1

The Nature of an Advanced Propellant

RICHARD T. HOLZMANN
1
Advanced Research Projects Agency, Washington, D.C.
Although propellant chemistry research concerns itself with
everything from the synthesis and characterization of new
molecules to their formulation and combustion in a rocket
motor or engine, advanced propellant chemistry is primarily
directed towards the search for new oxidizers. This intense
effort is dictated by the greater contribution to energy which
can be made by a small improvement here since the oxidizer
normally comprises 70-80% by weight of the propellant
combination. A semitheoretical approach to the ultimate
energy achievable in propellants is presented.
' " phe propellant chemist knows what is needed to make a tru l y advanced
* propellantthe energy of the cryogenics ( fl u ori ne/ hydrogen) , the
density of solids, and the ab i l i ty to tailor properties to the mission at hand.
T he energetics are a direct consequence of the simplified specific impulse
relationship:
_ F _ thrust
* ib weight rate of flow
whi ch is a major aspect of propellant performance expressed i n units of
pou nd per pou nd per second, or more commonly, just seconds. T he
overall efficiency of the rocket system, i n tu rn, depends on the combined
efficiencies of the combustion chamber (where the propellants are
b u rned) and the nozzle (where the thermal energy is converted to kinetic
energy). A s a rough approximation i n screening potential propellant
combinations, i t is frequently considered that specific impulse is propor-
tional to:
1
Present Address: Aerojet-General Corp., Chemical Products Division, Azusa, Calif.
1
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In Advanced Propellant Chemistry; Holzmann, R.;
Advances in Chemistry; American Chemical Society: Washington, DC, 1966.
2 ADV AN CE D P R O P E L L A N T CHE MI S T R Y
T hu s, simply stated, a hi gh heat release yi el di ng l ow molecular weight
products is most desirable.
T he total figure of merit of propellant system performance is usually
taken to be specific impulse mu l ti pl i ed b y propellant b u l k density to
some exponent whi ch may range from 0.05 to 1.0. T he actual value of
the exponent depends u pon a complex relationship among the propellant,
its properties, the mission, and design criteria. T hus, the hi gh density of
the propellant i n a volume- limited application such as an air-launched
missile is extremely important whereas for an upper-stage i t is not nearly
so cri ti cal .
T he mission si mi l arl y influences the essential properties of the pro-
pellant ingredients. T he mi l i tary require rocket motors or engines whi ch
wi l l withstand operational thermal cycl i ng and handl i ng. I n addition,
they must be safe under combat conditions i n that they wi l l not detonate
i n a fire or when struck b y bullets, for example. T hey must be capable
of storage for yearsideally under hermetically sealed conditions. T here
are many who presume that a more energetic advanced propellant
necessarily must be less safe owi ng to the explosion hazard. T hey are
confusing the thermodynamic and kinetic parameters. O n the other hand,
rockets for space applications do not have the serious restrictions inherent
i n a mi l i tary mission, and thus cryogenics find a notable use. C onse-
quently, advanced propellant chemistry is not generally concerned wi t h
cryogenics b u t rather wi t h conferring the energetics of the cryogenics on
earth-storable l i qu i ds and solids. Wi t h some levity then, one may strive
to make hydrogen and fluorine l i qu i d or solid at room temperature!
T hi s leads directly to the context of this symposium.
T he first several papers concern themselves wi t h a theoretical ap-
proach to extremely advanced oxidizers; the next group examine oxidizers
pri mari l y b y studying important physical and combustion characteristics
i n propellants. T wo papers follow on binders whi ch act as fuels as wel l
as conferring desirable physical properties on solid propellants. A t this
point there is no coverage of the light metal hydri de fuels.
T he next five papers explore the physi cal , combustion and detonation
properties of l i qu i d systems. T he balance of the symposium is concerned
pri mari l y wi t h the more energetic oxidizers based upon nitrogen-fluorine
and oxygen-fluorine b ondi ng. I t is from this area that the most significant
improvements wi l l one day come, for wi t h the oxidizer comprising 70- 80%
of the propellant combination, a relatively small improvement here is
magnified as compared wi t h the fuel. T he use of metals, mentioned
above, i n both solid propellants and i n l i qu i d slurries, has been wi del y
pu b l i ci zed and wi l l not be discussed here. T hei r use, incidentally,
originated i n explosives technology and is commonplace at the present
time.
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In Advanced Propellant Chemistry; Holzmann, R.;
Advances in Chemistry; American Chemical Society: Washington, DC, 1966.
1. H O L Z MA N N An Advanced Propellant 3
A s b road as the coverage of this symposium appears, there is mu ch
propellant chemistry whi ch has not been i ncl u ded. T he experimental
determination of thermodynamic properties such as heats of formation
and equ i l i b ri u m constants as wel l as the calculations of theoretical per-
formance have been presented at other symposia. T he appl i ed chemistry
related to modi fyi ng polymers, and hence mechanical and b u rni ng prop-
erties of solids, have other forums. T he actual firing of solid motors and
determination of thrust and efficiency have been omitted whi l e the re-
search into combustion instability and the transition from deflagration
to detonation are only al l uded to.
The Advanced P r opel l ant
T he i deal advanced propellant is then one whi ch yields a hi gh heat
release i n the chamber and converts this to translational kinetic energy
i n the nozzle whi l e generating l ow molecular weight "perfect" gases. T hi s
latter requirement is rarely satisfied owi ng to the presence of H F , C O ,
C O 2 and H 2 0 i n the metal-free systems and to condensed metal oxides
i n the metal systems. T hi s two-phase flow prob l em wi t h a metallized
propellant can easily result i n a 5% efficiency loss. Therefore, although
the metals have an extremely attractive heat release, a penalty of 5% is
imposed from the start, even presuming perfect combustion efficiency.
Everythi ng considered, a performance of 9 2 % is close to maxi mu m effi-
ciency. T he metal-free l i qu i d bipropellant systems, however, are capable
of achieving 97- 98% of theoretical performance.
L o w molecular weight "perfect" gases clearly point the way to
hydrogen, whi ch accounts for the extreme performance of a nuclear
propulsion uni t. I n this system, the reactor merely heats the lightweight
gas. A l t hou gh methane and ammonia have also been considered for
nuclear applications, decomposed methane has a molecular weight of
5.4, ammonia of 7 whi l e hydrogen has a molecular weight of 2. I f too
hi gh temperatures are employed, molecular hydrogen wi l l dissociate into
atoms and absorb addi ti onal energy. I n a chemical propulsion system
the hydrogen wi l l come, i n the case of solids, from the binder and
NH4 CI O4 and, i n l i qu i ds, from N 2 H 4 and its derivatives or pentaborane
or diboranethe latter b ei ng space-storable b u t not earth-storable. M u c h
of the simple theoretical comparisons of oxidizers are therefore based on
combustion wi t h N 2 H 4 or B 5 H 9 for l i qu i ds and on more complex systems
for solids.
Barrre ( I ) has pub l i shed the performance calculations shown i n
T ables I and I I .
I t can be seen that future storable l i qu i d propellant systems are i n
the 300-31 5 sec. range whi l e future solid systems are around 290 sec.
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In Advanced Propellant Chemistry; Holzmann, R.;
Advances in Chemistry; American Chemical Society: Washington, DC, 1966.
4
ADV AN CE D P R O P E L L A N T CHE MI S T R Y
Table 1. Storables
P r opel l ant Composi ti on
1.4
Present Ammonium perchlorate
455
Al 4* plastic 267
455
Solid Future Ammonium perchlorate
LiBe + plastic 290 377
H N O r U D M H 276 348
H N O s - N 2 H 4
283 362
Present N 2 0 4 - U D M H 285 336
N 2 O c - N 2 H 4
292 356
H j O j - U D M H 278 345
H , O r - N , H 4
282 355
L i qui d C 1 0, F - N , H 4
295 360
L i qui d
Future N 2 0 4 - B 6 H 9 306 337
H202BHf 312 311
Cl F g - N 2 H4
294 444
H 2 O - A l - f plastic 289 435
Present H N O r - A l + plastic 273 414
N o 2 a o 4 - N 2 H 4 295 428
Hybri d C l F r - L i H 293 445
Hybri d
Cl F r - L i 318 369
Future N 2 04 - B e H 2
351 530
H 2 0*- B e H t
375 566
L i qui d
Hybri d
Table II. Cryogenics
P r opel l ant Composi ti on I
O j - H 2 391
O r - N 2 H 4 335
F r - H 2 410
F j - N 2 H 4 363
O r F r U D M H 345
F r - L i H 363
Fr- O ^pl ast i c 343
F 2 - B e H 2 395
02 - B e H 2 371
F t - AI H, 353
lu
109
365
185
476
398
476
412
604
486
551
Table III
N 2 F 4
O F j
h.p. c.
- 74
- 145
NtH<
333
345
M i
333
359
B arrres analysis di d not mention N 2 F 4 or O F 2 since these are "soft"
cryogenics, i n that their b oi l i ng points are low. T hei r performance is
excellent, however, as T ab l e I I I shows.
T he performance of F 2 , O F 2 , and N F 3 or N 2 F 4 shows where the
synthesis potential of rocket oxidizers is.
A n attempt has been made here to determine the relative value of
an oxi di zi ng group as a propellant wi t h a model fu el , N 2 H 4 . H ydrazi ne
was chosen for si mpl i ci ty and avai l abi l i ty of calculations. T he AHf has
been chosen i n most cases b y analogy. Fo r example, to obtain one point
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In Advanced Propellant Chemistry; Holzmann, R.;
Advances in Chemistry; American Chemical Society: Washington, DC, 1966.
1. H O L Z M A N N An Advanced PropeUant
5
for an O, one may use one- thi rd of +30 kcal . / mol e, the / / , of 08 . Fo r
another point, one-half of 3.48 kcal . / mol e, the , of 02 ( 1 ) . In this
manner a series of curves were generated (Fi gur e 1). Inherent then i n
any calculation of this type is the nature of the group to whi c h the oxi di z-
i ng group of interest is bonded. Several conclusions whi c h can be dr awn
from such a curve woul d have been approximated " i nt ui t i vel y" by the
synthesis chemist by reason of his background knowledge.
< N
2
H
4
1000 psia
t h i f f i n
* . 14.7 psia )
+60 +40
+20 0 - 20
*Hf ( K C A L . / MO L I )
Figure I. Oxidizer group contributions
- 40
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In Advanced Propellant Chemistry; Holzmann, R.;
Advances in Chemistry; American Chemical Society: Washington, DC, 1966.
6 A D V A N C E D P R O P E L L A N T C HE MI ST R Y
Table IV. Relative Order of Oxidizing Power
F C 1 F 2
O F N O *
N F t C 1 0 4
GI F 4 N O ,
C I O ,
If one chooses a constant AHf> an index of oxi di zi ng power may be
obtained. Fo r a AHf = 10 kcal . / mol e, the order i n Tabl e IV is ob-
served.
If one chooses a target lm there appear to be certain groups whi c h, i f
embodied i n an oxidizer, woul d have difficulty i n attaining the objective.
If 310 sec. is chosen as the target, the groups i n Tabl e V woul d not be
expected to reach the objective unless combi ned wi t h the hi ghl y energetic
groups above them i n Tabl e IV.
Table V. Oxidizer Groups Not Expected to Yield 310 sees.
C 1 F 2
N O i
CIO4
N O *
C I O ,
The steepest slopes observed are those for F and i ndi cati ng
the dramatic contri buti on to impulse by a slight increase i n AHf. In
general, then, compounds have a more positive slope than CI com-
pounds, demonstrating the relatively better performance of as a
carrier atom over C I .
The value of such a curve (see Tabl e VI) may be tested by l ocati ng
the known oxidizers relative to the group contribution curves.
Table VI. Correlation of Known Oxidizers with Group Contributions
Oxi di zer L ocati on Cor r el ati on
F 2 on F excellent
O F 2 midway between O F and F excellent
N 2 F 4 on N F 2 excellent
O2 on excellent
N F 3 . . . poor
C1F| midway between C1F 4 and C1F 2 good
CIO3F above C1F2, much above CIO3 poor
N 2 0 4 close to N O 2 good
N 0 2 C 1 0 4 between N 0 2 and extrapolated CIO4 good
C 12 07 far removed from extrapolated C 104 and CIO* poor
Hypotheti cal oxidizers may be tested i n the same way. However, the
question arises as to what &Hf to choose, and this is the pri mary l i mi t a-
ti on. Havi ng the curve, woul d one have chosen AHf C1 2 07 = +5 5
kcal . / mol e or AHf N F 3 = 29 kcal . / mol e?
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In Advanced Propellant Chemistry; Holzmann, R.;
Advances in Chemistry; American Chemical Society: Washington, DC, 1966.
1. H O L Z MA N N An Advanced Propellant
7
I n conclusion, i t appears that the most desirable oxidizer is one whi ch
packs i n the maxi mu m fluorine bonded to itself ( F 2 ) , bonded to oxygen
( O F 2 , 0 2 F 2 , 0 3 F 2 , 0 4 F 2 ) , or bonded to nitrogen ( N F 3 , N 2 F 4 , N 2 F 2 ) i n
decreasing order of energy. T he fuel must pack i n the worki ng fluid
hydrogen whi l e b oth should have hi gh heats of formation and yi el d
products wi t h l ow heats of formation. Wi t h the covalent l i qu i ds and
gases our ab i l i ty to predict heats of formation is quite good; wi t h ionic
solids the u nknown contributions from lattice energy preclude this.
L i ter atur e Ci ted
(1) Barrre, M., Office Nationale d'Etudes et de Recherche Aerospatiales,
Missiles Rockets 15, 32 (1964).
RECEIVED May 1 0 , 1 9 6 5 .
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In Advanced Propellant Chemistry; Holzmann, R.;
Advances in Chemistry; American Chemical Society: Washington, DC, 1966.