47th AIAA/ASME/SAE/ASEE Joint Propulsion Conference & Exhibit

31 July - 03 August 2011, San Diego, California

AIAA 2011-5909

Analytical and Experimental Comparisons of HTPB and

ABS as Hybrid Rocket Fuels

Stephen A. Whitmore*, Zachary W. Peterson and Shannon D. Eilers

Utah State University, Logan, UT, 84322

Acrylonitrilebutadiene-styrene (ABS) thermoplastic is evaluated as a

potential fuel for hybrid rocket motors and compared to the widely used fuel
material Hydroxyl-Terminated Polybutadiene (HTPB). For this project Nitrous
Oxide (N2O) is used as the matching oxidizer. ABS is widely mass-produced for
non-combustion applications including household plumbing and structural
materials. Analytical predictions for enthalpies of formation, products of
combustion, and end-to-end motor performance are compared against staticburn test results for ABS fuel grain manufactured using Direct-Digital
Manufacturing (DDM). The chemistry and performances of the ABS fuel grains
are compared against fuel grains cast from HTPB. ABS grains were DDMfabricated from existing stock materials composed of 50:43:7 butadiene,
acrylonitrile, and styrene mole fractions. The grains were tested and compared
against HTPB grains of equal physical volume and dimension. Test results
demonstrate a higher burn-to-burn consistency for ABS fuel grains, but slightly
*

Associate Professor, Mechanical and Aerospace Engineering Department, 4130 Old Main Hill, UMC 4130,
Associate Fellow, AIAA.

Graduate Research Assistant, Mechanical and Aerospace Engineering Department, 4130 Old Main Hill, UMC
4130, Student Member, AIAA.

Graduate Research Assistant, Mechanical and Aerospace Engineering Department, 4130 Old Main Hill, UMC
4130, Student Member, AIAA.

Copyright 2011 by Utah State University. Published by the American Institute of Aeronautics and Astronautics, Inc., with permission.

reduced overall performance. The reduced performance is primarily attributed

to overall lower combustion efficiency for the ABS grains. The combustion
effectiveness of relative monomer compositions for the ABS fuel grains were
investigated; and equilibrium chemistry calculations conclude that for a given
oxidizer to fuel ratio, varying the butadiene mole-fraction in the ABS
formulation has a significant effect on the propellant performance.
Nomenclature

=free energy of formation curve fit intercept parameter

ABS

= acrylonitrilebutadiene-styrene

Aburn

= fuel grain surface burn area, cm2

Ac

= fuel chamber cross sectional area , cm2

Aexit

= nozzle exit area , cm2

Aox

= effective total oxidizer injector area, cm2

A*

= nozzle throat area, sonic choke area, cm2

= free energy of formation curve fit slope parameter

= carbon atom

Cd ox

= effective oxidizer injector discharge coefficient

CF

= thrust coefficient

cp

= specific heat of solid propellant fuel grain, J/kg-K

c*

= propellant characteristic velocity, m/sec

= steady state thrust, N

g0

= standard acceleration of gravity, 9.8067 m/sec2

=hydrogen atom

HTPB

= hydroxyl-terminated Polybutadiene

= heat of ablation /gasification, MJ/kg

Isp

= specific impulse, s

Isp effective = effective specific impulse, s

Itotal

= total impulse, N-s

Mfuel

= total fuel consumed during motor burn, kg

Mox

= oxidizerfuel consumed during motor burn, kg

MW

= molecular weight of combustion products

m! fuel

= solid fuel grain mass flow rate, kg/sec

m! ox

= oxidizer mass flow rate, kg/sec

= degree of polymerization

N2

= gaseous nitrogen

N2O

= nitrous oxide

= generic mole fraction

na

= acrylonitrile mole fraction

nb,

= butadiene mole fraction

ns

= styrene mole fraction

O/F

= oxidizer to fuel mass flow ratio

OH

= hydroxyl radical

Pr

= Prandtl number

Pox

= oxidizer injector upstream feed pressure pressure, kPa

P0

= combustion chamber pressure, kPa

Rg

= gas-specific constant, J/kg-K

Ru

= universal gas constant, 8314.4126 J/kg-K

r!

= fuel grain linear regression rate, cm/sec

= combustion temperature, K

T0

= adiabatic flame temperature, K

Vc

= combustion chamber internal volume, cm3

= Gibbs free energy of formation, kJ/mol

Ggg

=Gibbs polymerization free energy for gaseous state, kJ/mol

Gmono =Gibbs free energy for monomer, kJ/mol

!G 0 la

=Gibbs polymerization free energy, amorphous solid from liquid monomers, kJ/mol

Gpoly

=Gibbs free energy for polymer, kJ/mol

= mole specific enthalpy change, kJ/mol

Hf0

= standard enthalpy of formation, kJ/mol

Qc

= heat of combustion, kJ/mol

=mole specific entropy change, kJ/mol-K

!*

= combustion efficiency

= ratio of specific heats or combustion products

= dynamic viscosity, Nt-s/m2

= sample mean

fuel

= solid fuel grain material density, kg/m3

ox

= liquid oxidizer density, kg/m3

= sample standard deviation

I.

Introduction

ESS risky launch vehicles must be developed to operational readiness for commercial
spaceflight to become a viable market. A key to commercial spaceflight success is the cost-

efficient and safe operation of large rocket motors in civilian environments. Because of the
extreme risk and potentially negative environmental impact, large solid-propelled rocket motors
simply cannot be operated at civilian airports. Approximately 70% of catastrophic space-launch
failures are attributable to the vehicles power plant.1 NASA estimates that the Space Shuttles
liquid fueled main engines will fail catastrophically once every 1530 sorties per engine and its
solid rocket boosters will fail catastrophically once every 1,550 sorties per motor. While this
level of risk is acceptable for experimental and government-operated vehicles, it is unacceptable
for a potential commercial spaceflight operator.
Hybrid motors have the potential to fulfill this low-risk flight requirement. The inherent safety
of hybrid rocket motors greatly reduces the operational risk to a launch vehicle or any hybrid
rocket propelled missile or spacecraft. According to the U.S. Department of Transportation,

hybrid motors can be stored and operated without possibility of explosion or detonation.2 Other
advantages of hybrid rockets include the ability to be stopped, restarted, and throttled, easy (and
hence potentially cheaper) ground handling, and relative insusceptibility to grain flaws.
A. Current Hybrid-Motor Manufacturing Limitations
Hybrid rocket motors have been in development for more than two decades, but have seen
little commercial application mainly due to difficulty associated with of mass-producing fuel
grains. Motor-to-motor performance consistency has also been a commercial disincentive. To
date, the majority of mainstream hybrid motor development has focused on performance
characterization and improvement. Very little development effort has been directed towards
manufacturing methods to support volume production. The current production method involves
casting viscous or non-polymerized material by hand in a casing mold to form the fuel grain,
to be later manually assembled with other motor components (i.e., igniter, oxidizer tank, oxidizer
valve/injectors, post-combustion chamber, and rocket nozzle). This low-tech approach results in
market prohibitive production costs and a high degree of performance variability. Motortomotor response times, peak thrust, and total impulse levels can vary significantly. This high
degree of motor-to-motor variability may be acceptable for experimental or government vehicles
operated on a restricted-test range, but will not secure FAA certification for non-experimental,
commercial spaceflight operations. Finally, the current low-technology, labor intensive
fabrication processes used to cast and de-gas hybrid-motor fuel grains simply cannot produce the
numbers and varieties of motors required to support the ambitious launch rates necessary to
support what is expected to be a fast-growing commercial space industry.
Leveraging the recent rapid capability growth in factory automation and robotics, DirectDigital Manufacturing (DDM)3 offers the potential to revolutionize methods used to fabricate

hybrid rocket fuel grains. DDM technology can support high production rates with a much
greater degree of motor-to-motor consistency than is possible using traditional one-off motor
casting methods. If matured and commercialized, this technology will have a transformational
effect on hybrid rocket motor production by improving quality, consistency, and performance,
while reducing development and production costs.
II.

Chemical Analysis of Hydroxyl-Terminated Polybutadiene (HTPB) and AcrylonitrilebutadieneStyrene (ABS) as Hybrid Rocket Fuel Grains

Many modern thermosetting polymers and thermoplastics can be mass-produced with a

uniform consistency, but have not been evaluated as hybrid rocket fuels. The most commonly
used hybrid rocket fuel, Hydroxyl-terminated polybutadiene (HTPB) is a legacy thermosetting
polymer material frequently used as binder for solid rocket propellant grains. It remains the
hybrid fuel grain material of choice primarily because of industry familiarity with its chemical
and structural properties. HTPB is a solid homopolymer made by combining two components: 1)
a hydroxyl-terminated polymer of butadiene and 2) a cross-linking agent, either isocyanate or
methylene diphenyl diisocyanate (MDI), used to polymerize and set the material. No industry
standard value for the enthalpy of formation exists. The enthalpies of formation of HTPB have
been published, but vary widely -- from 64.88 kJ/g-mol4, and 363.17 kJ/kg5, to -31.57 kJ/g-mol6 - as the relative degrees of polymerization and curative treatments for the mix are modified.
HTPB, as a thermosetting polymeric material, cannot be shaped and manufactured using
DDM methods. HTPB must be mixed from its liquid base-components, degassed under vacuum,
and then cast and cured in a fuel grain mold. HTPB does not melt in the presence of heat; but
instead chars and ablates. HTPB burn properties can vary dramatically depending on the degree

of residual gas seeding in the cast material, and the length of time the material has cured. Typical
cure times exceed 10 days to two weeks.
Alternatively, Acrylonitrilebutadiene-styrene (ABS) is an inexpensive thermoplastic that can
be easily produced in wide variety of shapes. More than 1.4 billion kilograms of ABS material
were produced chemical and petrochemical industries world wide in 20107. ABS plastics are
readily shaped into complex geometries using DDM techniques. If ABS can be demonstrated to
be thermodynamically and structurally competitive with HTPB, it would represent a very
attractive option as a hybrid rocket fuel grain material. This material is widely mass-produced for
a variety of non-combustion applications including household plumbing, and structural materials.
To date, however, no detailed analysis of the performance of ABS as a rocket fuel has been
performed. This paper details the rocket-based combustion of ABS polymer variations with
Nitrous Oxide (N2O), and compares its performance against HTPB as a baseline. Both analytical
predictions8,9 and experimental verifications will be presented. Analytical predictions include
shifting-equilibrium chemistry effects, fuel regression rates, and unsteady thrust and impulse
predictions. For this initial study, simple cylindrical port grain configurations were modeled and
tested.
Because ABS is widely used as an industrial and domestic construction material, the heat of
combustion Qc, in the presence of oxygen has been documented for safety considerations.10
However, because ABS has not previously been purposely considered as a potential rocket fuel
grain marterial, there has been little to no work quantifying the materials standard enthalpy of
formation, Hf0. The enthalpy of formation is required to calculate the properties of the
combustion products when ABS is burned in the presence of nitrous oxide at various mixture
ratios and combustion pressures. As with HTPB it is expected that the ABS enthalpy of

formation will vary widely depending on the ratio of the various monomers that make up the
ABS polymer.
B. Group Addition Method for Calculating the Hf0 of Polymers
Because there are no reliable, industry standard values for the enthalpies of formation for both
HTPB and ABS; this study employs a systematic approach for calculating Hf0 using the Group
Addition methods developed by Van Krevelen and Chermin11,12. Van Krevelens method
calculates the Gibbs free energy of formation Gf, of a polymer in a gaseous state by summing
individual group contributions of common polymer-building molecular groups. The group
contribution to Gf is assumed as a linear function of temperature, with the form
!G 0f group = A + B " T

(1)

In Eq (1), A and B are linear-fit constants, and T is the temperature of formation. Using the
fundamental definition for Gibbs free energy,
!G = !H " T # !S .

(2)

Inspecting Eqs. (1) and (2) shows that the equation intercept is identical to the standard enthalpy
of formation, and the slope corresponds to the standard entropy of formation. In Eq. (2) S is the
entropy change, and H is the enthalpy of formation. Because the Gibbs free energy of a
polymer can be estimated as the summed contributions of the individual molecular groups
enthalpies of formation minus the contributions of entropy / temperature product; it follows that
the enthalpy of formation of the polymer is simply the summation of the contributions of the
individual groups to the enthalpy of formation.

The Gibbs free energy values given by Ref (11) are expressed for materials in a gaseous state.
Because polymers do not exist in a gaseous state, a correction is performed to account for
condensed states. Reference 12 applies a correction to the Gibbs free energy of polymerization of
the gaseous state, where the Gibbs free energy of polymerization is given by
!G o gg = !G o poly " !G o monomer

(3)

The Gibbs free energies of a polymer and its monomer equivalent,

!G o poly

o
and !G monomer are

obtained by summing the group contributions as described above. A correction term is then
added to the free energy of polymerization to account for the formation of an amorphous (noncrystalline) solid or liquid polymer from the gaseous polymer. The correction for the Gibbs free
energy of an amorphous solid polymer created from monomers in a liquid state is

!G 0 la = !G 0 gg " 40 # T

(4)

Inspecting equations (1), (2), and (4) shows that the Gibbs free-energy correction only affects the
entropy of formation and not the enthalpy or formation. Thus, it can be concluded that the
enthalpies of formation of a substance in an amorphous state is approximately the same as that
substance when in a gaseous state. Thus the enthalpies of formation can be calculated directly
from the presented data in Ref (11).
C. Calculating Hf0 for HTPB
To verify applicability of the group addition process for rocket combustion, the method
described in the previous paragraph was used to calculate the heat of formation of HTPB. Since
HTPB with Nitrous Oxide as the oxidizing agent is the most commonly used hybrid rocket
propellant combination; a large data based of performance data exists and can be used to verify

10

the additive group calculations. As an introduction to the group addition method, a detailed
calculation for HTB will be presented here.
A common polymer formulation of HTPB (ARCO R-45M13) has 50 repeating butadiene
units with a hydroxyl radical at each end14, thus the moniker hydroxyl terminated. Figure 1
depicts the molecular structure of the bonded HTPB chain showing the polymerized trans/cis 1,4
butadiene units, and the hydroxyl radicals attached to each end of the string. The cis/trans
structures have slightly different enthalpies of formation; however these differences are
considered negligible compared to the overall heat of polymerization, and were neglected for this
analysis. The corresponding chemical formula is C200H302O2, and the mean molecular weight is
2734 kg/kg-mol.

Figure 1. Chemical Structure of N=50 Polymerization of HTPB.

The major constituent of HTPB, 1,4 butadiene has the chemical formula,

( !CH 2 ! CH = CH ! CH 2 ! ) .
The heat of formation for each butadiene molecule is calculated by

11

#
&
2 ! % "44 kJ (
$
g " mol '

2 ! ( "CH 2 " )
2 ! ( "CH = ) + 2 ! ( 76

kJ
g " mol

________
Total )H f butadiene 32 kJ
g " mol

(5)

The heat of formation contribution of each hydroxyl group is

!H 0f

OH

" #176

kJ
g # mol

Each components mole fraction within the N=50 polymerization is

! nbutadiene $ ! 50 / 52 $ ! 96.15% $
# n
&=#
&=#
&
" OH % " 2 / 52 % " 3.85% % ,

(7)

and the molecular heat of formation is

!H 0 f

HTPB

= nbutadiene " !H 0 fbutadiene + nOH " !H 0 fOH

#
&
#
&
= ( 0.9615 ) " % 32 kJ ( + ( 0.0385 ) " % -176 kJ (
$ g-mol '
$
g-mol '
= 23.99

kJ
g-mol

The reduced chemical formula corresponding to the calculated value H0f

( 0.9615 ) ! (C4 H 6 ) + ( 0.0385 ) ! (OH ) = C3.8462 H 5.8077O0.0385

(7)
HTPB

is

(8)

Using Eq. (8) the corresponding heat of formation in mass units is calculated at 456.5 kJ/kg -- a
value that is approximately 25.6% higher than that value reported by Ref. (5). The H0f
presented by Eq. (7) neglects the chemical contributions of the curing agent used to polymerize
and set the grain material. However, the curing agent represents a small fraction of the cured

12

material approximately than 12% by mass15 -- and for the purposes of this discussion the
effects on H0f are considered to negligible.
D. Thermodynamic and Transport Properties of HTPB/Nitrous Oxide Combustion
The value for H0f

HTPB

calculated by Eq. (7), and the reduced molecular formula given by

Eq. (8) were directly input into the NASA program Chemical Equilibrium with Applications,
(CEA)16 with HTPB as 100% of the fuel component of the propellant. The CEA program was
configured to calculate the thermodynamic and transport properties of the combustion products
as a function of combustion pressure P0, and the mass flow oxidizer-to-fuel (O/F) ratio.
Calculated parameters include adiabatic flame temperature T0, ratio of specific heats , molecular
weight MW, characteristic velocity c*, dynamic viscosity , and Prandtl number Pr. Figure 2 plots
these thermodynamic and transport properties as a function of O/F ratio and the combustion
chamber pressure. Depending on the chamber pressure, the peak c* performance occurs at an O/F
ratio between 5.0 and 6.0. At 7000 kPa chamber pressure (580 psia) the corresponding
interpolated peak c* value is 1630 m/sec. This value agrees closely with the textbook peak
value of 1625 m/sec for hybrid HTPB/N2O combustion at 1000 psi chamber pressure (Ref. 4).
This 0.3% level of agreement supports the accuracy of the group addition H0f calculation
methods.

The CEA code has extensive internal libraries for reactant thermodynamic and transport properties including standard and
nonstandard temperature and pressure conditions. Unfortunately, the CEA thermochemical database does not have an entry for
and of the formulations of HTPB. Consequently, HTPB fuel-grain properties, including the atomic mole-fraction formula and
enthalpy of formation, must be externally input to the program.

13

Figure 2. Thermodynamic and Transport Properties of N2O/HTPB Combustion Products.

E. Calculating the Hf0 of Various ABS Polymer Formulations
For this preliminary analysis the ABS formulations were varied substantially to evaluate the
best performing propellant formulations for the material. The monomers that make up any ABS
thermoplastic are 1) acrylonitrile, 2) butadiene, and 3) styrene. The corresponding chemical
structures for these monomers are17

! acrylonitrile $ !CH 2 = CH ' C ( N $

# butadiene & = #
&
C4 H 6
#
& #
&
#" styrene &% #" C6 H 5CH = CH 2 &%

(9)

14

Figure 3 shows the representative chemical structure of the ABS polymer for various monomer
constituencies, where nb, na, and ns are the respective mole fractions of Acrylonitrile, butadiene,
and styrene.

Figure 3. ABS Chemical Structure.

Readily available industrial formulations of ABS tend to consist of approximately 1/2
butadiene; with a typical formulation consisting of 50% (mole fraction) butadiene, 43%
acrylonitrile and 7% styrene. While the authors recognize that the monomer ratio may not
produce a propellant with optimal energy content, the ready availability of this stock product
favored this formulation for analysis and testing during this phase of the project. Table II shows
monomer Hf0, heats of polymerization Qpolymerization, the corresponding polymer Hf0, mole
fractions, and enthalpy contributions of the three ABS constituent monomers using the 50:43:7
monomer-ratios and the group addition method. The enthalpy of formation is calculated as 62.63
kJ/g-mol, and the reduced chemical formula corresponding to the calculated value H0f ABS is

(C3.85H4.85N0.43.)

(10)

The equivalent mass-based enthalpy of formation is 1097.4 kJ/kg. This value is roughly 140%
higher than the corresponding value calculated form HTPB. The higher calculated enthalpy of
formation suggests that this ABS formulation will likely not burn as hot as will HTPB.

15

Table 1. Enthalpy of Formation Contributions of Acrylonitrile, Butadiene, and Styrene Copolymers in a 50%/43%/07% ABS Formulation

monomer
KJ / g mol

Q
polymerization
KJ / g mol

Acrylonitrile

172.6218

Butadiene

104.10(Ref.

Monomer

H 0f

H 0f

ABS Mole

Enthalpy
Contribution
KJ / g mol

polymer
KJ / g mol

fraction

74.3119

98.31

0.43

42.27

72.10 20

32.00

0.50

16.00

84.60(Ref. 19)

63.31

0.07

4.36

11)

Styrene

146.9121

ABS Total

62.63

F. Thermodynamic and Transport Properties for ABS/N2O Combustion

The value of H0f

ABS

calculated in Table 1 and corresponding chemical formula Eq. (10),

were input to CEA to calculate the thermodynamic and transport properties of the combustion by
products as a function of combustion pressure and O/F ratio. Calculated parameters include T0, ,
MW, c*, , and Pr. Figure 4 plots these ABS/N2O Combustion properties as function of O/F ratio
and combustion pressure. When these graphs are compared against the corresponding HTPBbased figures (Figure 2), two key features stand out: 1) the predicted c* is lower by slightly less
than 1%, and 2) peak c*values tend to occur at O/F ratios between 4.0 and 5.5. This optimal
point is significantly lower than the corresponding HTPB O/F optimal values that lie between
5.0-6.0. Slightly lower ABS-motor oxidizer flow levels should produce equivalent performance
when compared to the HTPB-motor.

16

Figure 4. Thermodynamic and Transport Properties of N2O/ABS Combustion Products.

III.

End to End Motor Performance Modeling

The motor models to be described here will be compared against motor burn data from staticfire tests to be described later in the Experimental Results and Discussion section. The motor
modeling equations are based on the enthalpy-balance regression rate model developed by Ref.
8, adjusted for non-unity combustion product Prandtl number. Assuming the nozzle throat
chokes immediately, as the propellant burns the generated gases cannot escape as fast as they are
produced and pressure within the fuel chamber builds. A balance between the gases coming into
the fuel port and the gases leaving through the choked throat calculates the time response of this
chamber pressure growth. Here the equation that describes the time evolution of the chamber
pressure is

17

( +1 &
$
!P0 Aburn r!
) 2 , ( #1 0 Rg T0
/ A*
$ " R T # P0 & # P0 /
=
( Rg T0 +
A C
2 "ox (Pox # P0 )
0+
'
!t
Vc % fuel g 0
* ( + 1.- 0 Vc ox dox
/ Vc
%
'
.

(11)

The oxidizer mass flow rate is modeled by the incompressible discharge coefficient formula
m! ox = Aox Cd

ox

2 !ox ( pox " p0 )

(12)

Equation (12) is reasonably accurate as long as the motor is burned using a top pressure that is
higher than the saturation pressure of the N2O at the injector temperature. For blow down
systems that use only the natural vapor pressure of the propellant, a more complicated two-phase
model is required to accurately model the injector mass flow22. The fuel grain mass flow is
modeled as
m! fuel = Aburn ! " fuel ! r!

(13)

where r is the linear fuel regression rate and fuel is the material density of the solid fuel grain.
The O/F ratio of the burning propellant, which varies significantly throughout the burn, is given
by

O/F =

Aox Cd 2 !ox ( pox " p0 )

m! ox
ox
=
m! fuel
Aburn # ! fuel # r!

(14)

Modeling the mixture ratio in this form allows for calculation of combustion product properties
at every time step using a table lookup of the equilibrium exhaust gas properties depicted in
Figure 2 and Figure 4. The crux of the hybrid motor model used here is the fuel grain regression
rate equation, corrected by Ref. (22) for non-unity Prandtl number

18

0.047 ( c p $%T0 # Tfuel &' +

r! =
*
hv
!fuel " Pr 0.153 )
,

0.23

$ Aox Cd
ox
.
A
.%
c

&5 ( + 5
2 !ox (Pox # P0 ) / * /' ) L ,

(15)

In Eq. (15) the parameters and Pr refer to the combustion product gas properties, the
parameters Pox and ox refer to the oxidizer liquid properties upstream of the injector, and cp, fuel,
Tfuel, and hv refer to the properties of the solid fuel grain.
Equations (11) through (15) are continuously integrated to calculate the chamber conditions,
and at each time frame the chamber properties are used with standard one-dimensional onedimensional De-Laval flow formulae23 to calculate the end-to-end rocket performance
parameters. Calculate parameters include thrust, exit properties, specific impulse, and choking
mass flow. Adjustments are made for non-zero nozzle exit angles, and heat loss within the
combustor. Nozzle throat dimensions are allowed to erode at prescribed rates.
IV.

Experimental Setup for HTPB and ABS Fuel Grain Static Fire Tests

A primary emphasis of this project was the experimental evaluation of ABS as a hybrid fuel
grain, and comparison of its performance relative to geometrically identical fuel grains cast from
HTPB. Multiple, identically-cast HTPB, and DDM-manufactured ABS fuel grains were static
fired in a test cell housed on the Utah State University campus. This section details the hybrid
motor case design and assembly, fuel grain fabrication methods, test cell instrumentation, and
test procedures. Tests results and model comparisons will be presented later in the results and
discussion section.
G. Motor Case, Injector, Nozzle, and Ignitor Assembly

19

For these tests a commercially available 98-mm solid-rocket motor24 was modified by
replacing the original ejection charge on the motor cap with a single port oxidizer injector. A
threaded pressure transducer was also installed in the modified motor injector cap. To reduce
run-to-run variability due to nozzle erosion, graphite nozzles fabricated from a single piece of
graphite replaced the original manufacturer-supplied phenolic nozzle. The nozzle was designed
to have a 4.2:1 expansion ratio and had a design throat diameter of 1.7 cm. Figure 5 shows the
original Cesaroni solid-rocket 98-mm motor case adapted for these hybrid motor tests.
Additional advantages of this configuration are a ready-made flight-weight motor and the
ability to rapidly reload between motor tests. Table 2 summarizes the mean motor and fuel grain
dimensions and mass properties.

Figure 5: Cesaroni Pro-98 Motor Case Adapted for Hybrid-Motor Tests.

Two small Estes-class 10-gram solid rocket ignition motors were inserted into the injector
cap. Electronic matches burned by a 12 volt DC signal ignited these small motors. The motors
and e-matches were replaced after each test firing. Figure 6 shows photographic images of the
nozzle assembly, injector/motor cap assembly, and the injector port, ignition motors, and
electronic-matches.

20

Table 2. Motor Case and Fuel Grain Dimensions.

Motor

Length,

Diameter, Nozzle

Nozzle

Nozzle

Injector

Nozzle

mm

mm

Throat

Throat

Expansion

Exit

Discharge

Area, A*,

Area, Aexit

Ratio**

Area,

Coefficient,

cm2

cm2

cm2

Cd ox

2.21

9.27

4.2

0.115

0.40

Heat of

Initial

Fuel Grain

98

702

Fuel

Length,

Diameter, Initial

Post

Grain

cm

cm

Port

Combustion Ablation /

Fuel

Material

Area, A*,

Chamber

Gasification,

Grain

Density,

cm2

Volume,

h, MJ/kg

Mass, kg

kg/m3

Case

cm3
HTPB

571.5

82.6

5.07

31.95

1.825

2.55

930.0

ABS

571.5

82.6

5.07

31.95

2.326

2.67

975.0

**

Based on the expected chamber pressure, this expansion ratio was optimized for the altitude of the test site, Logan Utah. Logan
has an altitude of approximately 1.47 km above mean sea level.

21

Figure 6. Nozzle and Motor Cap Assembly.

H. ABS Fuel Grain Fabrication and Test Grain Geometry
Multiple cylindrical ABS fuel grains were fabricated using a Stratasys Fortus27 FusedDeposition Modeling (FDM) system. Typically, these systems are used for 3-dimensional
modeling and rapid-prototyping. The Stratsys FDM systems use production-grade thermoplastic
materials that are sufficiently rugged for functional testing and end-use parts. Real production
thermoplastics are stable and have no appreciable warping, shrinkage, or moisture absorption.
The ABS stock material, Stratasys ABS-M30 thermoplastic, used for these tests approximately
the 50:43:7 chemical formulation presented earlier in Section II.F. The mean density of the ABS

22

stock material used for these test was approximately 975 kg/m3. This density was considered to
be sufficient to insure structural integrity of the fuel grain during the static test firings.
The fuel grain was fabricated to fit snugly into the motor case described in the previous
section. A post combustion chamber was pre-manufactured into the fuel grain. Each fuel grain
was approximately 57.15 cm in length, 8.26 cm in diameter, the initial fuel port diameter was
2.54 cm, and post combustion chambers were 5.66 cm in diameter and 1.27 cm deep. The mean
fuel grain weight was approximately 2.67 kg. To reduce the chances of initiating erosive
burning, the injector port was designed to protrude approximately 1 cm into the top of the fuel
grain port. Each fuel grain was bonded into a cardboard sleeve using high temperature silicone
adhesive. This sleeve is then inserted into a phonelic insulating liner, and then into the aluminum
motor casing. The nozzle and motor cap assemblies are seated with O-rings. The aluminum
motor case acts as the pressure vessel for the motor. Figure 7 presents the fuel images showing
the grain features with the major dimensions labeled.

Figure 7. ABS Fuel Grain Images with Dimensions.

I. HTPB Fuel Grain Fabrication and Test Geometry

23

As mentioned earlier in section II.C HTPB fuel grains were cast using the commercially
available Arco R45M polybutadiene resin and PAPI 94 MDI curative. Arco R45M is
polybutadiene diol manufactured by the Sinclair Petrochemicals Arco Division. The resin has a
polymerization factor of approximately 50 and a molecular weight of 2734 kg/kg-mol. PAPI 94
is a polymethylene polyphenylisocyanate produced by Dow Plastics Inc. The formulation
contains methylene diphenylene diisocyanate (MDI) in proprietary proportions. The curative has
an average molecular weight of 290 kg/kg-mol. The nitrogen, carbon, oxygen (N-C-O) bonds in
the MDI react with the hydroxyl (OH) terminations in the polybutadiene resin to cure the fuel
grain. For these tests activated charcoal was added to the mixture to insure opaqueness and
prevent radiative heating of the fuel grain and motor case liners. HTPB/MDI/charcoal mass
proportions were set at 87%/12.5%/0.5%, respectively. Past experience has determined that these
proportions assure adequate fuel grain cure and material hardness.28
The resin and curative were mixed in a commercial paint mixer that was sealed and fitted so
that the fuel mixture could be placed under a vacuum during the mixing process. A commercial
H-VAC vacuum pump was used to remove gas bubbles created in the fuel grain during the
mixing process. The de-gassed mixture was cast in the same cardboard sleeves used for the ABS
fuel grains with a 2.54 cm (1) polyvinyl chloride (PVC) pipe used as mandrel. Before casting
the mandrel was coated with a mold release agent to insure proper release after the fuel grain
cured. The HTPB fuel grain dimensions, including the post combustion chamber were identical
to the previously described ABS fuel grains. The mean density of the ABS stock material used
for these test was approximately 930 kg/m3, and the cast fuel grains had a mean mass of 2.55 kg.
After casting the fuel grain were heat cured and the hardness was continuously monitored
through out the cure process. The HTPB fuel grains took as much as 15 days to reach their final

24

hardness levels before static testing. Figure 8 presents cure hardness data for a traditionally
cast HTPB fuel grain to support this assertion. Here measured Shoredurometer hardness29
units are plotted in curing days. After 3 1/2 days, the material has reached only 50% of its final
hardness; and even after 12 days, the grain is still only 90% of its fully-cured hardness. Burning
a polymeric fuel grain before it fully cures can produce unpredictable ablation rates, and may
cause significant erosive burning. Erosive burning produces chaotic pitting and channeling along
the length of the fuel grain, and poses a significant potential hazard to the structural integrity of
the motor.

Figure 8. HTPB Fuel Grain Hardness as a Function of Cure Time.

J. Test Cell Apparatus and Instrumentation
As mentioned earlier, an existing test cell at Utah State University was used to perform the
motor characterization tests. Measurements obtained include chamber pressure, thrust, total
impulse, motor case temperatures, specific impulse, mass flow rate, consumed propellant mass,
and propellant regression rate. Following each motor test, the fuel grain were dissected and
visually inspected for erosive burning and structural failure. Representative fuel grain images

Arco Poly BD R-45 HT resin (87%), 12.5% Dow PAPI 94 polyethylene polyphenylisocyanate curative, 0.5% activated
charcoal powder. Data collected April 5-25 2011.

25

will be presented later in the Results and Discussion section. All tests results will be compared to
analytical predictions for the specific motor fuel grain materials in that section.
1. Hybrid Test Stand Oxidizer Delivery System
To allow sufficient mass flow rates with minimal line losses, a predetermined mass of N2O
Oxidizer was delivered to a closely coupled run tank from a series of K sized industrial
pressure cylinders. The run tank was pressurized by gaseous nitrogen (N2) to insure a constant
injector pressure during the entire length of the burn. The N2 top pressure was set by a manual
regulator; and was typically maintained near 5200 kPa (800 psi) for these tests. The top pressure
kept the N2O above saturation pressure for the entire run and insured a single-phase liquid flow
through the injector. The design motor chamber pressure was approximately 3440 kPa (500 psi),
The pneumatic run valve was triggered by an electronic relay, and was automatically controlled
by the instrumentation software. Oxidizer mass flow was sensed by vertical load cells mounted
on the run tank, and by an inline Venturi flow meter mounted in the oxidizer feed-line just ahead
of the injector. Figure 9 shows the piping and instrumentation diagram (P&ID) for the hybrid
motor test arrangement.

26

Figure 9. Oxidizer Piping and Instrumentation Diagram (P&ID) for Hybrid Motor Tests.
2. Hybrid Test Stand Thrust Balance
The 6-degree of freedom (6-DOF) thrust stand developed and modified for this project
provided real-time vertical (motor mass) and axial load (thrust) measurements. Originally a total
of 6 load cells were installed on ball-joint mounts to reduce axial cross coupling. The 6-load cells
allowed all load paths to be identified. For this series of tests only the axial and vertical loads
were of primary interest. To reduce vibration during the static load tests, the lateral load cells
were replaced with support rods mounted on ball shafts. The axial load was sensed by an
Omegadyne LCCD-500 (2225 Nt) load cell, and the vertical loads were sensed by two
Omegadyne LCCA-25 (110 Nt) load cells. The output response for these sensors is 3 mV/Volt,
and the sensors were excited using a 12-volt DC power source. Chamber pressure was sensed
using an MSI-600 (0-6900 kPa) absolute threaded pressure transducer mounted in the motor

27

cap (Figure 6). Omegadyne Type-K thermocouples were mounted at the aft-end of the motor
case to sense burn temperature and thermal soak-back following the end of the burn. Relevant
manufacturer's specifications including operating range and accuracy for each of these
instruments is listed in Table 2.
Table 3. Manufacturer Specifications for Static Thrust Stand Instruments
Instrument Model

Operating Range

Accuracy

LCCA-25

+25 lbf (110 N)

+0.037% of Full Scale

+500 lbf (2225 N)

+0.25% of Full Scale

(Lateral Loads)
LCCD-500
(Axial Loads)
MSI-600

0-1000 Psia (0-6900 kPa) +0.1% of Full Scale

(Chamber Pressure)
Two National Instruments data acquisition and control devices managed motor fire control,
and logged test data. An NI-compact DAQ 4-slot bus controller with multiple analog input (16bit), analog output, digital output, and thermocouple modules (24-bit) bus-cards managed the
majority of the measurements and valve control. The digital outputs from a separate NI USB6009 module were used to trigger the relays that fired the ignitor e-matches. Operators and
experimenters were remotely located in a secure control room separated from the test area.
Communications to the test stand were managed by an operator-controlled laptop via universal
serial bus (USB) using amplified extension cables. All control and measurement functions were
controlled by a LABview program hosted on the control laptop. Figure 10 shows a schematic
of the test stand, and an image of the motor being fired.

28

Figure 10. Static Test Mechanical and Instrumentation Schematic.

V.

Results and Discussion

As mentioned earlier in the introduction to Section IV, multiple, identically-cast HTPB, and
DDM-manufactured ABS fuel grains were static fired to compare the relative performances of
the two different fuel grain types. To date 20 successful separate static-tests including 6 ABS and
14 HTP fuel grains have been performed. The data from several of these tests has been
discounted due to known instrumentation, software, and test apparatus difficulties. Burn Profiles
from representative tests for both the HTPB and ABS fuel grains will be presented here. Postburn fuel grain images and total-fuel linear-regression data will be presented for all of the good
motor burns. Finally, test results will be compared to model predictions.
K. Thrust-Stand Time History Data
Figure 11 presents side-by-side comparisons of time-history data collected from 4representative HTPB and ABS static firings. The presented time history profiles include thrust,

29

accumulated impulse, injector and chamber pressures, and oxidizer mass flow (as measured by
the in-line Venturi system). Each of the HTPB fuel grain burns is approximately 10.25 seconds
in duration. For the ABS burns, both short (5.25 s) and long (10.25 s) burn profiles are presented.
Because there was a lot of initial uncertainty regarding the regression rates for the ABS fuel
grains; the initial ABS fuel burns were kept to a short duration to reduce the chances of motor
case burn through. Once visual inspection determined that the regression rates were sufficiently
slow to insure motor survival; the ABS burn times were lengthened to 10.25 seconds.
For each case the HTPB fuel grains exhibit a small, but well-defined net-advantage in overall
performance, including thrust, total impulse, and specific impulse. The mean steady state thrust
level for the HTPB grains is approximately 755.0 N, and 717.8 N for the ABS grains. This
difference represents an advantage of approximately 4.9% for the HTPB grains. The HTPB
grains have an effective ensemble mean specific impulse of approximately 204.1 s. This value is
approximately 6.6% higher than the mean for the ABS fuel grains (190.6 s). The effective
specific impulse is calculated by dividing the total impulse generated during the burn by the fuel
and oxidizer mass consumed,
I sp

effective

I total
g0 ! M fuel + M ox

).

(16)

The equivalent ensemble-mean vacuum specific impulse values are 225.7 s (HTPB) and 211.6 s
(ABS). The vacuum specific impulse calculation assumes nozzle exit area of 9.27 cm2, and an
ambient test pressure of 86 kPa.
It appears that the increased thrust for the HTPB fuel grains is not driven by a higher overall
mass-flow. The approximate oxidizer and fuel mass flow rates for the HTPB burns are 0.300 kg/s
(N2O), and 0.077 kg/s (HTPB) respectively. For the ABS burns the corresponding oxidizer and

30

fuel mass flow rates are 0.304 kg/s (N2O), and 0.086 kg/s (ABS) respectively. The corresponding
O/F ratios -- calculated by dividing the total consumed oxidizer mass by the total consumed fuel
mass are 4.19 for HTPB fuel grains and 3.75 for the ABS grains. Thus, the ABS fuel grains are
actually characterized by a slightly higher fuel mass burn rate. This comparison suggests that the
HTPB fuel grains burn at a higher flame temperature when compared to the ABS grains.
Calculating the characteristic velocity for the individual burns supports this assertion. Here the
characteristic velocity is approximated by

c* =

g0 ! I sp
CF

"P %
= g0 ! I sp ! A* $ 0 '
# F&

(17)

where P0 and F are the mean steady-state chamber pressure and thrust levels. The mean c* value
for the HTPB burns is approximately 1523.1 m/sec compared to 1488.7 m/sec for the ABS burns.
This difference is approximately 2.3%, or slightly less than 1/2 of the observed thrust difference.
The thrust and impulse data also demonstrate that the ABS fuel grain delivers a slightly
greater run-to-run consistency than do the HTPB fuel grains. The steady-state thrust standard
deviation for the ABS grains is approximately +17.2 N compared to +32.1 N for the HTPB
grains. Although not large, this improved run-to-run consistency is likely a positive benefit of
the FDM fabrication methods used to build the ABS grains. FDM is a precisely controlled by
robotic industrial process; as opposed to the labor intensive mixing, degassing, casting, and
curing process for the HTPB fuel grains. This consistency difference may also be a result of
HTPB being a thermo-setting material and ABS being a thermoplastic material. Unquestionably
this topic requires further research; but it appears that the digital manufacturing methods
demonstrate the potential for enhanced consistency in the fuel grain fabrication process. Table 4
summarizes the individual and ensemble results for the HTPB and ABS burn tests.

31

Figure 11. Burn Time History Comparisons for HTPB and ABS Hybrid Motors.

32

Table 4. HTPB and ABS Motor Burn Summary.

HTPB

Steady

Total

Consumed

Effective

Mean

Grain

Burn

Impulse,

Mass, kg

Isp, s

Steady

Burns

Time, s

Itotal, N-s

O/F Ratio

8747.4

Oxidizer:

VarHTPB4 10.25

c*, m/s

Thrust, N
211.4

787.7

1495.6

202.1

766.2

1488.3

199.5

732.3

1541.0

203.4

725.8

1567.3

Isp: 204.1

F: 753.0

c : 1523.1

Isp: 5.12

F: 32.09

c : 37.52

3.614
Fuel:0.80
O/F: 4.27
VarHTPB5 10.25

8294.6

Oxidizer:
3.392
Fuel:0.794
O/F: 4.27

VarHTPB6 10.25

8011.1

Oxidizer:
3.299
Fuel:0.795
O/F: 4.15

VarHTPB7 10.25

7955.2

Oxidizer:
3.211
Fuel:0.787
O/F: 4.07

HTPB Performance Mean and Standard Deviation

33

HTPB

Steady

Total

Consumed

Effective

Mean

Grain

Burn

Impulse,

Mass, kg

Isp, s

Steady

Burns

Time,

Itotal, N-s

sec
VarABS2

5.25

c*, m/s

Thrust, N
O/F Ratio

4289.1

Oxidizer:

193.4

733.2

1564.1

183.0

694.8

1497.5

187.2

714.7

1353.8

198.9

728.5

1539.4

Isp: 190.6

F: 717.8

c : 1488.7

Isp: 6.99

F: 17.2

c : 94.08

1.802
Fuel:0.480
O/F: 3.71
VarABS3

5.25

7532.0

Oxidizer:
1.801
Fuel:0.811
O/F: 4.18

VarABS4

10.25

7814.7

Oxidizer:
3.387
Fuel:0.854
O/F: 3.98

VarABS5

10.25

4431.9

Oxidizer:
3.443
Fuel:0.549
O/F: 3.14

ABS Performance Mean \and Standard Deviation

34

L. Comparison to Model Predictions

As presented above, a likely candidate justifying the higher overall HTPB thrust and specific
impulse appears to result from the c* efficiency of the combustion process. Defining the
combustion efficiency as

!* =

c*actual
c*ideal ,

(18)

the combustion efficiency of the hybrid model, Eqs. (11) through (15), was adjusted until the
predicted thrust and chamber pressure values matched the measured values. This procedure
determined that the HTPB fuel grains tend to an * efficiency near 95%, whereas the ABS fuel
grains have an * efficiency below 90%. Figure 12 presents model/static test comparisons to
support this conclusion. Here the thrust profiles from Figure 11 are overlaid against model
predictions for *=(100% and 92%) for the HTPB motor (Fig. 12a), and *=(100% and 86%) for
the ABS motor (Fig. 12b). The corresponding predicted c* profiles are plotted in Fig. 12c
(HTPB), and Fig. 12d (ABS). This efficiency difference is approximately 9.5%, and although
higher than the c* differences calculated earlier; still suggests that the ABS grains tested did not
burn as efficiently as the HTPB grains.

35

Figure 12 Model/Static Test Comparisons to for HTPB and ABS Hybrid Motors.
M. Fuel Grain Regression Measurements
The results and conclusions presented on Figure 11 and Figure 12, are further supported by
post-burn fuel grain regression measurements. Both the HTPB and ABS burned grains burned in
a linear manner, and no erosive burn patterns were noted. Following the end of each static test,
the motor was quenched and then split longitudinally to expose the burned grain pattern. The
final regression dimensions were measured at multiple points along the fuel grain; and the mean
end-to-end longitudinal fuel linear regression was calculated. Figure 13 shows side-by-side
comparisons of post-burn HTPB and ABS fuel grains. The regression measurement stations are
marked on each grain. For both the HTPB and ABS grains, fossilized surface flow patterns are
visible, and the transitions from laminar to turbulent flow patterns can be clearly seen. The burn
patterns are very similar with the ABS fuel grain showing an incipient erosion pattern just

36

downstream of the injector, and a slightly asymmetrical final burn profile (Fig. 13 b). For both
fuel grains the burn time was slightly longer than 10 seconds.

Figure 13 Burned HTPB and ABS Fuel Grains.

Figure 14 compares the longitudinal-mean regression measurements for all of the HTPB and
ABS burns against model predictions. Fig. 14a plots the total longitudinally averaged linear
regression against burn time. Dividing the total regression by the steady burn time approximates
the mean linear regression rate for each fuel grain. Fig. 14b plots the linear regression rate
against the mean port diameter. For the measured regression data, the mean port diameter is
approximated by the average of the initial and final fuel port diameters. The models show
reasonable agreement with the measured data, and the HTPB fuel grains are clearly demonstrated
to exhibit a faster overall linear burn rate when compared to ABS grains. These test results
directly supports the earlier data presented in Figs. 11 and 12. Even though the ABS formulation
has a greater material density, it simply does not burn as energetically as does the HTPB mixture.

37

As described earlier lower burn rate is likely a result of lower overall combustion efficiency for
the current ABS grain furmulation.

Figure 14. Predicted and Measured Linear Regression for HTPB and ABS Grains.
N. Heat of Combustion Calorimetric Measurements for the HTPB and ABS Fuel Grains.
A final series of tests were performed to add supporting data for the conclusions reached in
the previous sections. This section presents results from oxygen bomb calorimetry measurements
performed on sections of post-burn fuel HTPB and ABS fuel grains. Combustion with oxygen in
a sealed bomb is a very effective and reliable method for releasing all heat energy obtainable
from a sample, and the authors believe that these results verify the higher overall energy content
of the HTPB grain formulation when compared with the 50:43:7 ABS formulation evaluated in
these tests.
In this series of tests, a Parr model 1241 Oxygen Bomb Adiabatic Calorimeter was used to
burn multiple fuel samples selected at random from the burned fuel grains. The gross heat of
combustion was measured according to procedures outlined in ASTM D2382-8830. Table 5
summarizes these test results. The measured gross heats of combustion for HTPB and ABS agree
well with published values (Ref. 10). The approximately 5% higher heat of combustion for

Parr Instrument Co., Moline, Illinois

38

HTPB agrees well with the previously established performance and regression rate advantages.
Table 5. Oxygen Bomb Calorimetry Measurements for HTPB and ABS Fuel Grains.
Wire

Initial

Final

Consumed

Heat of

Weight,

Length,

Bomb

Bomb

Wire

Combustion,

Sample Grain

cm

Temp, C

Temp, C

Length, cm

Qc, kJ/kg

HTPB

0.307

15.24

22.255

23.551

6.99

42.36

HTPB

0.301

15.24

22.396

23.664

5.08

42.30

HTPB

0.283

15.24

22.273

23.465

7.37

42.25

HTPB

0.28

15.24

23.03

24.22

5.08

42.67

HTPB

0.48

15.24

22.07

24.16

5.08

43.64

Fuel

Qc = 42.64 kJ/kg

ABS Fuel Grain Combustion Statistics:

Qc =0.58 kJ/kg

Wire

Initial

Final

Consumed

Heat of

Weight,

Length,

Bomb

Bomb

Wire

Combustion,

Sample Grain

cm

Temp, C

Temp, C

Length, cm

Qc, kJ/kg

ABS

15.24

15.24

22.54

23.80

7.62

39.38

ABS

0.32

15.24

22.42

23.70

10.80

39.47

ABS

0.30

15.24

23.06

24.24

8.89

39.70

ABS

0.31

15.24

22.68

23.92

10.16

39.71

ABS

0.31

15.24

22.68

23.92

10.16

39.74

Fuel

ABS Fuel Grain Combustion Statistics:

Qc = 39.60 kJ/kg

39

 Qc =0.16 kJ/kg

O. Effect of Dissolved gaseous Nitrogen in the Nitrous Oxidizer Storage Tanks

The authors believe that the relatively low overall Isp and c* values for both HTPB and ABS
fuel grains, as presented in
Table 4 and Figure 12, indicate a dilution of the nitrous oxide storage tanks by the gaseous N2
used to pressurize the system. It is believed that during system verification and cold flow tests,
gaseous nitrogen from the pressurizing tanks (Item 1, Figure 9) was forced into the nitrous oxide
storage tanks (Item 2, Figure 9) during the process of supercharging and filling the oxidizer run
tanks (Item 6, Figure 9). This nitrogen gas became dissolved in the stored nitrous oxide.
To support this premise, CEA-based calculations were performed assuming that the
oxidizer consisted of 80% N2O and 20% N2 by mass. Figure 15 presents these results. Here the
c* values for the original propellant mixture (Figs. a, c) are compared to the c* values with a 20%
N2 dilution of the oxidizer. Clearly, there exists a significant impact on the propellant c*. The
peak O/F ratio is shifted to a much leaner value, and the maximum c* value drops by more
than 5% for both the HTPB and ABS calculations.

40

Figure 15. Effect of 20% Dissolved N2 in N2O Oxidizer on c*.

When the nitrous oxide storage tanks were replaced with a freshly-charged set of tanks. The
overall performances for both fuel grains improved dramatically. Figure 16 presents this result.
Here the model/static thrust comparisons of Figure 12 are repeated, but with the static thrust data
obtained using the fresh nitrous oxide tanks replacing the original data. The mean steady thrust
level for the HTPB motor has now increased from the original mean value of 755.0 N to 823.9 N.
The corresponding test and vacuum specific impulses have increased to 222.7 s and 244.3 s,
respectively. The combustion efficiency now begins to approach 100% of the theoretical value.
In a similar manner, the mean steady thrust level for the ABS motor has now increased from

41

717.8 N to 783.5 N, and the corresponding test and vacuum specific impulses have increased to
208.1 s and 229.2 s, respectively. The effective * for the ABS fuel grain has now increased to
approximately 95%. For the test cases presented in Figure 16, the HTPB motor still exhibits a
slight advantage compared to the ABS motor; with the new difference barely changing at 4.9%
for 6.2% for Isp, respectively.

Figure 16. Model/Static Test Comparisons to for HTPB and ABS Hybrid Motors with
Recharged N2O Tanks.
At the time of the writing of this report additional HTPB fuel grains have been cast and tested
using the recharged nitrous oxide tanks. The performance gains presented Figure 16 in have been
consistently observed in these follow-on tests. Additional ABS fuel grains are being fabricated
and will be tested as they become available. Test procedures to prevent the issue with nitrogen
gas dilution of the oxidizer storage tanks have been put in place to avoid this issue in future tests.
P. ABS Fuel grain Monomer Ratio Optimization
As the data presented for the earlier 50:43:7 butadiene/acrylonitrile/styrene monomer molefraction demonstrate; the energy content of this ABS formulation is slightly, but consistently
lower than the R-45m HTPB formulation. This final section examines the individual ABS

42

monomer mole fraction ratios to search for an optimal formulation. The mole-fractions of each
polymer were varied from 0 to 100% of the constituents of the polymer, such that the total
makeup of each of the formulations equals 100%. For example, if the first component was 50%
of the total constituency, the other two components were varied so that the sums of their mole
fractions totaled the other 50%. The group addition method was used to calculate Hf0 for the
various ABS polymerizations; and this data along with the corresponding molecular formulae,
was input into the CEA program for various oxidizer-to-fuel (O/F) ratios and combustion
pressures. The resulting values for the equilibrium species concentrations, thermodynamic
properties, and transport properties were used to calculate the propellants characteristic velocity
for each of the possible monomer combinations. The monomer ratios producing the higher c*
values give the more desirable propellant combinations.
Figure 17 plots the characteristic velocity for ABS/N2O combustion at 2500 kPa chamber
pressure as a function of butadiene mole fraction for various remaining acrylonitrile/styrene
(A/S) ratios. Calculations for different mixture ratios O/F=4.5 and O/F=6.0 -- are presented.
Clearly, for the lower O/F ratio (4.5), there exists an optimal butadiene content that peaks near a
30% total mole fraction and 90% A/S ratio. For lower A/S ratios this optimal point diminishes. In
contrast, for the higher O/F ratio (6.0) there is no optimal point, and increasing butadiene content
always leads to a better performing propellant. For the higher O/F ratio the propellant
performance is more or less independent of A/S ratio. For a 2500 kPa operating chamber pressure
and an O/F ratio of 6.0, 70% butadiene content results in a c* value 1618 m/sec, that exceeds the
HTPB c* value 1608 m/sec for the same operating pressure and O/F ratio (Fig. Figure 2). At this
juncture in the research, it is unclear what allowable fraction of butadiene will retain adequate
structural integrity for the fuel grain material. This analysis suggests that future preparations of

43

ABS may be better optimized for hybrid propellant performance; but also the mixture that
produces best results is closely coupled with the operating O/F ratio of the motor.

Figure 17. Effect on ABS Monomer Mole-Fractions on Combustion Performance.

VI.

Conclusion

A primary objective of this work was to investigate the viability of Acrylonitrilebutadienestyrene (ABS) as a hybrid rocket fuel material. ABS is an inexpensive thermoplastic that can be
easily produced in wide variety of shapes. ABS plastics are readily shaped into complex

44

geometries using Direct Digital manufacturing Techniques. Leveraging the recent rapid
capability growth in factory automation and robotics, Direct-Digital Manufacturing (DDM)
offers the potential to revolutionize methods used to fabricate hybrid rocket fuel grains. DDM
technology can support high production rates with a much greater degree of motor-to-motor
consistency than is possible using traditional one-off motor casting methods. Once matured
and commercialized, this technology will have a transformational effect on hybrid rocket motor
production by improving quality, consistency, and performance, while reducing development
and production costs. If demonstrated to be thermodynamically competitive with HydroxylTerminated Polybutadiene (HTPB), ABS presents a very attractive hybrid rocket fuel option.
The performance of ABS thermoplastic is compared to HTPB with Nitrous Oxide (N2O) as
the matching oxidizer. Multiple ABS grains were DDM-fabricated from existing ABS stock
materials composed of 50:43:7 butadiene, acrylonitrile, and styrene mole fractions. These grains
were static-tested and compared against traditionally cast HTPB grains of equal physical volume
and dimension. Both the HTPB and ABS grains burned in a linear manner, and no erosive burn
patterns were noted. Test results demonstrate a higher burn-to-burn consistency for ABS fuel
grains, but slightly reduced performance. For the original series of tests the hand-cast HTPB
grains exhibited approximately 4.9% greater steady thrust and 6.6% higher effective specific
impulse. End-to-end linear regression rate and bomb calorimetry measurements of the heats of
combustion support the static-fire burn performance data. In all cases the ABS formulation does
not regress as rapidly or burn with as much heat as does the HTPB material. Possible sources of
this inefficiency could be the higher heat of gasification for ABS, and a higher enthalpy of
formation for the stock ABS materials tested.

45

The authors believe that the relatively low overall Isp and c* values for both HTPB and ABS
fuel grains indicate a dilution of the nitrous oxide storage tanks by the gaseous N2 used to
pressurize the system. When the nitrous oxide storage tanks were replaced with a freshly charged
set of tanks, the overall performances for both fuel grains improved dramatically. With the
recharged tanks the performance margin between the HTOB and ABS fuel grains remained
essentially unchanged. At the time of the writing of this report additional HTPB fuel grains have
been cast and tested using the recharged nitrous oxide tanks. The performance gains with
recharged oxidizer tanks been consistently observed in these follow-on tests. Additional ABS
fuel grains are being fabricated and will be tested as they become available. Test procedures to
prevent the issue with nitrogen gas dilution of the oxidizer storage tanks have been put in place
to avoid this issue in future tests. Furthermore, nitrogen has been replaced by helium as the
pressurizing fluid.
This study concludes with an examination of the effects of relative monomer compositions for
the ABS fuel grains. This final section examines the individual ABS monomer mole fraction
ratios to search for an optimal formulation. Calculations for different mixture ratios were
presented. For the lower O/F ratio (4.5) there exists an optimal butadiene content that peaks near
a 30% total mole fraction and 90% A/S ratio. For the higher O/F ratio (6.0) there is no optimal
point, and increasing butadiene content always leads to a better performing propellant. For the
higher O/F ratio, 70% butadiene content results in an ABS c* that exceeds the HTPB c* for the
same operating pressure and O/F ratio. At this juncture in the research, it is unclear what
allowable fraction of butadiene will retain adequate structural integrity for the fuel grain
material. This analysis suggests that future preparations of ABS may be better optimized for
hybrid propellant performance; but also the mixture that produces best results is closely coupled

46

with the operating O/F ratio of the motor. In all cases the viability of industrially produced ABS
fuel grains has been clearly proven. Future studies will emphasize methods for increasing the
burn efficiency of the ABS fuel material formulation.
Acknowledgments

This work was partially funded under a grant from the Utah Governors Office of Economic
Development Technology Commercialization and Innovation Program (TCIP). Additional
funding was received from the NASA Experimental Program for Stimulating Competitive
Research (EPSCOR). The authors want to thank teaming partner Avridyne Technologies/Rocket
Crafters, Inc of Layton Utah for procuring the ABS fuel grains from Stratus, Inc.
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