Fig. 12 also indicated the non-collapsing situation of the two
curves. Furthermore, the data do not follow the conventional power-law relationship between the measured
regression rate and the instantaneous oxidizer mass flux when the data are given in a log-log plot.
2

Linear Regression Rate [mm/s]

Linear Regression Rate [mm/s]

2.0

1.8

1.6

1.4
XTC-05
XTC-07

1.5

1.25

rb vs. Gox,inst Test XTC-05


rb vs. Gox,inst Test XTC-07
1

1.2
100

200

300

400

500

600

Total Mass Flux [kg/m -s]

100

150

200

250

300

400

Instantaneous Oxidizer Mass Flux [kg/m2-s]

Figure 11. Dependency of the instantaneous


regression rate of aluminized HTPB fuels on
instantaneous total mass flux

Figure 12. Dependency of the instantaneous


regression rate of aluminized HTPB fuels on
instantaneous oxidizer mass flux
The aforementioned differences between the
regression rate versus total mass flux curves obtained
under different operating conditions is further
illustrated in Fig. 13, from the results of two
aluminized paraffin-based fuel test runs (XTC-21 and
XTC-22) conducted under different test conditions. In
this figure the two curves are even further apart
showing the strong dependency of instantaneous
regression rate on the instantaneous total mass flux.

Linear Regression Rate [mm/s]

1.75

IV.
XTC-21
XTC-22

Conclusions

(1) Nano-sized tungsten powder addition to HTPBbased fuel formulation in 13% by wt. shows an
increase of 38% in fuel regression rate compared to
3
the baseline HTPB fuel formulation. Volume limited
200
400
600
800
1000
1200
1400
1600
1800
Total Mass Flux [kg/m2-s]
propulsion systems would greatly benefit from the use
Figure 13. Dependency of the instantaneous of nano-sized tungsten powders in solid fuel
regression rate of aluminized paraffin fuels on formulations due to its high density, high heat of
instantaneous total mass flux
oxidation, and low oxidation temperature via
heterogeneous reactions. The benefit derived in high
density impulses and combustion efficiency makes this energetic powder a viable additive to advanced energetic
fuels.
(2) SEM/EDS micrographs of the newly processed energetic paraffin-based solid fuels have shown that the nanosized Silberline aluminum flakes are homogenously mixed in the fuel matrix. It was verified that the recently
developed mixing and casting procedures do not cause particle migration in the fuel matrix, producing grains that
have fairly uniform distribution of aluminum particles throughout the fuel.
4

10
American Institute of Aeronautics and Astronautics

(3) Paraffin-based solid fuels containing Silberline aluminum flakes showed an increase in linear regression rates
of about 30% over the baseline paraffin fuel formulation. An increase of about 60% is seen for the difference
between the aluminized paraffin and the Stanford curve fit results.
(4) The real-time X-ray radiography system enables the measurement of the instantaneous radius of the solid fuel
grain with a cylindrical center port. The radial increment of the regressing fuel surface can be correlated with time in
a power-law form. The exponent for time was found to be higher as the oxidizer mass flow rate is increased.
(5) An implicit relationship showing the dependency of instantaneous fuel regression rate on the total mass flux was
obtained. The functional relationships for aluminized HTPB and paraffin fuels were obtained in graphical forms.
Results show that the position and the curvature of these curves depend strongly upon the oxidizer mass flow rate
and initial port radius of the fuel grain. This shows that the conventional power-law relationship between the
average regression rate and average oxidizer mass flux cannot be applied to the instantaneous regression rates of
solid fuel burning in hybrid motor conditions.

V.

Acknowledgements

The authors would like to acknowledge Dr. Richard E. Bowen of NAVSEA and Mr. Carl Gotzmer and Mrs.
Nancy Johnson of the Naval Surface Warfare Center-Indian Head Division for their sponsorship of this research
project through CPBT corporation (under contract number N00174-02-C-0024) with a subcontract to PSU.

VI.

References

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Risha, G. A., Harting, G. C., Kuo, K. K., Peretz, A., and Koch, D. E., "Pyrolysis and Combustion of Solid Fuels in
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4
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5
Strand, L. D., Ray, R. L., Anderson, F. A., and Cohen, N. S., Hybrid Rocket Fuel Combustion and Regression
Rate Study, AIAA Paper 92-3302, June 1992.
6
Teague, W., Wright, A., Balkanli, D., and Hybl, L, Effect of Energetic Fuel Additives on the Temperature of
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Exhibit, Los Angeles, CA, 20-23 June 1999.
7
Risha, G. A., Harting, G. C., Kuo, K. K., Peretz, A., Koch, D. E., Jones, H. S., and Arves, J. P., Surface Heat
Release of HTPB-Based Fuels in Oxygen Rich Environments, Combustion of Energetic Materials, Eds. K. K. Kuo,
L. T. DeLuca, Begell House, Inc., pp. 101-115, 2002.
8
Risha, G. A., Evans, B., Boyer, E., Wehrman, R. B., and Kuo, K. K., Nano-Sized Aluminum- and Boron- Based
Solid-Fuel Characterization in a Hybrid Rocket Engine, AIAA 2003-4593, AIAA/SAE/ASME/ASEE 39th Joint
Propulsion Conference and Exhibit 20 23 Huntsville, AL, July 2003
9
Risha, G. A. Enhancement of Hybrid Rocket Combustion Performance Using Nano-Sized Energetic Particles,
Ph.D. Dissertation, The Pennsylvania State University, August 2003
10
Evans, B., Risha, G. A., Favorito, N., Boyer, E., Wehrman, R. B., Libis, N., Kuo, K. K., Instantaneous
Regression Rate Determination of a Cylindrical X-Ray Transparent Hybrid Rocket Motor, AIAA Paper No. 034592, AIAA/SAE/ASME/ASEE 39th Joint Propulsion Conference and Exhibit 20 23 Huntsville, AL, July 2003.
11
Risha, G.A., Boyer, E. B., Wehrman, R. B., and Kuo, K. K., Performance Comparison of HTPB-Based Solid
Fuels Containing Nano-Sized Energetic Powder in a Cylindrical Hybrid Rocket Motor, AIAA 2002-3576,
AIAA/SAE/ASME 28th Joint Propulsion Conference, Indianapolis, IN, July 7-10, 2002.
12
Karabeyoglu, M. A., Zilliac, G., Cantwell, B. J., DeZilwa, S., and Castellucci, P., Scale-Up Tests of High
Regression Rate Liquefying Hybrid Rocket Fuels, AIAA Paper No. 03-1162, 41st AIAA Aerospace Sciences
Meeting and Exhibit, Reno, NV, January 6-9, 2003.
13
Karabeyoglu, M. A., Altman, D., and Cantwell, B. J., Combustion of Liquefying Hybrid Propellants: Part 1,
General Theory, Journal of Propulsion and Power, Vol 18, No. 3, pp. 610-620, 2002.
14
Karabeyoglu, M. A., and Cantwell, B. J., Combustion of Liquefying Hybrid Propellants: Part 2, Stability of
Liquid Films, Journal of Propulsion and Power, Vol 18, No. 3, pp. 621-630, 2002.

11
American Institute of Aeronautics and Astronautics

15

Risha, G. A, Ulas, A., Boyer, E. B., Kumar, S., and Kuo, K. K., Combustion of HTPB-Based Solid Fuels
Containing Nano-sized Energetic Powder in a Hybrid Rocket Motor, AIAA 01-3535, AIAA/SAE/ASME/ASEE
37th Joint Propulsion Conference and Exhibit, Salt Lake City, UT, 8 11 July 2001.
16
Weast, R. C.(ed), CRC Handbook of Chemistry and Physics, 67th Edition, p. B-40, 1987.

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American Institute of Aeronautics and Astronautics