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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.

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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

A

=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

B

= free energy of formation curve fit slope parameter

C

= 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

2

F

= steady state thrust, N

g0

= standard acceleration of gravity, 9.8067 m/sec2

H

=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

N

= degree of polymerization

N2

= gaseous nitrogen

N2O

= nitrous oxide

n

= generic mole fraction

na

= acrylonitrile mole fraction

nb,

= butadiene mole fraction

ns

= styrene mole fraction

3

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

T

= combustion temperature, K

T0

= adiabatic flame temperature, K

Vc

= combustion chamber internal volume, cm3

ΔG

= Gibbs free energy of formation, kJ/mol

∆G◦gg

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

∆G◦mono =Gibbs free energy for monomer, kJ/mol
!G 0 la

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

∆G◦poly

=Gibbs free energy for polymer, kJ/mol

ΔH

= mole specific enthalpy change, kJ/mol

ΔHf0

= standard enthalpy of formation, kJ/mol

ΔQc

= heat of combustion, kJ/mol

ΔS

=mole specific entropy change, kJ/mol-K

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Approximately 70% of catastrophic space-launch failures are attributable to the vehicle’s power plant. kg/m3 σ = sample standard deviation L I. Introduction ESS risky launch vehicles must be developed to operational readiness for commercial spaceflight to become a viable market. kg/m3 ρox = liquid oxidizer density.550 sorties per motor.S. A key to commercial spaceflight success is the cost- efficient and safe operation of large rocket motors in civilian environments. According to the U. 5 .1 NASA estimates that the Space Shuttle’s liquid fueled main engines will fail catastrophically once every 1530 sorties per engine and its solid rocket boosters will fail catastrophically once every 1.!* = combustion efficiency γ = ratio of specific heats or combustion products µ = dynamic viscosity. Because of the extreme risk and potentially negative environmental impact. Nt-s/m2 µ = sample mean ρfuel = solid fuel grain material density. The inherent safety of hybrid rocket motors greatly reduces the operational risk to a launch vehicle or any hybrid rocket propelled missile or spacecraft. Department of Transportation. Hybrid motors have the potential to fulfill this low-risk flight requirement. it is unacceptable for a potential commercial spaceflight operator. large solid-propelled rocket motors simply cannot be operated at civilian airports. While this level of risk is acceptable for experimental and government-operated vehicles.

restarted. but have seen little commercial application mainly due to difficulty associated with of mass-producing fuel grains. commercial spaceflight operations. oxidizer valve/injectors. to be later manually assembled with other motor components (i. Leveraging the recent rapid capability growth in factory automation and robotics. Motor–tomotor response times. peak thrust. and relative insusceptibility to grain flaws. post-combustion chamber.2 Other advantages of hybrid rockets include the ability to be stopped. The current production method involves casting viscous or non-polymerized material “by hand” in a casing mold to form the fuel grain. This high degree of motor-to-motor variability may be acceptable for experimental or government vehicles operated on a restricted-test range. igniter. Current Hybrid-Motor Manufacturing Limitations Hybrid rocket motors have been in development for more than two decades. and total impulse levels can vary significantly. Motor-to-motor performance consistency has also been a commercial disincentive. oxidizer tank. This low-tech approach results in market prohibitive production costs and a high degree of performance variability. Very little development effort has been directed towards manufacturing methods to support volume production. but will not secure FAA certification for non-experimental.e. and throttled. A. and rocket nozzle). easy (and hence potentially cheaper) ground handling. the current low-technology. DirectDigital Manufacturing (DDM)3 offers the potential to revolutionize methods used to fabricate 6 . 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. the majority of mainstream hybrid motor development has focused on performance characterization and improvement. Finally.hybrid motors can be stored and operated without possibility of explosion or detonation. To date..

either isocyanate or methylene diphenyl diisocyanate (MDI). If matured and commercialized. 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. 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.17 kJ/kg5. degassed under vacuum.as the relative degrees of polymerization and curative treatments for the mix are modified. HTPB burn properties can vary dramatically depending on the degree 7 . Hydroxyl-terminated polybutadiene (HTPB) is a legacy thermosetting polymer material frequently used as binder for solid rocket propellant grains.57 kJ/g-mol6 . while reducing development and production costs. cannot be shaped and manufactured using DDM methods. to -31. but instead chars and ablates. The enthalpies of formation of HTPB have been published. this technology will have a transformational effect on hybrid rocket motor production by improving quality. No industry standard value for the enthalpy of formation exists. The most commonly used hybrid rocket fuel. as a thermosetting polymeric material.88 kJ/g-mol4. but have not been evaluated as hybrid rocket fuels. but vary widely -. and performance. and 363. HTPB is a solid homopolymer made by combining two components: 1) a hydroxyl-terminated polymer of butadiene and 2) a cross-linking agent. and then cast and cured in a fuel grain mold. It remains the hybrid fuel grain material of choice primarily because of industry familiarity with its chemical and structural properties.from 64. consistency. II. HTPB must be mixed from its liquid base-components. HTPB does not melt in the presence of heat.hybrid rocket fuel grains. used to polymerize and set the material. HTPB.

4 billion kilograms of ABS material were produced chemical and petrochemical industries world wide in 20107. Both analytical predictions8. however. 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. This material is widely mass-produced for a variety of non-combustion applications including household plumbing.10 However. Alternatively. Analytical predictions include shifting-equilibrium chemistry effects. because ABS has not previously been purposely considered as a potential rocket fuel grain marterial. Typical cure times exceed 10 days to two weeks. More than 1. Acrylonitrilebutadiene-styrene (ABS) is an inexpensive thermoplastic that can be easily produced in wide variety of shapes. To date. ABS plastics are readily shaped into complex geometries using DDM techniques. This paper details the rocket-based combustion of ABS polymer variations with Nitrous Oxide (N2O). If ABS can be demonstrated to be thermodynamically and structurally competitive with HTPB. fuel regression rates.9 and experimental verifications will be presented. ΔHf0. and compares its performance against HTPB as a baseline. in the presence of oxygen has been documented for safety considerations. it would represent a very attractive option as a hybrid rocket fuel grain material. no detailed analysis of the performance of ABS as a rocket fuel has been performed. For this initial study. As with HTPB it is expected that the ABS enthalpy of 8 . there has been little to no work quantifying the material’s standard enthalpy of formation. simple cylindrical port grain configurations were modeled and tested. and the length of time the material has cured. and unsteady thrust and impulse predictions. the heat of combustion ΔQc. and structural materials.of residual gas seeding in the cast material. Because ABS is widely used as an industrial and domestic construction material.

(2) Inspecting Eqs. 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. and the slope corresponds to the standard entropy of formation. A and B are linear-fit constants. and T is the temperature of formation. with the form !G 0f group = A + B " T . 9 . 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. Van Krevelen’s method calculates the Gibbs free energy of formation ΔGf.formation will vary widely depending on the ratio of the various monomers that make up the ABS polymer. !G = !H " T # !S . (1) and (2) shows that the equation intercept is identical to the standard enthalpy of formation. In Eq. The group contribution to ΔGf is assumed as a linear function of temperature. B. (1) In Eq (1). Group Addition Method for Calculating the ΔHf0 of Polymers Because there are no reliable. (2) ΔS is the entropy change. industry standard values for the enthalpies of formation for both HTPB and ABS. this study employs a systematic approach for calculating ΔHf0 using the “Group Addition” methods developed by Van Krevelen and Chermin11.12. Using the fundamental definition for Gibbs free energy. and ΔH is the enthalpy of formation. of a polymer in a gaseous state by summing individual group contributions of common polymer-building molecular groups.

the method described in the previous paragraph was used to calculate the heat of formation of HTPB. !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. Reference 12 applies a correction to the Gibbs free energy of polymerization of the gaseous state. Thus. Because polymers do not exist in a gaseous state. 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 .The Gibbs free energy values given by Ref (11) are expressed for materials in a gaseous state. 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. C. (4) Inspecting equations (1). Calculating ΔHf0 for HTPB To verify applicability of the group addition process for rocket combustion. Thus the enthalpies of formation can be calculated directly from the presented data in Ref (11). a correction is performed to account for condensed states. and (4) shows that the Gibbs free-energy correction only affects the entropy of formation and not the enthalpy or formation. a large data based of performance data exists and can be used to verify 10 . (2). Since HTPB with Nitrous Oxide as the oxidizing agent is the most commonly used hybrid rocket propellant combination. 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.

The heat of formation for each butadiene molecule is calculated by 11 . The corresponding chemical formula is C200H302O2. The cis/trans structures have slightly different enthalpies of formation. a detailed calculation for HTB will be presented here. thus the moniker “hydroxyl terminated.” Figure 1 depicts the molecular structure of the bonded HTPB chain showing the polymerized trans/cis 1. Figure 1. As an introduction to the group addition method. The major constituent of HTPB. Chemical Structure of N=50 Polymerization of HTPB.4 butadiene units. ( !CH 2 ! CH = CH ! CH 2 ! ) . and the mean molecular weight is 2734 kg/kg-mol.the additive group calculations.4 butadiene has the chemical formula. however these differences are considered negligible compared to the overall heat of polymerization. and were neglected for this analysis. A common polymer formulation of HTPB (ARCO R-45M®13) has 50 repeating butadiene units with a hydroxyl radical at each end14. and the hydroxyl radicals attached to each end of the string. 1.

0385 (7) HTPB is (8) Using Eq.a value that is approximately 25.85% % .0385 ) ! (OH ) = C3. (7) and the molecular heat of formation is !H 0 f HTPB = nbutadiene " !H 0 fbutadiene + nOH " !H 0 fOH # & # & = ( 0.99 kJ g-mol The “reduced” chemical formula corresponding to the calculated value ΔH0f ( 0. (5) The heat of formation contribution of each hydroxyl group is !H 0f OH " #176 kJ g # mol .8077O0.8462 H 5. Each component’s mole fraction within the N=50 polymerization is ! nbutadiene $ ! 50 / 52 $ ! 96. (5).9615 ) " % 32 kJ ( + ( 0.5 kJ/kg -.# & 2 ! % "44 kJ ( $ g " mol ' 2 ! ( "CH 2 " ) 2 ! ( "CH = ) + 2 ! ( 76 kJ g " mol ) ________ Total )H f butadiene 32 kJ g " mol . (8) the corresponding heat of formation in mass units is calculated at 456.9615 ) ! (C4 H 6 ) + ( 0.15% $ # n &=# &=# & " OH % " 2 / 52 % " 3.0385 ) " % -176 kJ ( $ g-mol ' $ g-mol ' = 23. However. The ΔH0f presented by Eq. the curing agent represents a small fraction of the cured 12 .6% higher than that value reported by Ref. (7) neglects the chemical contributions of the curing agent used to polymerize and set the grain material.

Calculated parameters include adiabatic flame temperature T0. dynamic viscosity µ.0 and 6. Consequently. HTPB fuel-grain properties. Depending on the chamber pressure.0. ratio of specific heats γ.material – approximately than 12% by mass15 -. the CEA thermochemical database does not have an entry for and of the formulations of HTPB. (7). Thermodynamic and Transport Properties of HTPB/Nitrous Oxide Combustion The value for ΔH0f HTPB calculated by Eq. Unfortunately. 13 . At 7000 kPa chamber pressure (580 psia) the corresponding interpolated peak c* value is 1630 m/sec.and for the purposes of this discussion the effects on ΔH0f are considered to negligible. This 0. 4). (8) were directly input into the NASA program “Chemical Equilibrium with Applications. must be externally input to the program. including the atomic mole-fraction formula and enthalpy of formation. and Prandtl number Pr. the peak c* performance occurs at an O/F ratio between 5. Figure 2 plots these thermodynamic and transport properties as a function of O/F ratio and the combustion chamber pressure. 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.” (CEA)16 with HTPB as 100% of the fuel component of the propellant§. This value agrees closely with the “textbook” peak value of 1625 m/sec for hybrid HTPB/N2O combustion at 1000 psi chamber pressure (Ref. molecular weight MW. and the “reduced” molecular formula given by Eq. D.3% level of agreement supports the accuracy of the group addition ΔH0f calculation methods. characteristic velocity c*. § The CEA code has extensive internal libraries for reactant thermodynamic and transport properties including standard and nonstandard temperature and pressure conditions.

Figure 2. E. Thermodynamic and Transport Properties of N2O/HTPB Combustion Products. and 3) styrene. The monomers that make up any ABS thermoplastic are 1) acrylonitrile. 2) butadiene. Calculating the ΔHf0 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 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 .

and ns are the respective mole fractions of Acrylonitrile. where nb. The higher calculated enthalpy of formation suggests that this ABS formulation will likely not burn as hot as will HTPB. with a typical formulation consisting of 50% (mole fraction) butadiene. ABS Chemical Structure. The enthalpy of formation is calculated as 62. and styrene. and the “reduced” chemical formula corresponding to the calculated value ΔH0f ABS is (C3. mole fractions. heats of polymerization ΔQpolymerization.63 kJ/g-mol. This value is roughly 140% higher than the corresponding value calculated form HTPB. na.4 kJ/kg. While the authors recognize that the monomer ratio may not produce a propellant with optimal energy content. Table II shows monomer ΔHf0.85N0.Figure 3 shows the representative chemical structure of the ABS polymer for various monomer constituencies. and enthalpy contributions of the three ABS constituent monomers using the 50:43:7 monomer-ratios and the group addition method. 15 . the corresponding polymer ΔHf0. the ready availability of this stock product favored this formulation for analysis and testing during this phase of the project. 43% acrylonitrile and 7% styrene. Figure 3. Readily available industrial formulations of ABS tend to consist of approximately 1/2 butadiene.85H4.) (10) The equivalent mass-based enthalpy of formation is 1097. butadiene.43.

16 . When these graphs are compared against the corresponding HTPBbased figures (Figure 2). 19) 63.10(Ref.0.00 84.36 11) Styrene 146.Table 1. (10).6218 Butadiene 104. Slightly lower ABS-motor oxidizer flow levels should produce equivalent performance when compared to the HTPB-motor.00 0.31 0. 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. Enthalpy of Formation Contributions of Acrylonitrile.5.3119 98. Monomer ΔH 0f ΔH 0f ABS Mole Enthalpy Contribution KJ / g − mol polymer KJ / g − mol fraction 74. Figure 4 plots these ABS/N2O Combustion properties as function of O/F ratio and combustion pressure.0 and 5.50 16.10 20 32. MW. Thermodynamic and Transport Properties for ABS/N2O Combustion The value of ΔH0f ABS calculated in Table 1 and corresponding chemical formula Eq. 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. Butadiene. This “optimal point” is significantly lower than the corresponding HTPB O/F optimal values that lie between 5.63 F.07 4.9121 ABS Total 62.0-6. and Styrene Copolymers in a 50%/43%/07% ABS Formulation monomer KJ / g − mol ΔQ polymerization KJ / g − mol Acrylonitrile 172. and Pr.27 72.43 42. γ.31 0. µ.60(Ref. Calculated parameters include T0. c*.

Assuming the nozzle throat chokes immediately. Thermodynamic and Transport Properties of N2O/ABS Combustion Products.Figure 4. adjusted for non-unity combustion product Prandtl number. The motor modeling equations are based on the enthalpy-balance regression rate model developed by Ref. 8. Here the equation that describes the time evolution of the chamber pressure is 17 . 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. as the propellant burns the generated gases cannot escape as fast as they are produced and pressure within the fuel chamber builds. 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. III.

which varies significantly throughout the burn.( +1 & $ !P0 Aburn r! ) 2 . The fuel grain mass flow is modeled as m! fuel = Aburn ! " fuel ! r! .0 Vc ox dox / Vc % ' . ( #1 0 Rg T0 / A* $ " R T # P0 & # P0 / = ( Rg T0 + A C 2 "ox (Pox # P0 ) 0+ ' !t Vc % fuel g 0 * ( + 1. The O/F ratio of the burning propellant. The crux of the hybrid motor model used here is the fuel grain regression rate equation. corrected by Ref. (13) • where r is the linear fuel regression rate and ρfuel is the material density of the solid fuel grain. 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. is given by O/F = Aox Cd 2 !ox ( pox " p0 ) m! ox ox = m! fuel Aburn # ! fuel # r! . (11) The oxidizer mass flow rate is modeled by the incompressible discharge coefficient formula m! ox = Aox Cd ox 2 !ox ( pox " p0 ) . (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.. (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. (22) for non-unity Prandtl number 18 .

0.0. Tfuel.23 $ Aox Cd ox . exit properties. Nozzle. and comparison of its performance relative to geometrically identical fuel grains cast from HTPB. fuel grain fabrication methods. This section details the hybrid motor case design and assembly. G. . ρfuel. and test procedures. (15) the parameters µ and Pr refer to the combustion product gas properties. Adjustments are made for non-zero nozzle exit angles. Motor Case. 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. IV. identically-cast HTPB. and DDM-manufactured ABS fuel grains were static fired in a test cell housed on the Utah State University campus. test cell instrumentation. Multiple. Injector.153 ) . and hv refer to the properties of the solid fuel grain. Equations (11) through (15) are continuously integrated to calculate the chamber conditions. Calculate parameters include thrust. and Ignitor Assembly 19 .% c 4 1 &5 ( µ + 5 2 !ox (Pox # P0 ) / * /' ) L . 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 choking mass flow. the parameters Pox and ρox refer to the oxidizer liquid properties upstream of the injector. (15) In Eq.047 ( c p $%T0 # Tfuel &' + r! = * hv !fuel " Pr 0. and cp. Tests results and model comparisons will be presented later in the results and discussion section. and heat loss within the combustor. specific impulse. Nozzle throat dimensions are allowed to erode at prescribed rates. A .

Table 2 summarizes the mean motor and fuel grain dimensions and mass properties.2:1 expansion ratio and had a design throat diameter of 1.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. Two small Estes-class 10-gram solid rocket ignition motors were inserted into the injector cap. Figure 5: Cesaroni Pro-98 Motor Case Adapted for Hybrid-Motor Tests. graphite nozzles fabricated from a single piece of graphite replaced the original manufacturer-supplied phenolic nozzle. The motors and e-matches were replaced after each test firing. and electronic-matches. ignition motors. Additional advantages of this configuration are a ready-made “flight-weight” motor and the ability to rapidly reload between motor tests. To reduce run-to-run variability due to nozzle erosion.7 cm. A threaded pressure transducer was also installed in the modified motor injector cap. injector/motor cap assembly. Figure 6 shows photographic images of the nozzle assembly. The nozzle was designed to have a 4. Electronic matches burned by a 12 volt DC signal ignited these small motors. and the injector port. 20 . Figure 5 shows the original Cesaroni solid-rocket 98-mm motor case adapted for these hybrid motor tests.

55 930. cm2 Volume. kg kg/m3 Case cm3 HTPB 571. 21 . A*.07 31.47 km above mean sea level. Logan has an altitude of approximately 1. cm2 cm2 cm2 Cd ox 2. MJ/kg Mass. this expansion ratio was optimized for the altitude of the test site.Table 2. Diameter.326 2. Motor Case and Fuel Grain Dimensions.40 Heat of Initial Fuel Grain 98 702 Fuel Length. Initial Post Grain cm cm Port Combustion Ablation / Fuel Material Area.21 9. Chamber Gasification. Nozzle Nozzle Nozzle Injector Nozzle mm mm Throat Throat Expansion Exit Discharge Area.5 82.0 ** Based on the expected chamber pressure.07 31.825 2. hν. Logan Utah.67 975. Diameter. Aexit Ratio** Area. Coefficient.95 1.6 5.6 5.5 82.115 0. Grain Density. Motor Length.2 0. Area.95 2. A*.27 4.0 ABS 571.

used for these tests approximately the 50:43:7 chemical formulation presented earlier in Section II. The Stratsys FDM systems use production-grade thermoplastic materials that are sufficiently rugged for functional testing and end-use parts.Figure 6. The mean density of the ABS 22 .F. H. The ABS stock material. Stratasys ABS-M30® thermoplastic. Real production thermoplastics are stable and have no appreciable warping. ABS Fuel Grain Fabrication and Test Grain Geometry Multiple cylindrical ABS fuel grains were fabricated using a Stratasys Fortus®27 FusedDeposition Modeling (FDM) system. Nozzle and Motor Cap Assembly. shrinkage. Typically. or moisture absorption. these systems are used for 3-dimensional modeling and rapid-prototyping.

I. and post combustion chambers were 5. A post combustion chamber was pre-manufactured into the fuel grain.66 cm in diameter and 1.26 cm in diameter. the initial fuel port diameter was 2. The aluminum motor case acts as the pressure vessel for the motor. The mean fuel grain weight was approximately 2. HTPB Fuel Grain Fabrication and Test Geometry 23 . The fuel grain was fabricated to fit snugly into the motor case described in the previous section. ABS Fuel Grain Images with Dimensions.15 cm in length.stock material used for these test was approximately 975 kg/m3. The nozzle and motor cap assemblies are seated with O-rings. the injector port was designed to protrude approximately 1 cm into the top of the fuel grain port.67 kg. This density was considered to be sufficient to insure structural integrity of the fuel grain during the static test firings. Figure 7. 8. and then into the aluminum motor casing.54 cm.27 cm deep. Each fuel grain was bonded into a cardboard sleeve using high temperature silicone adhesive. This sleeve is then inserted into a phonelic insulating liner. Each fuel grain was approximately 57. Figure 7 presents the fuel images showing the grain features with the major dimensions labeled. To reduce the chances of initiating erosive burning.

Before casting the mandrel was coated with a mold release agent to insure proper release after the fuel grain cured. The mean density of the ABS stock material used for these test was approximately 930 kg/m3.C HTPB fuel grains were cast using the commercially available Arco R45M® polybutadiene resin and PAPI 94® MDI curative. Past experience has determined that these proportions assure adequate fuel grain cure and material hardness. The resin has a polymerization factor of approximately 50 and a molecular weight of 2734 kg/kg-mol.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. The HTPB fuel grain dimensions.5%/0. The HTPB fuel grains took as much as 15 days to reach their final 24 . The curative has an average molecular weight of 290 kg/kg-mol. A commercial H-VAC vacuum pump was used to remove gas bubbles created in the fuel grain during the mixing process.5%. carbon.54 cm (1”) polyvinyl chloride (PVC) pipe used as mandrel. The de-gassed mixture was cast in the same cardboard sleeves used for the ABS fuel grains with a 2. and the cast fuel grains had a mean mass of 2. HTPB/MDI/charcoal mass proportions were set at 87%/12.55 kg. The nitrogen. After casting the fuel grain were heat cured and the hardness was continuously monitored through out the cure process. PAPI 94 is a polymethylene polyphenylisocyanate produced by Dow® Plastics Inc. 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. including the post combustion chamber were identical to the previously described ABS fuel grains. oxygen (N-C-O) bonds in the MDI react with the hydroxyl (OH) terminations in the polybutadiene resin to cure the fuel grain.As mentioned earlier in section II. respectively. Arco R45M is polybutadiene diol manufactured by the Sinclair Petrochemicals Arco Division. The formulation contains methylene diphenylene diisocyanate (MDI) in proprietary proportions.

thrust. mass flow rate. J. Figure 8. an existing test cell at Utah State University was used to perform the motor characterization tests. and even after 12 days. 0. HTPB Fuel Grain Hardness as a Function of Cure Time. Representative fuel grain images †† Arco Poly BD R-45 HT resin (87%). the fuel grain were dissected and visually inspected for erosive burning and structural failure. motor case temperatures. specific impulse. the grain is still only 90% of its fully-cured hardness. Measurements obtained include chamber pressure. After 3 1/2 days. Data collected April 5-25 2011.hardness levels before static testing. 12. 25 .5% activated charcoal powder. and poses a significant potential hazard to the structural integrity of the motor. total impulse.5% Dow PAPI 94 polyethylene polyphenylisocyanate curative. Here measured Shore–durometer hardness29 units are plotted in curing days. Test Cell Apparatus and Instrumentation As mentioned earlier. Burning a polymeric fuel grain before it fully cures can produce unpredictable ablation rates. consumed propellant mass. Figure 8 presents “cure hardness” data for a traditionally cast HTPB†† fuel grain to support this assertion. and propellant regression rate. and may cause significant erosive burning. Erosive burning produces chaotic pitting and channeling along the length of the fuel grain. the material has reached only 50% of its final hardness. Following each motor test.

All tests results will be compared to analytical predictions for the specific motor fuel grain materials in that section. 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 top pressure kept the N2O above saturation pressure for the entire run and insured a single-phase liquid flow through the injector. and was automatically controlled by the instrumentation software. Figure 9 shows the piping and instrumentation diagram (P&ID) for the hybrid motor test arrangement. The design motor chamber pressure was approximately 3440 kPa (500 psi).will be presented later in the Results and Discussion section. 26 . The run tank was pressurized by gaseous nitrogen (N2) to insure a constant injector pressure during the entire length of the burn. and was typically maintained near 5200 kPa (800 psi) for these tests. The pneumatic run valve was triggered by an electronic relay. 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. The N2 “top pressure” was set by a manual regulator. 1.

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. Oxidizer Piping and Instrumentation Diagram (P&ID) for Hybrid Motor Tests. and the vertical loads were sensed by two Omegadyne® LCCA-25 (110 Nt) load cells.Figure 9. To reduce vibration during the static load tests. and the sensors were excited using a 12-volt DC power source. The axial load was sensed by an Omegadyne® LCCD-500 (2225 Nt) load cell. Chamber pressure was sensed using an MSI®-600 (0-6900 kPa) absolute threaded pressure transducer mounted in the motor 27 . For this series of tests only the axial and vertical loads were of primary interest. The 6-load cells allowed all load paths to be identified. the lateral load cells were replaced with support rods mounted on ball shafts. Originally a total of 6 load cells were installed on ball-joint mounts to reduce axial cross coupling. The output response for these sensors is 3 mV/Volt. 2.

Communications to the test stand were managed by an operator-controlled laptop via universal serial bus (USB) using amplified extension cables. digital output. 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. All control and measurement functions were controlled by a LABview® program hosted on the control laptop. An NI-compact DAQ® 4-slot bus controller with multiple analog input (16bit). and thermocouple modules (24-bit) bus-cards managed the majority of the measurements and valve control. Figure 10 shows a schematic of the test stand. Table 3. Relevant manufacturer's specifications including operating range and accuracy for each of these instruments is listed in Table 2.037% of Full Scale +500 lbf (2225 N) +0. analog output. The digital outputs from a separate NI USB6009® module were used to trigger the relays that fired the ignitor e-matches. 28 . Operators and experimenters were remotely located in a secure control room separated from the test area.1% of Full Scale (Chamber Pressure) Two National Instruments data acquisition and control devices managed motor fire control. Manufacturer Specifications for Static Thrust Stand Instruments Instrument Model Operating Range Accuracy LCCA-25 +25 lbf (110 N) +0.cap (Figure 6). and logged test data. and an image of the motor being fired.25% of Full Scale (Lateral Loads) LCCD-500 (Axial Loads) MSI-600 0-1000 Psia (0-6900 kPa) +0.

The presented time history profiles include thrust. 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. 29 . identically-cast HTPB. Static Test Mechanical and Instrumentation Schematic. To date 20 successful separate static-tests including 6 ABS and 14 HTP fuel grains have been performed. test results will be compared to model predictions. K. multiple. Thrust-Stand Time History Data Figure 11 presents side-by-side comparisons of time-history data collected from 4representative HTPB and ABS static firings. Finally. Results and Discussion As mentioned earlier in the introduction to Section IV. V. software.Figure 10. and DDM-manufactured ABS fuel grains were static fired to compare the relative performances of the two different fuel grain types. The data from several of these tests has been discounted due to known instrumentation. and test apparatus difficulties.

including thrust. Once visual inspection determined that the regression rates were sufficiently slow to insure motor survival. (16) The equivalent ensemble-mean vacuum specific impulse values are 225. and specific impulse. total impulse. Because there was a lot of initial uncertainty regarding the regression rates for the ABS fuel grains. It appears that the increased thrust for the HTPB fuel grains is not driven by a higher overall mass-flow. The mean steady state thrust level for the HTPB grains is approximately 755. Each of the HTPB fuel grain burns is approximately 10. and 717. For each case the HTPB fuel grains exhibit a small.6 s (ABS). both short (5. and an ambient test pressure of 86 kPa.6% higher than the mean for the ABS fuel grains (190. the ABS burn times were lengthened to 10.9% for the HTPB grains.300 kg/s (N2O). This value is approximately 6.25 s) burn profiles are presented.25 seconds in duration. I sp effective = I total g0 ! M fuel + M ox ( ).accumulated impulse.7 s (HTPB) and 211. The HTPB grains have an effective ensemble mean specific impulse of approximately 204.0 N. and 0. and oxidizer mass flow (as measured by the in-line Venturi system). For the ABS burns the corresponding oxidizer and 30 .25 s) and long (10. The approximate oxidizer and fuel mass flow rates for the HTPB burns are 0.1 s. The vacuum specific impulse calculation assumes nozzle exit area of 9.8 N for the ABS grains.6 s). The effective specific impulse is calculated by dividing the total impulse generated during the burn by the fuel and oxidizer mass consumed. the initial ABS fuel burns were kept to a short duration to reduce the chances of motor case burn through.077 kg/s (HTPB) respectively. For the ABS burns.27 cm2.25 seconds. This difference represents an advantage of approximately 4. injector and chamber pressures. but well-defined net-advantage in overall performance.

or slightly less than 1/2 of the observed thrust difference. This difference is approximately 2. Table 4 summarizes the individual and ensemble results for the HTPB and ABS burn tests. and curing process for the HTPB fuel grains. but it appears that the digital manufacturing methods demonstrate the potential for enhanced consistency in the fuel grain fabrication process. 31 . (17) where P0 and F are the mean steady-state chamber pressure and thrust levels. The steady-state thrust standard deviation for the ABS grains is approximately +17. the ABS fuel grains are actually characterized by a slightly higher fuel mass burn rate. this improved run-to-run consistency is likely a positive benefit of the FDM fabrication methods used to build the ABS grains. as opposed to the labor intensive mixing. Calculating the characteristic velocity for the individual burns supports this assertion. The mean c* value for the HTPB burns is approximately 1523. and 0.calculated by dividing the total consumed oxidizer mass by the total consumed fuel mass – are 4. The corresponding O/F ratios -.7 m/sec for the ABS burns.086 kg/s (ABS) respectively. 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.1 N for the HTPB grains.fuel mass flow rates are 0. This consistency difference may also be a result of HTPB being a thermo-setting material and ABS being a thermoplastic material. FDM is a precisely controlled by robotic industrial process.3%.75 for the ABS grains. Here the characteristic velocity is approximated by c* = g0 ! I sp CF "P % = g0 ! I sp ! A* $ 0 ' # F& .2 N compared to +32. casting.1 m/sec compared to 1488. This comparison suggests that the HTPB fuel grains burn at a higher flame temperature when compared to the ABS grains.304 kg/s (N2O). Unquestionably this topic requires further research. Although not large.19 for HTPB fuel grains and 3. degassing. Thus.

Figure 11. 32 . Burn Time History Comparisons for HTPB and ABS Hybrid Motors.

0 203.1 766.4 725.2 1488.09 σ c : 37.211 Fuel:0.12 σ F: 32.3 µ Isp: 204.299 Fuel:0. N 211.3 1541. N-s O/F Ratio 8747. HTPB Steady Total Consumed Effective Mean Grain Burn Impulse. s Steady Burns Time.2 Oxidizer: 3.7 1495.8 1567.07 HTPB Performance Mean and Standard Deviation * * 33 .614 Fuel:0. kg Isp. HTPB and ABS Motor Burn Summary.25 8294.787 O/F: 4.794 O/F: 4.25 7955.Table 4.0 µ c : 1523.27 VarHTPB5 10.25 c*.25 8011.6 Oxidizer: 3.80 O/F: 4.3 199. s Itotal.52 3.392 Fuel:0.4 787.15 VarHTPB7 10.6 202.4 Oxidizer: VarHTPB4 10. m/s Thrust.1 µ F: 753.27 VarHTPB6 10.795 O/F: 4.1 Oxidizer: 3.5 732. Mass.1 σ Isp: 5.

N-s sec VarABS2 5.25 c*.71 VarABS3 5.443 Fuel:0. N O/F Ratio 4289.25 7532.480 O/F: 3.854 O/F: 3.811 O/F: 4.25 7814.4 733.8 1497.7 σ Isp: 6.4 µ Isp: 190.8 198.7 Oxidizer: 3.549 O/F: 3.2 714.0 Oxidizer: 1.9 Oxidizer: 3. Mass.08 1.HTPB Steady Total Consumed Effective Mean Grain Burn Impulse.18 VarABS4 10. s Steady Burns Time.99 σ F: 17.801 Fuel:0.6 µ F: 717.0 694. Itotal.802 Fuel:0.387 Fuel:0.1 Oxidizer: 193.1 183.2 1564.2 σ c : 94. m/s Thrust.8 µ c : 1488.98 VarABS5 10.5 1539. kg Isp.9 728.25 4431.14 ABS Performance Mean \and Standard Deviation * * 34 .5 187.7 1353.

Comparison to Model Predictions As presented above. 12c (HTPB). and η*=(100% and 86%) for the ABS motor (Fig. still suggests that the ABS grains tested did not burn as efficiently as the HTPB grains. a likely candidate justifying the higher overall HTPB thrust and specific impulse appears to result from the c* efficiency of the combustion process.L. (11) through (15). 12a). Eqs. Here the thrust profiles from Figure 11 are overlaid against model predictions for η*=(100% and 92%) for the HTPB motor (Fig. The corresponding predicted c* profiles are plotted in Fig. and Fig. whereas the ABS fuel grains have an η* efficiency below 90%. 35 . Figure 12 presents model/static test comparisons to support this conclusion. This efficiency difference is approximately 9. This procedure determined that the HTPB fuel grains tend to an η* efficiency near 95%. was adjusted until the predicted thrust and chamber pressure values matched the measured values.5%. and although higher than the c* differences calculated earlier. 12d (ABS). 12b). (18) the combustion efficiency of the hybrid model. Defining the combustion efficiency as !* = c*actual c*ideal .

For both the HTPB and ABS grains. The burn patterns are very similar with the ABS fuel grain showing an incipient erosion pattern just 36 . fossilized surface flow patterns are visible. Figure 13 shows side-by-side comparisons of post-burn HTPB and ABS fuel grains. M. Fuel Grain Regression Measurements The results and conclusions presented on Figure 11 and Figure 12. The final regression dimensions were measured at multiple points along the fuel grain. and no erosive burn patterns were noted. Following the end of each static test. The regression measurement stations are marked on each grain. are further supported by post-burn fuel grain regression measurements.Figure 12 Model/Static Test Comparisons to for HTPB and ABS Hybrid Motors. Both the HTPB and ABS burned grains burned in a linear manner. and the transitions from laminar to turbulent flow patterns can be clearly seen. the motor was quenched and then split longitudinally to expose the burned grain pattern. and the mean end-to-end longitudinal fuel linear regression was calculated.

37 . the mean port diameter is approximated by the average of the initial and final fuel port diameters. 14b plots the linear regression rate against the mean port diameter. 13 b). Dividing the total regression by the steady burn time approximates the mean linear regression rate for each fuel grain.downstream of the injector. Figure 14 compares the longitudinal-mean regression measurements for all of the HTPB and ABS burns against model predictions. Fig. it simply does not burn as energetically as does the HTPB mixture. For both fuel grains the burn time was slightly longer than 10 seconds. Even though the ABS formulation has a greater material density. Fig. and the HTPB fuel grains are clearly demonstrated to exhibit a faster overall linear burn rate when compared to ABS grains. and a slightly asymmetrical final burn profile (Fig. 11 and 12. For the measured regression data. These test results directly supports the earlier data presented in Figs. 14a plots the total longitudinally averaged linear regression against burn time. Figure 13 Burned HTPB and ABS Fuel Grains. The models show reasonable agreement with the measured data.

Moline. a Parr model 1241®‡‡ Oxygen Bomb Adiabatic Calorimeter was used to burn multiple fuel samples selected at random from the burned 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. A final series of tests were performed to add supporting data for the conclusions reached in the previous sections. The gross heat of combustion was measured according to procedures outlined in ASTM D2382-8830. Table 5 summarizes these test results. Predicted and Measured Linear Regression for HTPB and ABS Grains.As described earlier lower burn rate is likely a result of lower overall combustion efficiency for the current ABS grain furmulation. The approximately 5% higher heat of combustion for ‡‡ Parr Instrument Co. Heat of Combustion Calorimetric Measurements for the HTPB and ABS Fuel Grains. N. 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. This section presents results from oxygen bomb calorimetry measurements performed on sections of post-burn fuel HTPB and ABS fuel grains. Figure 14. 10). In this series of tests. Illinois 38 . The measured gross heats of combustion for HTPB and ABS agree well with published values (Ref..

Sample Grain g cm Temp.301 15.32 15.24 22. Table 5.99 42. kJ/kg 1 ABS 15. Bomb Bomb Wire Combustion.HTPB agrees well with the previously established performance and regression rate advantages.03 24.62 39.24 8.36 2 HTPB 0.60 kJ/kg 39 . C Length.30 15. cm ΔQc.92 10.64 Fuel µ Δ Qc = 42.89 39.24 23.74 Fuel ABS Fuel Grain Combustion Statistics: µ Δ Qc = 39.30 3 HTPB 0.396 23. C Length.08 42. C Temp.16 5.31 15.80 7.24 23. C Temp.37 42.273 23. Wire Initial Final Consumed Heat of Weight.24 22.24 15.307 15.22 5.16 39.80 39.28 15.58 kJ/kg Wire Initial Final Consumed Heat of Weight.255 23.465 7.08 42.551 6.07 24.64 kJ/kg ABS Fuel Grain Combustion Statistics: σ Δ Qc =0.70 4 ABS 0.70 10.24 22.54 23.24 22.283 15.68 23.08 43.664 5. Sample Grain g cm Temp.67 5 HTPB 0.48 15.24 22. Oxygen Bomb Calorimetry Measurements for HTPB and ABS Fuel Grains.92 10.25 4 HTPB 0.38 2 ABS 0.16 39.42 23. Bomb Bomb Wire Combustion.31 15. cm ΔQc. Length.06 24.24 22.71 5 ABS 0. kJ/kg 1 HTPB 0. Length.47 3 ABS 0.68 23.24 22.24 22.

Figure 15 presents these results. 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. Figure 9) during the process of supercharging and filling the oxidizer run tanks (Item 6. Figure 9) was forced into the nitrous oxide storage tanks (Item 2.σ Δ Qc =0. It is believed that during system verification and cold flow tests. Clearly. Figure 9). This nitrogen gas became dissolved in the stored nitrous oxide.16 kJ/kg O. To support this premise. The peak O/F ratio is shifted to a much “leaner” value. there exists a significant impact on the propellant c*. 40 . a. CEA-based calculations were performed assuming that the “oxidizer” consisted of 80% N2O and 20% N2 by mass. indicate a dilution of the nitrous oxide storage tanks by the gaseous N2 used to pressurize the system. Here the c* values for the original propellant mixture (Figs. as presented in Table 4 and Figure 12. gaseous nitrogen from the pressurizing tanks (Item 1. and the maximum c* value drops by more than 5% for both the HTPB and ABS calculations. c) are compared to the c* values with a 20% N2 dilution of the oxidizer.

0 N to 823. Here the model/static thrust comparisons of Figure 12 are repeated.9 N.3 s.Figure 15. When the nitrous oxide storage tanks were replaced with a freshly-charged set of tanks. Figure 16 presents this result. the mean steady thrust level for the ABS motor has now increased from 41 . The corresponding test and vacuum specific impulses have increased to 222. The overall performances for both fuel grains improved dramatically. Effect of 20% Dissolved N2 in N2O Oxidizer on c*. The combustion efficiency now begins to approach 100% of the theoretical value. In a similar manner. The mean steady thrust level for the HTPB motor has now increased from the original mean value of 755. but with the static thrust data obtained using the “fresh” nitrous oxide tanks replacing the original data. respectively.7 s and 244.

with the new difference barely changing at 4. 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. respectively.9% for 6. This final section examines the individual ABS 42 . ABS Fuel grain Monomer Ratio Optimization As the data presented for the earlier 50:43:7 butadiene/acrylonitrile/styrene monomer molefraction demonstrate. 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 effective η* for the ABS fuel grain has now increased to approximately 95%. Figure 16. but consistently lower than the R-45m HTPB formulation.8 N to 783.717.2 s. respectively.5 N. The performance gains presented Figure 16 in have been consistently observed in these follow-on tests. P. Additional ABS fuel grains are being fabricated and will be tested as they become available.2% for Isp.1 s and 229. the energy content of this ABS formulation is slightly. Model/Static Test Comparisons to for HTPB and ABS Hybrid Motors with Recharged N2O Tanks. and the corresponding test and vacuum specific impulses have increased to 208. For the test cases presented in Figure 16. the HTPB motor still exhibits a slight advantage compared to the ABS motor.

The mole-fractions of each polymer were varied from 0 to 100% of the constituents of the polymer.0 -. such that the total makeup of each of the formulations equals 100%. 70% butadiene content results in a c* value 1618 m/sec. 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 . there exists an optimal butadiene content that peaks near a 30% total mole fraction and 90% A/S ratio. that exceeds the HTPB c* value 1608 m/sec for the same operating pressure and O/F ratio (Fig. The group addition method was used to calculate ΔHf0 for the various ABS polymerizations. thermodynamic properties. In contrast. the other two components were varied so that the sums of their mole fractions totaled the other 50%. and increasing butadiene content always leads to a better performing propellant. For a 2500 kPa operating chamber pressure and an O/F ratio of 6.5). Figure 2).0) there is no optimal point. for the higher O/F ratio (6. For lower A/S ratios this optimal point diminishes. and this data along with the corresponding molecular formulae.5 and O/F=6. Clearly.monomer mole fraction ratios to search for an optimal formulation. if the first component was 50% of the total constituency. For the higher O/F ratio the propellant performance is more or less independent of A/S ratio.0. For example. Calculations for different mixture ratios – O/F=4. for the lower O/F ratio (4. 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. At this juncture in the research.are presented. The resulting values for the equilibrium species concentrations. and transport properties were used to calculate the propellant’s characteristic velocity for each of the possible monomer combinations. The monomer ratios producing the higher c* values give the more desirable propellant combinations. was input into the CEA program for various oxidizer-to-fuel (O/F) ratios and combustion pressures.

ABS is an inexpensive thermoplastic that can be easily produced in wide variety of shapes.ABS may be better optimized for hybrid propellant performance. Conclusion A primary objective of this work was to investigate the viability of Acrylonitrilebutadienestyrene (ABS) as a hybrid rocket fuel material. but also the mixture that produces best results is closely coupled with the operating O/F ratio of the motor. Figure 17. ABS plastics are readily shaped into complex 44 . VI. Effect on ABS Monomer Mole-Fractions on Combustion Performance.

9% greater steady thrust and 6. but slightly reduced performance. The performance of ABS thermoplastic is compared to HTPB with Nitrous Oxide (N2O) as the matching oxidizer. and styrene mole fractions. consistency. Possible sources of this inefficiency could be the higher heat of gasification for ABS.6% higher effective specific impulse. and a higher enthalpy of formation for the stock ABS materials tested. Multiple ABS grains were DDM-fabricated from existing ABS stock materials composed of 50:43:7 butadiene. this technology will have a transformational effect on hybrid rocket motor production by improving quality. 45 . 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. In all cases the ABS formulation does not regress as rapidly or burn with as much heat as does the HTPB material. If demonstrated to be thermodynamically competitive with HydroxylTerminated Polybutadiene (HTPB). End-to-end linear regression rate and bomb calorimetry measurements of the heats of combustion support the static-fire burn performance data. For the original series of tests the hand-cast HTPB grains exhibited approximately 4. These grains were static-tested and compared against traditionally cast HTPB grains of equal physical volume and dimension. and no erosive burn patterns were noted.geometries using Direct Digital manufacturing Techniques. Direct-Digital Manufacturing (DDM) offers the potential to revolutionize methods used to fabricate hybrid rocket fuel grains. while reducing development and production costs. Once matured and commercialized. Test results demonstrate a higher burn-to-burn consistency for ABS fuel grains. and performance. acrylonitrile. Both the HTPB and ABS grains burned in a linear manner. ABS presents a very attractive hybrid rocket fuel option. Leveraging the recent rapid capability growth in factory automation and robotics.

This analysis suggests that future preparations of ABS may be better optimized for hybrid propellant performance. At the time of the writing of this report additional HTPB fuel grains have been cast and tested using the recharged nitrous oxide tanks. 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. but also the mixture that produces best results is closely coupled 46 . This study concludes with an examination of the effects of relative monomer compositions for the ABS fuel grains.5) there exists an optimal butadiene content that peaks near a 30% total mole fraction and 90% A/S ratio. nitrogen has been replaced by helium as the pressurizing fluid. When the nitrous oxide storage tanks were replaced with a freshly charged set of tanks. At this juncture in the research. Furthermore. For the higher O/F ratio (6. and increasing butadiene content always leads to a better performing propellant. it is unclear what allowable fraction of butadiene will retain adequate structural integrity for the fuel grain material. With the recharged tanks the performance margin between the HTOB and ABS fuel grains remained essentially unchanged.0) there is no optimal point. 70% butadiene content results in an ABS c* that exceeds the HTPB c* for the same operating pressure and O/F ratio. Calculations for different mixture ratios were presented. the overall performances for both fuel grains improved dramatically. The performance gains with recharged oxidizer tanks been consistently observed in these follow-on tests.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. This final section examines the individual ABS monomer mole fraction ratios to search for an optimal formulation. For the higher O/F ratio. Additional ABS fuel grains are being fabricated and will be tested as they become available. For the lower O/F ratio (4.

A. S. Baumgartner.org/wiki/Direct_digital_manufacturing. References 1 I-Shing Chang.wikipedia. 66{80. pp 706-714. In all cases the viability of industrially produced ABS fuel grains has been clearly proven. \Estimation of the free enthalpy (Gibbs free energy) of formation of organic compounds from group contributions. 8th ed. Dept. N. 13 Allan. J. September/October 2000.. 45. D. Vol. K. 2: Hazards.. Future studies will emphasize methods for increasing the burn efficiency of the ABS fuel material formulation. 2010. 4 Sutton. Inc. Chapt... 20. May 1988... “Sandwich Propellant Combustion: Modeling and Experimental Comparison. pp. 2. S. 5 Ramakrishna. 7 Feldman. No.basf. R. 1951. Vol. 3: Risk Analysis.” Polymer Testing. 4th ed. N. Elsevier Science Ltd. ofTransportation. S. G. P. S. 2 Anon.." Chemical Engineering Science. Presented at the 42nd AIAA/ASME/SAE/ASEE Joint Propulsion Conference & Exhibit 9-12 July.” AFRPL-TR-72-89.. No. 2011].de/basf2/html/plastics/englisch/pages/presse/04_261. Vol. California. Meyer. 4. E. “An Engineering Model for Saturated N2O Propellant Feed Systems. No. [Cited 23 June 2011]. 14 Wingborg..htm. D. S. No... [Cited 13 June.. D. and Mukunda. 00620693. V. D. 11 Van Krevelen. 4..” BASF News Releases. 2006.. Whitmore. 2002. July-August 2010. Vol. John Wiley & Sins..with the operating O/F ratio of the motor. “HTPB Polymer Improvement. A. pp.. 47 . (2000). Rocket Propulsion Elements.. 2009. Proceedings of the Combustion Institute. The authors want to thank teaming partner Avridyne Technologies/Rocket Crafter’s. H. 26... Paul. “Thrust Modulation in a Nitrous-Oxide/Hydroxyl-Terminated Polybutadiene Hybrid Rocket Motor. and Chandler. S.. Their Numerical Estimation and Prediction From Additive Group Contributions. O.S. G. Accession No.." AIAA J. “Plastics-Materials of the 21st Century.. A. “Investigation of Space Launch Vehicle Catastrophic Failure. URL: http://www. Sacramento. P. 2008. A. Vol.. 3 “Direct Digital Manufacturing. 29. and Jijenhuis. E. Properties of Polymers: Their Correlation with Chemical Structure. J. Vol. Spacecraft and Rockets. "Correlation of Hybrid Rocket Propellant Regression Measurements with EnthalpyBalance Model Predictions. and Lyon. W. Hackett. 6 Rajesh. pp 2963-2973. K. “Hazard Analysis of Commercial Space Transportation. 5..” Journal of Fire and Materials. September/August. September 1972. H. Vol. 1010-1020.” AIAA Journal of Propulsion and Power. and Chermin. PB93-199040. P..” AIAA Paper 95-3128. M. S. 12 Krevelen. 24. W. 8 Eilers. “Increasing the Tensile Strength of HTPB with Different Isocyanates and Chain Extenders. “Heats of Combustion of High Temperature Polymers. Additional funding was received from the NASA Experimental Program for Stimulating Competitive Research (EPSCOR). 9 Whitmore. 245–252. 1. Acknowledgments This work was partially funded under a grant from the Utah Governor’s Office of Economic Development Technology Commercialization and Innovation Program (TCIP).” http://en. and Biblarz..” AIAA 2006-4503. 16. R. W. K. 1: Operations.” U.. Inc. pp. Vol. Chapt. E. Inc of Layton Utah for procuring the ABS fuel grains from Stratus. July 1995. 10 Walters.

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