AIAA 2004-3821

40th AIAA/ASME/SAE/ASEE Joint Propulsion Conference and Exhibit
11-14 July 2004, Fort Lauderdale, Florida

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

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

I.

Introduction

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

*

M.S. Student, AIAA Student Member.
M.S. Student

Ph.D. Candidate, AIAA Student Member
§
Ph.D. Research Associate, AIAA Member
**
Distinguished Professor of Mechanical Engineering, AIAA Fellow

1

Copyright © 2004 by Brian Evans , Nicholas A. Favorito , Eric
Boyer , Grant
A. Rishaof
, Robert
B. Wehrman,
Kenneth K. Kuo. Published by the American Institute of Aeronautics and Astron
American
Institute
Aeronautics
andand
Astronautics

In addition to the 19 fuel formulations previously tested. It is advantageous to use IPDI curing agent in casting fuel grains that contained particles with a high specific surface area. nano-sized tungsten powders and nano-sized rod shaped aluminum have been acquired and tested as performance enhancing additives in HTPB-based solid fuels. The regression rate can than be correlated to the instantaneous oxidizer mass flux. To accomplish this goal there have been two main methods of fuel burning rate enhancement: 1) Nano-sized particle addition for increasing the heat that is released near the surface of the fuel.5 inches) in lengths up to 457. The objective of this research is to find means of further enhancement of the mass-burning rate of solid fuel formulations for use in hybrid rocket motor propulsion systems. The HTPB was formulated using R45-M resin with either Isonate 143L® methylene diphenyl isocyanate (MDI) or isophorone diisocyanate (IPDI) curing agent with T-12® catalyst. et al.5 mm (2. HTPB-Based Solid Fuel Processing The XTC hybrid rocket motor was used to burn two baseline solid fuel formulations. which have shown to increase regression rates to 3 times that of traditional polymeric fuels such as HTPB. Low burning rates of solid fuels have been shown to be enhanced by the addition of energetic metal powders. II. This allows for the instantaneous regression rate to be determined as a function of time. in order to create a center-perforated grain.11 have evaluated 19 different HTPB-based fuel formulations using a LongGrain Center-Perforated (LGCP) hybrid rocket motor. With the X-ray Translucent Casing (XTC) hybrid rocket motor the surface of the fuel is imaged throughout the duration of the combustion test. Hybrid Rocket Motor Casting Procedures 1. Also the grains were cast utilizing a previously developed novel low-melting point wax mandrel process.13. Due to the relatively low mass-burning rate of polymer-based solid fuels. the burning rates of the current solid propellant grains in the existing systems are limited due to the less efficient burning-rate modifiers that have been utilized in the conventional solid propellants. 2) Paraffin-based solid fuel formulations have an inherently high mass-burning rate due to the hydrodynamically unstable liquid layer that is formed on the surface of the fuel during combustion.field. a large fuel burning surface area is required to attain a given thrust level.10. Another means of increasing the mass-burning rate of solid fuels is by the use of paraffin wax-based solid fuels. In addition the use of non-polymeric fuels such as paraffin wax increase the burning rate of solid fuels by many hundred percent.8.9. such as the nano-sized tungsten. The casting process for solid-fuel formulations for the XTC motor grain is similar to the LGCP motor. such as hydroxyl-terminated polybutadiene (HTPB) and hydroxyl-terminated polyether (HTPE) compared to solid propellants. Previous studies conducted by Risha. one of which is the cured HTPB.3 mm (4. This will increase the linear regression rate of the fuel and thus the mass flow-rate of propellant. requiring a relatively large fuel surface area for a desired thrust level. The large increase in fuel regression rate that is attained helps to alleviate the need for complex port geometries required with current polymer-based fuel formulations. because of the ability to vary the working time of the solid fuel. but high density impulses. A.5 inches) and an inner diameter of 63. As mentioned. In addition. Method of Approach B. Typical test durations for the XTC ranged from 5 to 7 seconds depending on the fuel formulation and the injected oxidizer mass flux.14 Evaluation of various fuel formulations with either and/or both of these mass-burning rate enhancement techniques has led to the development of novel solid fuel formulations with greatly enhance mass-burning rates. the mixing of the oxidizer species with those generated from surface pyrolysis/evaporation of the molten fuel also controls the combustion rate.12 The combination of paraffin-based solid fuels and nano-sized energetic particles drastically increases the regression rates of solid fuel formulations. 3) their susceptibility to mechanical damage and subsequent flame spreading into the damaged regions and potential catastrophic motor failure. Grains were cast in paper phenolic tubes that have an outer diameter of 114.2 mm (18 inches). 2) the propellant grain cannot be extinguished once the grain is ignited. Several other undesirable features of the solid-propellant rocket systems are: 1) not being capable of thrust modulation.15 The solid fuel was mixed following the same procedure for introducing particles into the resin and degassing. The utilization of various energetic nano-sized powder additives in the fuel formulation is one way to alleviate this problem by increasing the fuel regression rate. the major disadvantage of the existing solid-fuel grain formulations is the relatively low mass-burning rate of the fuel. Objective of Research Existing solid propellant missiles have relatively low specific impulses. 2 American Institute of Aeronautics and Astronautics . and 4) solid fuel mechanical properties are sacrificed because of relatively low loading densities. In addition.

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

the smaller quantity of nano-sized particles required for a series of evaluation test firings in the LGCP hybrid rocket motor is highly beneficial. For this reason.17 to 4. percent by weight added to the solid fuel. 3) had similar initial operating conditions. and performance enhancement can be found in References 8 and 9. In addition. All constant mass flow rates. which is similar to the Figure 3.24 MPa (300 to 600 psig). the a b c range of oxidizer mass flux was determined and scaled accordingly so that the larger scale XTC motor (see Fig. All through the use of this micrographs are 250 mm in height and width and are at 500x magnification venturi. X-ray imaging setup used with XTC hybrid range used for the LGCP and will allow for comparison in performance. which is sufficient for the desired oxidizer mass fluxes. for evaluation using the LGCP hybrid rocket motor. Micrographs of unburned outer surface of paraffin fuel layer a)SEM kg/s can be obtained micrograph. the use of a non-polymeric fuel formulation has also been implemented. The dominating parameter that dictates the mass-burning rate in a hybrid rocket motor is the oxidizer mass flux. 18 fuel formulations were evaluated previously and a complete list of the particle type. b) carbon elemental map. 20 types of nano-sized particles have been evaluated using the LGCP motor. two new types of nano-sized tungsten particles have been evaluated as well: one is a neat tungsten particle with no oxide coating and the other with a 5% oxide coating by weight. Fuel Formulation Consideration and Thermochemical Calculations of Paraffin-Based Fuels with Silberline and Nano-Sized Tungsten Particles For examining the burning rate enhancement by a new type of particle. Testing and analysis of paraffin-based fuel formulations have been 4 American Institute of Aeronautics and Astronautics . Inc. b) carbon elemental map. Micrographs of unburned inner surface of paraffin fuel layer a)SEM order to attain the desired micrograph. rocket motor a b c D. c) aluminum elemental map. Hybrid Rocket Motor Experimental Setup A variable-throat venturi with upstream pressure and temperature measurements was employed in the gaseous oxygen feed system in Figure 1.42 Figure 2.C. Since there is no discernable pressure effect. micrographs are 250 mm in height and width and are at 500x magnification From previous experiments using the LGCP motor. c) aluminum elemental map. Oxidizer mass fluxes ranging from Blast Shield X-ray Image 60-290 kg/m2-s have been tested in the XTC Source Intensifier hybrid rocket motor to obtain a range of data for a given fuel formulation. The solid-fuel regression results of the HTPB-based fuels with these two new particles can be compared to our previous data to determine the benefit on combustion performance using tungsten particles. Because of this. the steady-state chamber pressure of the XTC can be similar to or much greater then that of the LGCP while still maintaining approximately the same linear regression rate. Paraffin-based solid fuels have been shown to increase the burning rate several times over that of traditional polymeric fuels such as HTPB. To further enhance the burning rate of new fuel formulations. These particles were obtained from Nano-Mat. A comparison of the effectiveness of these two types of particles and their burning characteristics is included below. the chamber pressure has been selected to range from approximately 2. Flow rates of up to 0.

is also very advantageous in volume-limited systems.5 3 3. 260 5 American Institute of Aeronautics and Astronautics . For these candidates.5 3 3.9.5 4 4. Discussion of Results The energetic powder additive to the HTPB-based fuel that has shown the largest increase in burning-rate enhancement in previous series of tests is the Viton®-A 240 coated Alex® aluminum nano-sized powders with an increase of 120% in mass-burning rate and 123% increase in the average linear 220 1 1. A number of other candidates Figure 5. Technanogies aluminum.5 4 4. Burning rate enhancement is also expected for paraffin300 based solid fuel formulations containing different amounts of aluminum particles.5 5 aluminum to paraffin based fuels can O/F indeed be highly beneficial in volume limited systems as the density impulse Figure 4. 340 The addition of Silberline® aluminum particles has shown to increase the linear regression rate of HTPB-based solid fuel 320 formulations by approximately 30% over the baseline pure HTPB fuel. which include Silberline® aluminum flakes. 280 Besides the increase in the regression rate of the solid fuel.11 The addition of Viton®-A has proven to be beneficial in increasing the average mass burning and linear regression rates. A wide range of average oxidizer mass fluxes (60-290 kg/m2-s) have been evaluated for comparison to results obtained in the LGCP hybrid rocket motor for particle addition to HTPB-based solid fuels and to further extend the range of data. even over comparable 300 weight percentages of Silberline® aluminum.8.3 Density Impulse [g-s/cm ] 3 Density Impulse [g-s/cm ] considered in both the LGCP and XTC hybrid rocket motors. The large increase in density Isp that is observed. Thermochemical calculations of density Isp of varying increases very significantly (8%) with a percentages of Silberline® aluminum nano-particles added to 20% aluminum addition by weight. The number of particles in a 13% by weight 340 tungsten addition is much lower than that of a 13% by weight aluminum addition due to the significantly higher molecular weight of 320 tungsten. Figure 4 shows a comparison PF w/ 10% SILBAL of density impulses for varying percentages PF w/ 7% SILBAL of Silberline® aluminum nano-sized flakes.5 2 2. As can be seen the addition of 220 1 1.5 2 2. Thermochemical calculations of density Isp of varying also exhibited significant performance percentages of tungsten nano-particles added to paraffin increase compared to the baseline solid fuel HTPB. PF w/ 4% SILBAL 240 Pure Paraffin Fuel All data presented is for liquid oxygen as the oxidizer and a chamber pressure of 1000 psia. Figure 5 shows a comparison of density paraffin Isp of pure Paraffin to various weight percentages of nano-sized tungsten particles.5 5 regression rate at an oxidizer mass flux of O/F 112 kg/m2-s. an average increase in linear regression rate of 60-70% was seen. 280 PF w/ 20% W addition PF w/ 13% W addition PF w/ 17% W addition PF w/ 10% W addition PF w/ 7% W addition PF w/ 4% W addition Pure Paraffin Fuel III. the density impulse of the PF w/ 20% SILBAL metallized fuel is also higher than the PF w/ 17% SILBAL 260 PF w/ 13% SILBAL baseline case. Viton®-A coated Silberline® aluminum flakes.

It is noted that fuels containing the tungsten particles with oxide coating showed a 3 slightly lower mass-burning rate than those with the pure tungsten powder. This is expected since the active tungsten content is less than that of the neat 2 particles. which is approximately 660 C.5%B C+6.5%WARP-1 (SF5) 13%NTECH50 (SF18) anticipated that the solid fuels with 50.5 formulation. baseline HTPB fuel cast with MDI curing agent. Even though the HTPB with 13% tungsten powder showed only moderate increase in regression rate (about 38% at the average oxidizer mass flux level of Gox~140 kg/m2-s) with respect to the pure HTPB. The data for various solid-fuel formulations observed plume jet did not show particle streaks. A fair comparison should be based upon the equal molar percentage rather than equal weight percentage. Combustion efficiency data shows values from 77-87%.8 ~2. The combustion of tungsten is also suitable for a rocket motor application due to the strong heterogeneous reactions that begin at approximately 400-500 C and at higher temperatures.14% by weight of aluminum. As mentioned above. is higher than the temperature for onset of oxidation of tungsten the particles will start to under go heterogeneous combustion as soon as they are exposed to the oxidizing atmosphere of the 4 4 4 6 American Institute of Aeronautics and Astronautics . To ensure that the IPDI curing agent did not alter the performance of the baseline HTPB solid fuel formulation. Comparison of average linear regression rate possible based upon test data obtained. 6 and shows little variation in burning rate from SF1. Comparing a 13% by weight tungsten fuel formulation with an equimolar 1 concentration solid fuel formulation with aluminum. resulting in slightly lower energy release. which shows complete particle combustion within the rocket motor chamber.4% by weight 13%C-ALEX (SF13) Pure HTPB (SF1) 13%C-Boron (SF14) 13%ALEX (SF2) tungsten fuel formulation would be needed. Their slopes are quite 2.65%Boron (SF19) 13%SILBAL (SF7) tungsten particles by weight should show a Pure HTPB/IPDI (SF20) 13%CLAL (SF8) 13%NMATWPure (SF21) 13%WARP-1 (SF9) considerable increase in mass-burning rate. nano-sized tungsten powders were cast in an HTPB-based solid fuel formulation using an IPDI curing agent with T-12 catalyst. though. rapid oxidation occurs.380 C) and extremely high boiling temperature (5. The comparison of data in Fig. 6.4% 13%Boron (SF6) 5. a 50.927 C). Since the surface temperature of HTPB.5 that of a 13% by weight aluminum or boron because the molecular weight of tungsten is so much higher. a series of three baseline HTPB solid fuels were cast and tested using the IPDI and T-12 in similar amounts as the tungsten nano-sized powder containing grains. At the equivalent amount of tungsten particles having the same volume as the aluminum particles. tungsten would be difficult to melt and vaporize due to its high melting temperature (3. Higher percentage particle addition is Figure 6.9kJ/cm3). one can expect a much higher burning rate enhancement. which falls in the upper half of previously reduced data. For a volume limited system this is extremely beneficial. Solid Fuels Containing Nano-Sized Tungsten Particles The addition of nano-sized tungsten powder to solid-fuel formulations is beneficial due to the high volumetric heat of oxidization (88. This pure HTPB fuel formulation is named SF20 and the data is contained in Fig. the 13% of tungsten by weight has much fewer particles than 13% aluminum particles. If not for these strong heterogeneous reactions occurring at relatively low temperatures. based upon information from reference 1616. Comparison of the burning rate enhancement of the two newly developed fuels containing nano-sized tungsten powders with the data of HTPB-based fuels containing other energetic powders is shown in Fig. The number of particles contained in a 13% by weight tungsten fuel formulation is much less than 1. When 13%AVAL (SF15) 13%B C (SF3) 13%IHD-AR (SF16) 6.5%WARP-1 (SF4) taking this factor into consideration. 6 is still based upon the traditional weight percentage consideration of fuel/propellant 3. since 13%NMATW5 (SF22) 13%Cat-B C (SF10) 13%TECHAL (SF11) Pure Paraffin w/ 2% Carbon Black (SF23) equimolar basis is a more suitable means of 13%Al325 (SF12) comparison. If an equimolar 60 80 100 120 140 160 180 concentration of tungsten were to be added to equal the number of moles contained in a 13% by Average Oxidizer Mass Flux [kg/m2-s] weight aluminum fuel grain.5 similar.Average Regression Rate [mm/s] E. it is 13%NTECH80 (SF17) 6. which is approximately 6% higher than that of aluminum. the aluminum fuel would only contain 0.

6 paraffin solid-fuel data of Karabeyoglu.4 3.1 rates in comparison to baseline paraffin NS-117-PFC2-100 108.05 3.10 1458. The measured chamber pressure and resultant burning rate data is given in Table 1. Silberline® Average Average aluminum particle addition. both the LGCP and the XTC hybrid rocket motors have been utilized.22 3.14 153.9 2. XTC-23-PF-SILBAL-13 217.4 2.ave baseline paraffin fuel. The testing of paraffin-based solid Table 1. % of Silberline® nano-sized aluminum flakes. was conducted in the LGCP motor.54 168.ave Chamber rb Thrust Test No.31 1899.21 1041. the data obtained from paraffin-based solid fuels containing Silberline® aluminum flakes is not included here. It is quite obvious that the baseline paraffin solid fuels in the LGCP hybrid rocket motor demonstrated a significantly higher regression rate than any of the HTPB-based fuel formulations containing nano-sized particles. Later on this delamination problem was solved by improvement of processing procedures. the regression rates of 6 PSU’s data are higher due possibly to the 5 difference in processing techniques and the slight difference in fuel formulations.56 1. Average Linear Regression Rate [mm/s] F.8 al.9 presented in Table 1 are plotted in Fig. Table 1 shows the average oxidizer mass fluxes and linear regression NS-121-PFC2-100 64. however.motor combuster. and Stanford paraffin burnseen for the formulations containing 13% by wt. complete combustion is anticipated even at much higher particle loadings because of the means of ignition and heterogeneous combustion.58 3.0 rates measured for these tests.79 2.1 tests firings exhibited very high regression NS-116-PFC2-100 122.5 is evident that there is a noticeable increase in the linear regression rate of the solid-fuel 2 ® formulations containing Silberline nano-sized aluminum flakes compared to the baseline 1. paraffin fuel containing 13% by wt.0 4. Paraffin-based solid fuel formulation test conditions and fuels in the XTC motor focused on paraffin-based fuel formulations resultant average regression rates containing 13% by wt. For clarity purpose. An increase of about 60% 12 7 American Institute of Aeronautics and Astronautics .34 1081. 7 XTC-20-PF-SILBAL-13 148. Initial baseline paraffin solid fuel testing. rate curve fit Silberline® particles.5 paraffin fuel formulations if the data were 60 80 100 125 150 175 200 250 300 extrapolated to a higher mass flux level. Paraffin-Based Solid Fuel To evaluate the burning rate characteristics of paraffin-based solid fuels. The 4 difference in the amount and size of carbon black powder of these two fuels could cause the 3 surface energy release amount to be different.3 7.1 solid fuels. 2 rocket motor firings that were conducted.09 162. Based upon this. an increase of ~30% is ® Silberline aluminum flakes. [kg/m -s] [mm/s] Pressure [N] five of the tests produced useful results.69 806.12 of the Stanford University are also plotted on the same figure for comparison purposes.9 against the data obtained for the baseline XTC-21-PF-SILBAL-13 166. The resultant linear regression rate data obtained from LGCP motor tests with the baseline paraffin solid fuel is also included in Figure 6 for direct comparison with the HTPB-based solid fuels containing different types of nano-sized energetic particles. Of the XTC Gox. [MPa] The five aluminized paraffin solid-fuel NS-115-PFC2-100 72. The Stanford data curve fit has the 8 Paraffin Fuel w/ 2% Carbon Black (SF23) same slope as the PSU data for nonaluminized 7 Paraffin Fuel w/ 13% Silberline Aluminum (SF24) Stanford Paraffin Regression Rate Data paraffin fuel. containing 2% carbon black by weight.16 3.4 6.6 paraffin-based solid fuel formulations.9 2. It 2. Further testing was completed in the XTC hybrid rocket motor with paraffin-based fuel containing 13 wt.84 2.11 131. et. By 2 Average Oxidizer Mass Flux [kg/m -s] extrapolating the curve fit obtained for the Figure 7.4 4. but is shown later in the text. The XTC-22-PF-SILBAL-13 290.13 3. Comparison of average linear regression rates of baseline paraffin fuel formulation to the Gox.0 4.42 2. The earlier tests of the paraffin fuels in this series exhibited certain amounts of delamination of the fuel from the paper phenolic grain tube or between interfaces of consecutive casting layers. The data XTC-17-PF-SILBAL-13 190. value of 190 kg/m2-s.

Grain surface of a recovered paraffin-based solid fuel with 13% Silberline aluminum showing wrinkled pattern (Test No. one of the governing parameters is the oxidizer flow velocity. This dictates the size of the wave structure that occurs on the fuel surface (see Fig.98 indicating a good match to Figure 9. Figure 9 shows the deduced instantaneous port 8 radii (in terms of change of port radius) versus time of these two tests. Silberline® aluminum were analyzed in order to get a correlation of the instantaneous fuel port radius near the aft end of the grain as a function of time. The flow rate of Test XTC-22 is about XTC-21-PF-SILBAL-13 4. which was chosen to be small enough to give sufficient resolution for the curve fit and large enough to show the radial variation of the fuel surface. The deduced instantaneous radius is fit as a power law of time according to: r (t ) − r0 = a (t − tign ) n (1) Tests XTC-05 and XTC-07 were conducted with HTPB-based solid fuel grains containing 13% by weight Silberline® aluminum flakes. Instantaneous Regression Rate Determination Analysis of the visual data obtained from four XTC test firings with HTPB-based and paraffin-based solid fuel formulations containing 13% by wt.758 0.640 0.O2 flow 40 mm Figure 8. 10 using the same power law curve fit Test No. a n function. Another observation that can be made regarding the burning trends of the paraffin-based fuel formulations is the difference in slope of the curve fits. Deduced instantaneous port radii as functions of the data.793 0.25 second increments. Images are analyzed at ~0. Again it was found that the XTC-05-SILBAL-13 1.752 25% higher than that for Test XTC-21.9207 exponent n is higher for the higher oxidizer flow XTC-07-SILBAL-13 1. The XTC-07 Instantaneous Change in Port Radius slopes of the two Silberline® aluminum fuel grain 0 tests expressed by parameter a are quite similar. This was accomplished by processing the video images from the real-time X-ray radiography system using a commercially available special effects package that did not alter the actual fuel surface location. The power-law curve fit parameters a and 4 n for Tests XTC-05 and XTC-07 are presented in Table 2. this inversion greatly enhances the clarity of the fuel grain surface. The fitting parameters a and n are also shown in Table 2. This difference in slope is caused by the aluminum particles in the paraffin fuel combustion process.762 0. G. Power-law curve fit parameters for XTC fuel tests (Tests XTC-21 and XTC-22) is shown motor tests with aluminized HTPB and paraffin fuels in Fig. It 0 2 4 6 was noted that both curve fits have a high R2 Time from Ignition [sec] value greater than 0. 8) and also the size of the particles that are stripped from the surface waves of the molten fuel layer and entrained into the combustion zone. XTC-22-PF-SILBAL-13 7. In baseline paraffin fuel formulations. XTC-PF-10-SILBAL-13) is seen for the difference between the aluminized paraffin and the Stanford curve fit results.9708 Change in Port Radius [mm] 10 8 American Institute of Aeronautics and Astronautics . time for test firings XTC-05 and XTC-07 A similar plot for the two aluminized paraffin Table 2. The difference between 6 the oxidizer flow rates of these two tests is approximately 13% with Test XTC-05 being higher. This time step is altered if an image is difficult to measure a distinct fuel grain surface location. The special effect inverts the image density of the original picture. The exponent of the power law correlation for the higher flow rate test is slightly 2 XTC-05 Instantaneous Change in Port Radius greater than that for the lower flow rate test.8772 rate case.

a data analysis procedure has been developed. (1) with respect to time. the regression rate decreases as time increases. py = m& ox + ρ p rb As = m& ox + 2π L ρ p an ( t *) n −1 ⎡ ro + a ( t *)n ⎤ ⎣ ⎦ (4) Substituting Eq. Even though this expression is much more complex than the conventional expression of regression rate in terms of power-law of oxidizer mass flux. time for test firings XTC-21 and XTC-22 From this equation it can be seen that if the exponent n is less than unity.5 2. we have Change in Port Radius [mm] 10 8 6 4 2 XTC-21 Instantaneous Change in Port Radius XTC-22 Instantaneous Change in Port Radius rb = 0 0. Deduced instantaneous port radii as functions of where: t* ≡ t − tign . (2) to express t* in terms of regression rate. we have 1 ⎡ r (t*) ⎤ n −1 t* = ⎢ b ⎣ an ⎥⎦ (6) Eliminating t * from Eq. we obtain the following relationship between rb (t*) and Gtotal (t*) Gtotal (t*) = m& ox ⎧ ⎪ ⎡ rb (t*) ⎤ ⎣ an ⎥⎦ π ⎨ ro + a ⎢ ⎪⎩ n n −1 ⎫ ⎪ ⎬ ⎪⎭ 2 + 2 L ρ p rb (t*) n ⎧ ⎫ ⎪ ⎡ rb (t*) ⎤ n −1 ⎪ + r a ⎨o ⎢⎣ an ⎥⎦ ⎬ ⎪⎩ ⎭⎪ (7) This equation is in an implicit form of regression rate dependency on the total mass flux. In order to express regression rate in terms of the total mass flux. (5).5 n −1 dr n −1 = an ( t − tign ) = an ( t *) dt Time from Ignition [sec] ( (2) ) Figure 10. (3) yields.0 0. Since the instantaneous regression rate of the solid fuel is governed by the local energy transfer rate and mass diffusion processes occurring in the port of the hybrid motor. 9 American Institute of Aeronautics and Astronautics . Gtotal (t*) = m& ox + 2π L ρ p an ( t *) ⎡ ro + a ( t *)n ⎤ ⎣ ⎦ n 2 π ⎡ ro + a ( t *) ⎤ ⎣ ⎦ n −1 (5) Inverting Eq. port diameter. The total mass flux at an axial location is the total mass flow rate divided by the instantaneous port area. it is derived without major assumptions. oxidizer mass flux.0 2. one has to make certain order-of-magnitude approximations of exponent n. By differentiating Eq. the axial distance and the power-law parameters.To determine a correlation of the regression rate with respect to important operating parameters (such as the instantaneous oxidizer mass flux. hence Gtotal = m& total n π ⎡ ro + a ( t *) ⎤ ⎣ ⎦ (3) 2 where the total mass flow rate is the sum of the instantaneous oxidizer mass flow rate and the fuel flow rate from surface pyrolysis.0 1. and total mass flux). initial port radius.5 1. it should depend strongly upon the total mass flux at the given station. namely m& total = m& ox + m& fuel . (4) into Eq.

Volume limited 200 400 600 800 1000 1200 1400 1600 1800 Total Mass Flux [kg/m2-s] propulsion systems would greatly benefit from the use Figure 13. shows an increase of 38% in fuel regression rate compared to 3 the baseline HTPB fuel formulation.5 1. The benefit derived in high density impulses and combustion efficiency makes this energetic powder a viable additive to advanced energetic fuels. In this figure the two curves are even further apart showing the strong dependency of instantaneous regression rate on the instantaneous total mass flux. and low oxidation temperature via heterogeneous reactions.Using Eq.4 XTC-05 XTC-07 1.inst Test XTC-05 rb vs. the data do not follow the conventional power-law relationship between the measured regression rate and the instantaneous oxidizer mass flux when the data are given in a log-log plot. high heat of instantaneous total mass flux oxidation. 4 10 American Institute of Aeronautics and Astronautics .inst Test XTC-07 1 1. Dependency of the instantaneous of nano-sized tungsten powders in solid fuel regression rate of aluminized paraffin fuels on formulations due to its high density. (2) SEM/EDS micrographs of the newly processed energetic paraffin-based solid fuels have shown that the nanosized Silberline® aluminum flakes are homogenously mixed in the fuel matrix. however.6 1. We have looked into the possibility for using instantaneous oxidizer mass flux to replace the total mass flux. Furthermore.8 1. 13. the functional relationships between regression rate and total mass flux are quite different as indicated by the difference of curvature and location of these two sets of data in Fig.75 8 7 6 5 IV. the results shown in Fig. Gox. 12 also indicated the non-collapsing situation of the two curves. the deduced instantaneous regression rates of the two aluminized HTPB-based fuel test runs (XTC-05 and XTC-07) are plotted versus the instantaneous total mass flux in Fig. XTC-21 XTC-22 Conclusions (1) Nano-sized tungsten powder addition to HTPBbased fuel formulation in 13% by wt.2 100 200 300 400 500 600 2 Total Mass Flux [kg/m -s] 100 150 200 250 300 400 Instantaneous Oxidizer Mass Flux [kg/m2-s] Figure 11. Dependency of the instantaneous regression rate of aluminized HTPB fuels on instantaneous oxidizer mass flux The aforementioned differences between the regression rate versus total mass flux curves obtained under different operating conditions is further illustrated in Fig. (7). producing grains that have fairly uniform distribution of aluminum particles throughout the fuel. Dependency of the instantaneous regression rate of aluminized HTPB fuels on instantaneous total mass flux Figure 12. Gox. 9). 11.25 rb vs. Even though the slopes (a) of the fuel radius change versus time are nearly identical (see Table 2 and Fig. from the results of two aluminized paraffin-based fuel test runs (XTC-21 and XTC-22) conducted under different test conditions. 9 Linear Regression Rate [mm/s] 1.0 1. 11. 2 Linear Regression Rate [mm/s] Linear Regression Rate [mm/s] 2. It was verified that the recently developed mixing and casting procedures do not cause particle migration in the fuel matrix.

5 Strand. A. Harting. B.. AIAA/SAE/ASME 28th Joint Propulsion Conference. B. Nancy Johnson of the Naval Surface Warfare Center-Indian Head Division for their sponsorship of this research project through CPBT corporation (under contract number N00174-02-C-0024) with a subcontract to PSU.and Boron. K. C. P. AIAA Paper No. IN." AIAA Paper No. 1997. 125-132. E. F. T. V. 14 Karabeyoglu. 034592. 2000.. The exponent for time was found to be higher as the oxidizer mass flow rate is increased. D. Harting... N.. "Pyrolysis and Combustion of Solid Fuels in Various Oxidizing Environments. AL. Journal of Propulsion and Power.. E. Dissertation.. K. DeZilwa. “Nano-Sized Aluminum. G.. J. Favorito. A. B. Libis. Journal of Propulsion and Power. “Scale-Up Tests of High Regression Rate Liquefying Hybrid Rocket Fuels”. 41st AIAA Aerospace Sciences Meeting and Exhibit.. Wright. K. 2002. K. G. S. Kuo.. E. "Regression Rate Behavior of Hybrid Rocket Solid Fuels. K. The functional relationships for aluminized HTPB and paraffin fuels were obtained in graphical forms. Reno.. A.. J. S.. G. H. References 1 Kuo. and Castellucci. Zilliac. Boyer. 98-3184. G.” Invited von Kármán Lecture in the Proceedings of the 37th Israel Annual Conference on Aerospace Sciences. and Risha. pp. pp. “Hybrid Rocket Combustion Study. G. 610-620.. D. 34th AIAA/ASME/SAE/ASEE Joint Propulsion Conference.” AIAA Paper 92-3302. and Arves.. L.. R. OH. L. R.. AL. J. pp. Indianapolis. B.. 3.. Results show that the position and the curvature of these curves depend strongly upon the oxidizer mass flow rate and initial port radius of the fuel grain.A. K. and Hybl. G. and Koch. pp. Lu. R. NV..” AIAA 99-2138.. A." Journal of Propulsion and Power. January 6-9. K. D. “Enhancement of Hybrid Rocket Combustion Performance Using Nano-Sized Energetic Particles. Cleveland. S. 13 Karabeyoglu. AIAA/SAE/ASME/ASEE 39th Joint Propulsion Conference and Exhibit 20 – 23 Huntsville. B. D. K. B. 621-630. “Combustion of Liquefying Hybrid Propellants: Part 1. 3 Risha.. B. July 7-10. R.. and Kuo. and Kuo.Based Solid-Fuel Characterization in a Hybrid Rocket Engine. 3. Johnson.. II-1 to II-31. 2 Chiaverini. A. G. “Surface Heat Release of HTPB-Based Fuels in Oxygen Rich Environments. “Performance Comparison of HTPB-Based Solid Fuels Containing Nano-Sized Energetic Powder in a Cylindrical Hybrid Rocket Motor. S... K. J. July 13-15. B. “Effect of Energetic Fuel Additives on the Temperature of Hybrid Rocket Combustion. Wehrman. A. pp. No. 12 Karabeyoglu. N. Boyer. N. Kuo. 03-1162.. E. 11 American Institute of Aeronautics and Astronautics . June 1993.. 7 Risha. W. Ray. (5) An implicit relationship showing the dependency of instantaneous fuel regression rate on the total mass flux was obtained. AIAA/SAE/ASME/ASEE 35th Joint Propulsion Conference and Exhibit.. 2002...... The radial increment of the regressing fuel surface can be correlated with time in a power-law form. “Instantaneous Regression Rate Determination of a Cylindrical X-Ray Transparent Hybrid Rocket Motor”. R. M. L. Vol 18. B. and Cantwell. Wehrman. N. and Cohen. AIAA Paper No. A. “Combustion of Liquefying Hybrid Propellants: Part 2...(3) Paraffin-based solid fuels containing Silberline® aluminum flakes showed an increase in linear regression rates of about 30% over the baseline paraffin fuel formulation. Begell House.. Richard E... 11 Risha. E. An increase of about 60% is seen for the difference between the aluminized paraffin and the Stanford curve fit results. K. 2002. Y. Evans. L. Balkanli. No. Acknowledgements The authors would like to acknowledge Dr. D.. Jones. Eds...” AIAA 2002-3576. CA. L. Anderson. 6 Teague. Inc. Stability of Liquid Films”. N. A..” Combustion of Energetic Materials. June 1992. July 2003 9 Risha.. VI. (4) The real-time X-ray radiography system enables the measurement of the instantaneous radius of the solid fuel grain with a cylindrical center port.. G. G. No. G. July 2003. A. 1. Serin. August 2003 10 Evans. 20-23 June 1999. L. A. The Pennsylvania State University. P..D.. M. 2002. K.. K. 8 Risha. Vol 18.. DeLuca. 2003. Kuo. “Importance and Challenges of Hybrid Rocket Propulsion Beyond Year 2000. A. D.. Cantwell. 4 Strand. 1998. and Cohen.. Carl Gotzmer and Mrs. This shows that the conventional power-law relationship between the average regression rate and average oxidizer mass flux cannot be applied to the instantaneous regression rates of solid fuel burning in hybrid motor conditions. C. M. D. K. C. Wehrman. K. “Hybrid Rocket Fuel Combustion and Regression Rate Study. Peretz... Kuo.” Ph..” AIAA Paper 93-2412. A. and Cantwell. General Theory”. Boyer. Koch. Los Angeles. February 26-28. Bowen of NAVSEA and Mr.” AIAA 2003-4593. Ray. A. Vol 16. Risha. K. K. Altman. Peretz. AIAA/SAE/ASME/ASEE 39th Joint Propulsion Conference and Exhibit 20 – 23 Huntsville. M. Kuo.. 101-115. J..

E. S. CRC Handbook of Chemistry and Physics.. C.” AIAA 01-3535. 67th Edition. A. B.. Salt Lake City.. K. 12 American Institute of Aeronautics and Astronautics . Kumar.. K. Boyer. 8 – 11 July 2001.15 Risha. “Combustion of HTPB-Based Solid Fuels Containing Nano-sized Energetic Powder in a Hybrid Rocket Motor.(ed). 16 Weast. 1987. G. A. AIAA/SAE/ASME/ASEE 37th Joint Propulsion Conference and Exhibit. R. p. and Kuo. Ulas. UT. B-40.