AD-A153 051 co

TECHNICAL REPORT BRL-TR-2641

_LI .
SWi

LIQUID PROPELLANTS FOR USE IN GUNS

A REVIEW

Nathan Klein D
" ~DTIC :L.:
February 1985 P

Low
Reproduced From B
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US ARMY BALLISTIC RESEARCH LABORATORY

ABERDEEN PROVING GROUND, MARYLAND

.T 04' .,Aq 071.,

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I. REPORT NUMBER 12.GOVT ACCESSION NO. 3. RECIPIENT'S CATALOG NUMBER
TECHNICAL REPORT BRL-TR-2641 !D-,4/11.5 5/
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Final
LIQUID PROPELLANTS FOR USE IN GUNS - A REVIEW
6. PERFORMING ORG. REPORT NUABER

7. AUTHOR(,) S. CONTRACT OR GRANT NUMBER(*)

Nathan Klein.

9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT, PROJECT, TASK
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US Army Ballistic Research Laboratory
ATTN: ALMR-IBD 1L162618AH80
Aberdeen Proving Ground, MD 21005-5066
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If. SUPPLEMENTARY NOTES

IS. KEY WORnS (Continue an reverse *)de if neceseary and Identify by olock nimber)

hydroxylammonium nitrate artillery

HAN caseless ammunition
monopropellants stability
aqueous systems fuels, oxidizers
20. AUSTN ACT (CVmrnxe a- rerm side if nersmy am Id"sWii by block minbe)
The use of liquid propellants in guns is reviewed both historically and in
terms of the characteristics and properties required of such materials. The
physical and chemical characte-istice required of propellant formulations is
strongly predicated on application in a particular'weapons system and, based
on such system requirements, the aqueous monopropellants consisting of the
nitrate salts of hydroxylsmine and an aliphatic, tertiary amine are shown to
,'currently hold the greatest promise for use in a :eeium-ti-large caliber

Do re*., 1473 £ Dr onO wGE I O V S S iSOO L E.T •"

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. ... SCU.... CLASSIFICATIO. OF THIS PAGEMINO.R Data
 UNCLASSIFIED
SECURITY CLASSIFICATION OF THIS PAGE(Uim Date Enteed)

20. Abstract (Cont'd):

arAt;lery gun. Rationale for the selectiun of these compounds is described

and .he properties and reactions of these mixtures are discussed. The review
does not discuss the gun systems considered but Is limited to the propellants,
their properties, and reactions.

UNCLASSIFIED
SECURITY CLA&SIFICATION OF THIS PA0erlUn Date Entered)

',-.. .- .. •",
: -, . . "- ,."....,. ,. . -, ,..•.- .. . . . . . , .. . ... .. .. .:. . .- , .. .. .. ,.. . .. . . . -. . .. ,. ;.
 TABLE OF CONTENTS

Io INTRODUCTION . ....................................................... 5
IIo BACKGROUND .... o ... . ..... o.oo,.~~o.. o .. 7

A. Nitrogen Chemistry. .o. ... ...... .. ....................... ... . .8

B. Nitrate Ester Containing Formplations ........................... 9

IIIo WATER MISCIBLE MIXTURES..... . 00..0... ......... . ..0 . .. o..o.. ..11

A. Solution Structure *.. o o........ ...... ....... o....... ....... o... o.... I
B 'Acid-Base Reactions.. ..... .o ... . ... ....... .o. .......... 12
C. Nitrate Salts as Oxidizers......... ...... .. .... .... -,....14

IV. THE HYDROXYLAMMONIUM NITRATE PROPELLANTS.. ... .....

o. ...... ........... .15
.

A. Thermochemistry of the HAN Propellants......................... 16

Bo Fuel Components .......... .... ... ............................. . . ... 18

V. PROPELLANT CHEMISTRY.. .o...... .... . ... ............ ................. .. 19

A4 Experimental Studies .... . ..... . .... .. .... ... ........................ 20

B. Effect of Fuel Structure on R~action Rate....................... 22
C. Effects of Impurities on StabtJity .. o............................26

FA CoMats nd.P.o uci...i.i...... ............. '...o

..... . ....... 29
G. Dem ilita .............................. o...... 28

C. StabilityFla... n.B.s................................ooo.....28
..
D To i c t . .o
...
oo '28
E. Vicosty .. 29
F. Cost and Producib3lity.. ......... .. ...
ooie 29
G. Demilitarization and Disposal-...... ...... ................ 29
H. . . ... ........
Muzzle Flash and Blastooo

ACKNOWLEDGEMENT ..... ... .... ...... o.............. ......... o.... t..... .30

REFERENCES o . .. . o . o o o~ . o o o ~ o . .* . o. . oo . s31

DISTRIBUTION LIST~ o , .. . o o o o. o o o o s o o o . oo . o oo . .35

E•PZL E C T E" z-et + +d':,+

SAPR 2 5 N95,:1 ,._

IIHI +1it , A~a C e,

 I. INTRODUCTION

The concept of a gun using liquid rather than solid propellant is

attractive from both theoretical and practical considerations and has thus
received serious attention to a greater or lesser degree since World War
II. Much of the incent.ive for consideration of liquids as propellants for
guns derived from the Fgreatly enhanced interest in rocketry that developed
during ann immediately aifter the war and a history of the development of gun
liquid propellints parellels the search for suitable materials to be used in
rocket motor's. Relatively little consideration was given to t~z sometimes
profound differences tetween' rockets and guns. The majority of the early work
dealt with engineer,.ng studies of gun systems, attempted to establish
ballistic properties, and in most cases were empirical and simply considered
the fact that the liquid would contain substantiE-ly more energy per unit.
volume than would ýi solid propellant. A fair variety of gun concepts were
studied, cove ing a range of complexity from the simple system of a cased
liquid charge tV the rather esoteric, direjt injection of a hypergolic
bipropellant mixi.ure into a gun chamber. The usually inadequate
consideration ,gi~en to the properties and characteristics of the propellants
in these early siudies probably led to the failure of many of these concepts.

Rationale -or the development of a liquid propellant gun, as with any new
weapons system, must invoke some substantial improvement over systems already
in existence.; Historically, the use of caseless ammunition, a significant
increase in wizzle velocity, and improved logistics, have been the incentives
for developnnt of this fairlv radical gun concept. Caseless ammunition
presents a inumber of potential advantages to the user since it is more
versatile. /
For example, artillery zoning is controlled by the quantity of
propellant 4metered into the gun rather than by the use of fixed bag charges
and is th Is infinitely variable. In addition, propellant is shipped and,
handled it; bulk requiring substantially less space both in storage depots and
in 'the vehicle that houses the gun. Commonality of propellant for guns of
differentv caliber is readily obtained. In a vehicle, the propellant can be
stowed in tanks of virtually any shape rather than in racks and, of course,
cartridg.'e case disposal is non-existent. As to increased muzzle velocity, a
matter pf considerable importance if the weapon system is to be either a tank
or anti-aircraft gun, it was generally felt that the higher energy content
availaole in a number of the propellant formul'ations considered would
translate in some reasonably straight-forward way into increased muzzle

-ý . 'Barr,, E.J. Wilson, Jr,., et aZ, "Liquid Fuel Catapult" Experiment,

Ini3., Richmond; VA, T.P.No.31, 1947.

2
JI,.C. Clark, 1,anition. Rutger~s Univere.ity-Piea., New, Briunswick, NJ, 1972.

'C.R. Newmazn, "Investigation of Application of Liquid Pr~opellants to 90 mi

Tank Guns," Detroit Controls Corp., Redwood City, CA, Rpt., Nr. RC-184, 1956.

/4B.A. Niemeier, D.L. Swanson, and H.B. Forney, "Liquid Propellant Small
/ Caliber Gun With Repetitive Fire," Experiment Inc., Richmond, VA, T.P.No 58,
/ 1953.

.5

• .. •..o •. ., o °° '' * . . . . . *...*• • • . L . . , . o • ,, . . . .

velccity, an argument-by-analogy to solid propellants. Improved performance
in general was frequently cited as an incentive for liquid propellant gun
development, but such improvements are sufficiently vague that it couid
encompass virtually any characteristic considered important to a potential
user an•d will not be addressed until specific propellant formulations are
discassed.

Rec:int successes in gun technology and in the devplopment of suitable

propellants have been achieved and a review of these subjects at this time
would appear beneficial to the gun community. Gun technology will not be
discussed to any extent in this report although it is clearly undnrstood that
the liquid propellant for use in a gun is to be intimately linked with the gun
system. Liquid propellant gun technology has been reviewed recently 5 and the
reader is. referred to that publicatior if detailed information on the subject
is desired.

Since discussion is to be limited to gun propellants, two rather

elementary censtraints can serve to begin such discussion. First, all
propellants are defined as self-contained, that is, all of the fuel and
oxidizer must be present in the mixture at the time it is to be used, and
second, gun propellants should be limited in composition to the elements C, H,
0, and N. Although a propellant is self-contained in fuel and oxidizer, the
fuel/oxidizer ratio is a major factor in its performance both in a gun and as
a material that must be stored and handled. Energy content is near maximum
when the ratio of fuel and oxidizer is balanced, that is, when neither
material is present in excess, and such mixtures are called stoichiometric.
The restriction regarding composition is imposed because the presence of other
elements, notably the halogens, sulfur, or phosphorus, in significant
concentration, will severely corrode the gun and unacceptably limit gun
life. This restriction is not new nor is it unique to liquid propellants, but
is of considerable importance in that it rather severely limits choices of
propellant components.

One appears to have substantially more freedom in designing and

formulating liquid propellants than one has with solids. For example, a
bipropellant is a mixture in which the fuel and oxidizer are stored separately
and are mixed only at the time of use, whereas a monopropellant is a material
in which fuel and oxidizer are combined either as a single compound or as a
mixture that, on at least a macroscopic level, is homogeneous. A bipropellant
can, if desired, be hypergolic; that is, the mixture, upon its creation,
promptly begins reacting so that no' igniter is needed in order to fire the
gun. Monopropellants cannot, of course, be hypergolic. Since solid
propellants are premixed, all' solid. propellants are monopropellants. There
are, potential advantages, to the use of bipropellants that have resulted in
their serioss consideration from time to time. Unplanned initiation in
storage, either accidentally or 'as a result of' enemy action, is usually a
remote -possibility and presents little hazard because neither component is

5W.F. Morvison, J.D. Knapton, and M.J. Bulman, "Liquid Propellant Gans," in
ru, Pwnuls,1p3, ZaahAinnlay,, L.StiefeZ, ed., Progress i:n Aeronautics 'nd
Astronautics Series, (in press).

6
capable of releasing significant amounts of energy by itself. In contrast,
unplanaed initiation of a monopropellant, can ! quite dangerous. The
separation of fuel and oxidizer also permits consideration of mixtures with
extremely high energy content. Comparable energy content in a monopropellant
is beyond practical. consideration because stability generally decreases as
energy content increasrs. Hypergolic bipropellants consisting of hydrazine
and hydrogen peroxide, or hydrazine and nitric acid, 6 were examined in the
1950s, showing the strong dependence of this early work on rocketry and, not
3urprisingly, abandoned because the mixtures were exceedingly difficult to
handle and control. Non-hypergolic biprope.lants, cr•nsisting of nitric acid
and various hydrocarbons, have been studied in greater
detail and reasonably
successful results obtained,7 although this system was also eventually
abandoned. The logistics of a bipropellant system are far more complex since
two liquids must be stored, transported,, and accurately pumped into the gun
chamber and the extremely high energy contenc achievable is often through use
of materials with sufficiently noxious properties as to be practical only in
certain unique applications, usually ones in which operating personnel have no
direct contact with the gun, such as an aircraft cannon. Although both bi-
and monopropellants have been considered for use in liquid propellant guns,
the logistic and engineering difficulties associated with bipropellant use are
such that present emphasis in liquid propellant development: centers almost
exclusively' on monopropellants and, therefore bipropellants will not be
discussed further.

The development of propellants has been evolutionary with understanding

slowly acquired as a result of past failures or partial successes. It would
seem doubtful at this time that a universal propellant, suitable for use 'in a
number of diverse gun systems, that is, systems with different principles of
operation, can be. developed in the near future. Active research is presently
underway in the area of liquid propellant development and characterization
and, although the material presented will be current, it is far from complete.

II. BACKGROUND

Compounds of the elements C,H,O, and N to which discussion is to be

restricted, must be considered in terms of their use either as fuel or as
oxidizer, or possibly, as both. Carbon and hydrogen are exclusively fuels
since any reasonable compound of either of these elements in a propellant
composition can only be in form such that both carbon and hydrogen would be
oxidized. Oxygen itself can serve as oxidizer either in the form of molecular
02, an impractical substance-An a liquid, propellant gun because of, the
cryogenic requirements associated with the use of 02 as a liquid, or as
hydrogen peroxide which, because of stability constraints and difficulties in
handling, is aiso not a practical material. Thus, the element nitrogen is
left as the sole oxidizer source.

OT.M. Broxholm, £.C. Elmore, and W.H. Giedt, "Liquid Propellant Gun Systems,"
Detroit Controls Corp., Redwood City, CA, RC No. 170, 1955.

7H.D. Mallory, J. Ballistics, Vol 5, p 1213, 1981.

. . . . ,,. . .. . . . ,.. . , . * . *., . . , *. Ill

A. Nitrogen Chemistry

Nitrogen exists in total of eight oxidaLion states in, more or less,

stable form, examples of which are shown in Table 1.

TABLE 1. OXIDATION STATES OF NITROGEN

Oxidation State Examples

-J NH 3 , NH 4 +
-2 N2 H4 , N2 H5 +N 2 H6 ++
-1 NH2014, NH3 OH+
0 N2
+1 N2 0, N2 H2 0 2 .
+2 NO
+3 HONO, NO2 7
+4 NO2 , N2 0 4
+5 HNO 3 , NO3 -, NO2 , R-NO3

With the exception of the -3 and +5 states,, nitrogen is capable of both

oxidation and reduction. It can, therefore, serve as fuel or as oxidizer as
conditions warrant, thereby producing an extremely rich and complex
chemistry. As can be seen from the Table, the +5..tate, either in its ionic
forms as N03- or NO2 +, or as the nitrate ester, R-N0 3 , is readily available to
serve as ox 4 dezer. The oxidation states between 0 and +4 present compounds
that are either gaseous or not especially stable.

It is not fortuitous that nitrate is the oxidizer of choice since this

property causes nitric acid, the parent compound from which the nitrates are
made, to be one of the basic industrial chemicals wigh annual production of
6.9 million tonnes in 1982 in the United States. A variety of HNO 3
concentrations are available, oxidizing ability increasing with increasing
concentration. The reason that nitric acid is a powerful oxidizer and that
oxidizing ability increases with concentration is because of the dissociation
leading to the formation of nitronium ion:

HNO 3 - NO2 + + OH- . 11

This dissociation is in competition with the more commonly known acid

dissociation:

HNO 3 ÷ H+ + NO3- 121

which produces nitrate and accounts for the acidic properties of the acid.
The reaction shown in equ&tion [2) is oversimplified, and is, in fact,
incorrecL. The hydrogen ion, commonly written H+, is always associated with
some solvent,, usually water, and is never observed as a -free proton under
conditions in which chemical reactions are usually considered. The
equilibrium that Is the combination of reactions (1] at..! (21 is strongly

8 Chem. and Eng. News, A-m ichn Chmian-a-y-, Washi•ngton, DC, Vol. 62,
No. 18, p 11, 1983.

• ... i. >...:...
•. .•,: .• ... .... •..> .• . .. !,.• . •, •. -,.-.:.' 8 . . . .. . ,
influenced by the type and quantity of other materials. The presence, in
nitric acid, of a base. of which water is an example, strongly favors reaction
[21 whereas the presence of acids, such as H SO4 or F favors reaction [11,
a matter that will repeatedly be stressed in much of the discussion of
propellant chemistry that will be presented. The cor:osivity of the acid is
due, in part, to both reactions [1) and [2] with one or the other being
dominant under specific circumstances.

Nitric acid itself, although c-n excellent oxidizer, has virtually no

potential for use in a functioning gun propellant. The requirements that it
would impose on the system becatise of its extreme corrosivity to equipment,
and the hazard it would pose to personnel is such that its use is essentially
dismissed. Nitrates, either as ions, or as nitrate esters in nonionic media
are, therefore, the sole potential oxidizers in a liquid propellant
formulation.

B. Nitrate Ester Containing Formulations

A5 previously stated, monopropellants are homogeneous liquids that

contain both oxidizer and fuel. The oxidizer of choice is nitrate and the
mixture may or may not be miscible with water. Considerations begin with
those monopropellantq that ar immiscible with water. In such case" the
nitrate is preL-nt as the nitrate ester of some relatively simple, organic
molecule. Molecular weight must be kept low because the material is to be a
liquid over a fairly broad temperature range. Examples of the liquid range of
several nitrate esters are presented in Table 2

TABLE 2. PROPERTIES OF SELECTED NITRATE ESTERS

Molecular Meltiag Boiling

Compound Weight Point (C) Point (C)

CH 3 -NO 3 77 -82 65 d
CH3 -CH 2 -NO 3 S1 -94 88
CH3 -CH 2 -CH 2 -NO 3 105 lII
(CH 3 ) 2 -CH-N0 3 105 -82 102
CH 3 -('H, 2 -CH 2 -CH 2 -NO 3 119 07 136
(CH 3 -CH 2 )(CH 3 )CH-NO 3 119 124
(CH3)2-CH-CH2-NO3 119 - 123
(CH 3 ) 2 -C-Nih 3 119 21 (5 mm)
CH OH3)-CH N0 3 '107 <-20 91 (20 mm)

(LH2-NO3)2 , , 152 '-22.8 199 d

CH2(OH)-CH(OH)-CH2-NO3 137 54 155
(CH 2 -OH) 2 -CH-NO 3 137 58 155
CI 3-CH(NO
CH3-(CH )-CH -NO3 •166
2 -NO 3 ) 2 2
-42 92 (10 mm)
6,6 -38 108 (10 M)
CH2(OH)2-CH(NO3)-CH 2 -N0
3 182 - 146 (15 mm)
CH(OH)-(CH -NG ) 182 26 146 '(15 mm)
CH(NO 3 )-(Ca2 -N8 3 52 227 13.5 145 d

""Encyclopedia of Explosives and Re'ated Items," PATR 2700, U.S. Army

Armaments Research and Development Command, Dover, NJ, 1983.

.... ,,lII.... . .. . . ..
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
The nitrate e3ters do not exhibit the corrosivity of the acid because they are
not ionic although the energy of the nitrate group is, to a large extent,
retained. This well recognized property leads to tneir use in solid
propellants, liquid and solid exDpisives, and to their early consideration as
liquid propellant ingredients 10.LI As seen from the Table, a limited number
of nitrate ester. oxhitit both sufficiently iQw freezing point and high
boiling point to be used as the pure compounds and most of the formulations
considered 1 2 were mixtures.

Many of the nitrate esters are readily detonable, a trait far less common
in ionic nitrates. Possibly. the fact that nitrate esters are uniiolecular,
covalent compounds relates to their tendency toward detonability. Discrete
species migration and combination, both requiring a finite time for
completion, is not needed for reaction of these compounds as it is with ionic
nitrates. in any case, these materials mugc be either fairly foel rich, thus
decreasing their sensitivity, or dilute. with more or less inert organic
material, or both, in order to be used. Either of these courses of action
lowers the energy contenlt of the propellant and make this type of material
less than an ideal choice for the use intendied. In addition, the. nitrate
esters are physiologically active causing profound changes in cardiovascular
function and, in Fact, compounds closely related to materials that have been
considered are used as drugs. The toxicity of nitrate esters is avoided as a
practical matter in solid propellants, in which they are the major, energetic
components, either because vapor pressures are extremely low or because the
charge is packaged in such manner that the propellant is not handled directly
by opirating personnel. Since the method of employment envisioned for liquid
propellarnts is fundamentally different, i.e., the use of caseless ammunition,
toxicity considerations are far mere restrictive and nitrate ester containing
mixtures can not be seriously considered as candidate propellants. They have
been extensively used in test fixtures, however, because or their ready
availability, non-corrosivity, and the fact that maaiy of the parameters that
must be determined in detail in the working gun can De determined using this
type of formulation. Thus, the propellant OTTO 11, which contains propylene,
glycol dinittate as a major component, has been employed rather extensively in
gun development studies. 1 3 This mixture is fuel rich in order to decrease
detonability and tbUs does not burn cleanly. Based on the results obtained,
it would appear doubtful that a non-aqueous monopropel ant could be used in a
fielded weapon system.

1 0 "Evaluation of New Propellajno For Liquid Propellant un Systems," Redel

Inc., North Hollywood, CA, Contract Report No, CPR-4, 1955.

"11"Investigationof Propellant-Reactions For Liquid Pro ellant Gun Systems,"

Redel Inc., Anaheim, CA, Report on Contract NOrd-1214 , 1956.
12
"Discussion of a Cool Burning Flashleas Liquid Monop pellant for Fixed
Ammunition," Expc;riment inc., Richmond, VA, TM-814, 1956.

1
*J. Manday, I. Magoon, W.F. Norrison, and J.D. Knapton, "Preliminary Report
on Test Firing of a 105 MM Regenerative Fixture," Pro eedingaof 2Oth JANNAF
Combustion Meeting, CPIA Pub. 383, Vol II, p 161,. 19 3.

i0

"-. ......
. .. ... ..... . "
".
. .. . . *.'.*.".."..-*..... .
 A summary of the discussion to this point indicates that there seems
little potential application for either bipropellants or for mortopropellants
containing significant quantities of the nitrate esters in a liquid propellant
gun. This essentially leaves one class of prope'lants to be considered,
namely, the ionic mixtures in which miscibility with water is the common
feature. The oxidizer of choice remains nitrate and, in. subsequent
discussion, the choice of counter-ions for nitrate will be reviewed.

II. WATER MISCIBLE MIXTURES

The aqueous monopropellants are generally ionic mixtures. Nitrate

remains the oxidizer of choice but is now used as the nitrate ion, NO3-. The
nitrate-nitronium equilibrium, discussed earlier, applies to the nitrate ion
in much the same way as it does to the acid. A variety of cations can be
considered as the counter-ion for NO3- with other substances present tc give
the desired physical and cheirical properties to the completed mixture. Since
much of the discussion that follows deals with various ionic compounds, it is
well to present a brief dcescription of ionic materials in water at this point.

A. Solution Structure

A single crystal of ice at atmospheric pressure is a well ordered

structure with an extensive network of hydrogen bonds linking an unshared
electron pair of an oxygen atom to one of the hydrogen atoms of a neighboring
water molecule. Because of the unshared electron pairs on the oxygen atom, a
higher electron density resides in its vicinicy and results in a significant
dipole moment for the molecule. These hydrogen bonds are substantially weaker
than the covalent bonds of the water molecule but are strong enough to
profoundly affect the physical properties of the crystal. As the ice crystal
is warmed and melts, the hydrogen bonding network is not promptly destroyed
but is instead reduced to small groups of molecules called clusters. These
cluster3 give liquid water its unique and rather. unusual physical
properties. Incidentally, hydrogen bonding is not a phenomenon unique to
water and is seen in ipany organic compounds, accounting, for example, for the
relatively high, boiling points of alcohols and carboxylic acids.

If ionic material is added to water, the molecules in the immediate

vicinity of the ions rotate, orienting either positive or negative dipoles
toward the ion depending, of course, on the Ion's charge. This arrangement of
ions surrounded by dipole oriented, water molecules is the structure that one
finds in dilute, aqueous solutions. In some cases the attraction of the ion
for the solvent water causes disruption of the hydrogen bonding network of the,
water clusters without creating a more highly -organized network. Such ions
are called "structure breaking." , In other cases, the arrangement of the
hydration sphere, invol,,es larger numbers of water molecules than enisted in
the clusters and sucm ions are commonly called "structure making.'" As the
concentration of ionic material increases, insuffidient water remains
available to maintain this process and the properties of the mixture 'change,

. 1 4 J.L. Kavanaugh, Water and Solute-Wate' Interactiones Hciden-Day Inc.,

San Francieco, CA, 4,964.

11

....- -. ,., . .. . . .. . . . . . . . . . ..-.

. . . . _...........
. ...... , *. ¾ . .... ..'"" • ...•- " • • ••. ..-" •..... = " 1
 making it difficult or impossible to describe the properties of concentrated
solutions by extrapolation from dilute solution data. Much of presently
accepted solution theory is based on extremely dilute solutions and fails to
account for observed'properties of concentrated salt-water mixtures.

If a salt with adequate thermal stability is heated, the salt melts,

forming a liquid. Such molten salts routinely have vastly different
" properties from those of their aqueous solutions. Combinations of molten
"* salts frequently form eutectic mixtures with properties that are not simply
the sum of those of their pure components. If a molten salt has a
sufficiently low melting point then eutectic mixtures with water can be
obtained. In such cases one often can obtain liquids over almost the entire
composition range from pure water to pure salt, the liquid state being
retained at temperatures well below the freezing points of both pure
components.

B. Acid-Base Reactions

Returning now to the aqueous monopropellants, the nitrate anion, serving

as oxidizer, must be coupled with one or more suitable cations. Available
cations are hydronium and ammonium, either as such or as one of '.ts numerous
homologs. The coupling of the nitrate ion with hydronium results in nitric
- acid, already discussed and dismissed as too corrosive' for use in an
. application that involres the close proximity of operating personnel.
Ammonium as the co'ipling cation produces, in the simplest case ammonium
nitrate, NH4 NO3.

The ammonia molecule contains three covalent N-H bonds and a lone pair of
electrons. Protonation of the lone electron pair produces the ammonium ion,
. NH4 +. The three covalent bonds are capable of undergoing substitution for the
hydrogen, thus producing a variety of compounds, many with chemical and
physical properties markedly different from those of ammonia. Replacement of
one or more of the hydrogens with carbon results in the amine's, a large family
of organic compounds. most of which are basic. In addition, an N-H bond can
be replaced by N-N forming the hydvazines, or by an N-0 forming the
* hydroxylamines. The limitation that only the elements C,H,O, and N be used in
*. propellant formulation thus still leaves a fair number of compounds to serve
as candidates.

A simple description of the' reactions of acids with certain types of

"bases involves the dissociation of the acid:
HA + H20 + + A-
0+3O+ [31

-' and the reaction:

H3O+ + B + HB+ + 1120 [4]

* The-bases, B, considered in reaction [4] are ones in which an unshared pair of

* electrons are available' for reaction with the hydrogen ion, as, for example,
* ammonia and its homolog's. The ease with which the electron pair attracts the
proton is a measure of the strength of the base and the ease with which the
* acid dissociates is a measure of the strength of the acid. Equilibrium
"constants exist, for both reactions [3] and [4] and the. constant pertinent -to
12
 equation [4] is defined as:

[H201 S[HB+]151
Kb [B] [H3 0+]"

The species HA, B, and their ions are in equilibrium and the concentrations of
the various entities in solution under a given set of conditions is a result
"of such equilibria. For convenience, the, equilibrium constants are often
given as pK, where pK - -log K. A list of such values, pertinent to the
discussion at hand is given in Table 3.

TABLE 3. BASICITY OF VARIOUS AMINES1 5

*Compound pKb

(CH3-CH 2 ) 2 -NH 3.07

(CH3-CR 9 ) 3 N 3.28
C•13-NH2 3.38
CH3 -CH 2 -CH2 -CH 2 -NH2 3.39
S(CH 3 -CH2 )(CH 3 )CH-Nh 2 3.44
(Cft 3 ) 3 C-NH2 3.54
(CH3 ) 2 CH-CH 2 -NH2 3.59
(CH3 ) 3 -N 4.20
NH3 4.76
NH2 -NH2 6.06
(CH2 (OH)-CH 2 ) 3 N 6.24
NR2 -OH 8.04

The table is arranged in order of decreasing basicity. One sees that all of
the simple, aliphatic amines are more basic than is ammonia, differences being
"due primarily to steric effects. The presence of an Olt group on the beta
carbon of the amine causes trie~hanolamine, (CHi(OH)-CH 2 ) 3,N, to be 30 times
less basic than ammonia and replacement of an amine hydrogen by an, OH group
causes hydroxylamine, NH2OH, to be-almost 2000 times less basic than ammonia.

A strong acid when reacted with a strong base, results in a mixture that
' consists almost, exclusively of the salt, HB+A7. If either the acid, the base,
or both are weak, then the 'result of their mixing could contain significant
quantities of the original materials at the expense of the desired salt.
Considering that' the physical and chemical properties of the starting
* materials are usually quite different from those of their salts, this latter
" point becomes far from trivial. Ammonia and its homologs are basic, although
to different degrees. Thus, all of these compounds are capable of forming
salts with acids and, except for hydroxylamine, these salts would be expected
to be stable even if the acids were fairly weak. Since hydroxylamine is a

a15'ange' ,Handbook of Chemistry," 12th ed., J.A. Dean, ed., pp 5-15, Mc Graw
Hill Book Co., New York, 1979.

13
 very much weaker base than are the other compounds, stable salts would be
formed only with strong acids. Attempts to produce the hydroxylammonium salts
of the carboxlic acids, for example, fail to give stable products even with
formic acid,1 the strongest acid in this group. All of the ba,--ýs listed in,
Table 3 would, however,. be expected to yield the appropriate nitrates and,
*- indeed, this is the case.

*' C. Nitrate Salts as Oxidizers

Resuming the discussion of the nitrates of ammonia and its inorganic

homologs, the first of which, the ammonium ion, NH4 +, leads to NH4 NO3. This
salt melts at 170 C and forms solutions with water to a maximum concentration
* of approximately 10 mole/liter, 18 the melting point of the salt being too high
to permit the formation of eutez•ic mixtures that are liquid at or near room
temperature. At 10 Molar, the concentration of nitrate is not sufficiently
high to permit consideration of ammonium nitrate as an oxidizer in the
application under discussion.

Turning next to hydrazinium nitrate, N2 H5 NO3 we find a melting point of

62 C,19 almost adequate for the use being considered, although water-N.H.HNO3
mixtures would probably solidify at too high a temperature 2 0 to saltisfy
requirements for an operational gun propellant. An additional drawbac Ito
consideration of N2 H5 N0 3 is the fact that it is fairly easily detonated" a
most undesirable trait. The combination Of melting point and detonability
4 would discourage consideration of hydrazinium nitrate as a propellant
*- oxidizer.

The considerations that caused elimination of N2 H5 N03 also eliminate the

dinitrate of hydrazine, N2 H6 (NO3 ) 2 , which has an even higher melting point of
80 C and is more easily detonate'd than is the mononitrate. This leaves
hydroxylammonium nitrate, Ni 3 OHNO 3 , (HAN), as the only remaining inorgani
nitrate salt containing only the elements H,O, and N. HAN melts at 48 C,
and forms salt mixtures with water that are liquids at room temperature
covering a concentration range from almost pure salt to pure water. In
addition, HAN-H 2 0 mixtures show no tendency to detonation covering a range of

16
R.A. Robinson and V.E. Borher, J. Phys. Chem.,Vol 65, p 1279, 1961.

1 7N. klein and E'. Freedman, ýfA New. Class of Improved Liquid Grun Propellants,"
Proceedings 1984 JANNAF Propulsion Conference, CPIAPublication (in press).
18 Grayson, ed.,
"Kirk-•Othmer Encyclopedia of Chemical Technology," 3rd ed., M.
Vol 2,, p. 525, J.Wiley Sons, New York, 1978.
S19AL.F. Audrieth and B.A. Ogg, The Chemistru of Hydrazine, J.Wiley Sons, New
York, 1951.
20
R.P. Seward, .J. Am. Chem.. Soc., Vol 77, p 905, 1955.

2
* 1L. Medard, , •mnria ( Poudres (Paris), Vol 34, p 147, 1952.

22
S M. Berthelot and B. Andre, Comot. Rendues, Vol 110, p 830, 1890.

114
S

stimuli that exceeds what might reasonably be expected in a gun

application? 3 The potential of HAN as a major propellant component is great
enough that substantial investigation has been devoted to it.

IV. THE HYDPVXYLAMMONIUM NITRATE PROPELLANTS

The use of a HAN-based aqueous system as a gun propellant was first

proposed by personnel at the Naval Ordnance Station, Indian Head, Md. Such
systems had been developed originally for other applications and the proposed
use was not the result of an analysis of the characteristics required but was
essentially empirical. The system was sufficiently promising that detailed
studies were undertaken. 'As an understanding 'of the system developed,
"modifications and improvements were made based on desired properties and
characteristics. At present, properties and reactions of HAN-based
propellants are sufficiently understood that mixtures, to a large degree, can
be tailored for specific purposes.

HAN, the nitrate salt of hydroxylamine, possesses many of the chemical

properties of its parent compounds, although few, if any, of their physical
propertles. Hydroxylamine is ammonia with one of the hydrogens replaced by
OH. The electronegativity of the hydroxyl group, relative to the hydrogen it
replaces, accounts for the markedly decreased basicity of hydroxylamine. This
Sdecreased basicity causes HAN-water mixtures to be considerably more acidic
than are NH4 NO3 mixtures of comparable concentration. Hydrogen-bonding
b•between the OH group and solvent water may. also contribute to the extremely
high solubility of HAN.
Hydroxylamine can be viewed as a cross between hydrazine, NH2 -NH2 , and
A hydrogen peroxide, HO-OH, and indeed, its chemical properties are much as one
would expect from such a hybrid, having some of the oxidizing character of the
peroxide and some of the reducing character of hydrazine. NH2 -OH is a much
weaker oxidizer than is nitrate and reactions of NH3 OH+ and NO3 - show
oxidation of NH3OH+ and reduction of NO3 -. HAN-water mixtures ace, therefore,
monopropellants:

NH3 OHNO 3 e N2 + 2H 2 0 + 202 [61

although rather poor -ones because of theit excess oxygen content and
additional fuel is needed to extract the energy available from the, system.
Equation [6] does not represent the chemistry of the system. Products
obtained from various ex erimental studies in,-lude all of Ithe *oxides of
nitrogen as. well as NH4 and indicate an extrenely 'complex sequence of
reactions.
p iThe -fuel selected for use with HAN should not compromise the excellent
physical properties of 'the HAN-water system and be totally compatible with
it. Compounds of choice for this purpose are the nitrate salts of simple,

2
23W.j.
j Cruice, "Classification of Liquid Gun Propellants and Raw Materials for
Transportat ion and Storage," ARBRL-CR-00454, U.S. Army Ballistic Research
Laboratory, Aberdeen Proving Ground, Md., 1981..(AD A1O0 729)

15
 aliphatic amines. Since such amines are somewhat more basic than ammonia,
their nitrate salts are expected to be highly ionized and not "subject to
hydrolysis to any significant extent. Saturated, aliphatic functional groups
are also sufficiently insensitive to oxidation that their presence would not
be expected to compromise the stability of the mixture under normal handling
and storage conditions.

A. Thermochemistry of the HAN Propellants

T hermodynamics has been applied to the study of propellants for many

years 2 4,2 and plays a major role in interior ballistics modelling. Since
dic.cussion is to be limited to propellants and their properties, only a
portion of such models, namely the closed chamber approximation, will be used,
where it is assumed that a sample of propellant is placed in a chamber of
known volume and burned. o-,petus, flame temperature, pressure, the chemical
composition of the products and their average molecular weight, among other
valuablE data, are calculated.2 6 The dAN-based propellants have all been
"evaluated using the BLAKE code.
The ratio of fuel-to-oxidizer in any propellant is a major factor in its
performanee and such is also the case for the HAN-based propellants. An
example cal-ulation of the effect of varying this ratio on impetus, where the
fuel is an atiphatic ammonium nitrate, is presented in Figure 1. The Figure
also shows the effect of varying wat.er content. Maximum impetus is obtained
or the fuel-rich side of stoichiometry. The use of HAN and the nitrate salt
of an aliphatic amine results in stoichiometry according to the following
general equation:

0 C O nO 3n+1
.2 (-) N22H444 4 + a(2n+4)N203
C N 2 nCO22 + (3n-- N2 + (4n+l) H20 [7]

where n is the number of carbon atoms in the aliphatic amine. It occurs in

"the example calculation when the HAN/fuel ratio is 4 because the value of n
ased was 3.

2 4AC. Cranz, Leh'buch der Baltistik, Vol 2, J.Sp'inge' VerlLng, Berlin, 1926.

25
J. Corne., Theory of the Interior Ballistics of Guns pp .35-129, J.WiZey,
and Sons, New York, 1950.
26
I* E. Freedman, "BLAKE, a Ballistic Thermodynamic Code Based on TIGER,"
Proceeding of International Symposiwn on Gun Propellants, 1973.

"" 16

,.,.
 WATER
1050

1000
1o20%

, 950

"CL 25%
E 900

850

1 I .
2. 3 4
HAN/FUEL Ratio

Figure 1. Calculated Impetus As A Function Of Stoichiometry. And

Water Content

Although not shown in the Figure, the calculations also indicate that
propellants formulated in accordance with equation [7] will have essentially
the same flame temperature and impetus regardless of the structure of the
amine used or of the value of n. Impetus is proportional to the pressure,
volume, and temperature of the product gases. It thus, follows that a
propellant that generates hotter gases, or gases with a lower average
molecular weight will produce h gher impetus values. The matter is
substantially more complex than wo ild bei inferred from this rather simple'
statement. One observes from the calculation that impetus values are strongly
dependent on water content. For the most part, the water is considered in the
calculation as in inert diluent so hat it would be reasonable to expect that
: . impetus decreases with increasing wvter content. A more critical inspection
of the data- reveals that not only is maximum impetus always obtained when the
mixture contains a slight excess of fuel, but that the fuel/oxidizer ratio at
" maximum impetus is also dependent an water content. One can assume' that a
decrease in oxidizer/fuel ratio ca ses a decrease in the average molecular
weight of the product gases because fuel-rich mixtures favor the production of
carbon monoxide and hydrogen, rat er than carbon dioxide and water (the
"water-gas" reaction), and thus, max mum impetus appears on the fuel rich side
"cf stoichiometry for these, as for almost all, propellants. This, however,
should not cause the location of t maximum impetus value in Figure 1 to be
water dependent. The water apparently plays a larger role than that of an
inert diluent, acting possibly as a heat. absorber and thus lowering the
1T

I.
temperature of the product gases, or possibly, that the water-gas equilibrium
is disturbed by the presence of additional water. The combination of these
various effects is neither readil; predicted nor easily explained.

In addition to making near maximum impetus available, stoichiometry

provides a number of other desirable characteristics. Since no excess fuel is
present in the mixture, the combustion products venting from the gun are not
combustible and therefore little or no secondary muzzle flash and blast is
expected. There has been a -ather severe penalty for attempting to achieve
stoichlometry in solid propellant formulations, or in liquid formulations
containing nitrate esters, namely that such formulations tend to be shock
sensitive and detonable. Since shock sensitivity or detonability are not, a
priori, conditions associated with stoichiometry for all systems, there is no
reason to require that aqueous liquid propellants be fuel rich. Indeed, HAN-
based, stoichiometric, formulations give no indication of detonability under
23
conditions that could reasonably be expected in a gun environment.

B. Fuel Components

Mixtures of HAN with specific fuel's can be easily prepared since the
components are miscible in almost all proportions. Stoichiometry fixes the
oxidizer/fuel ratio but the water content is determined by the desired
properties of the mixture. A water content below 5% by weight is generally
not considered practical because the temperature range over which the mixture
will remain liquid will be too small. Virtually any amine can be use. as the
fuel source. Aromatic amines are not sufficiently reactive to be. seriously
considered and the quaternary ammonium salts have been found to be almost
totally unreactive in formulations of the HAN type. Heterocyclic amines could
potentially serve as fuels but have not been thoroughly investigated at this
time. The aliphatic amines, the basis of the. formulation described in
equation [7], hz.:e been investigated and are the fuels of choice at present.
These compounds for-s stable nitrate salts only if the molecular weight of the
amine is fairly low. As the number of carbon atoms in the aliphatic chain
increases, the salts !end to become thermally unstable, undergoing internal
oxidation-reduction and producing tars and heavy oils. There is no reason, a
prio'i, to restrict the presence of functional groups on the aliphatic
amine. In fact, a formulation containing the nitrate salt of triethanolamine
is currently in use. Equation [71 is, of course, not applicable if such
functional groups are F•tesent.

There are no physiological hazards presented from the HAN-based

propellants other than by ingestion, a rather minor risk in that it would seem
reasonable to discount the probability that operational personnel would drink
these liquids. The propellants are miscible with water in, all proportions and
are biodegradable 2" so that disposal presents no unique problem.

27
D.L. Kaplan, D.J. Emerson, P. Riley, and A.M. Kaplan, "Decomposition of Four
Ammonium Nitrate Propellants," NAT1CK/TR-83/045, U.S. Army Natick Research
and Development Center, Natick, MA, 1983.

. . .. ~ .. .' 4t . . . . . . ~ ~ ,~*****. % . . . . . . . . .
 The required characteristics of propellants are determined by their
intended use and physical properties must be consistent with these
characteristics. The physical properties themselves, however, are determined
by the materials that comprise the formulation and cannot be changed unless
the formulation is changed. Thus, it becomes necessary to identify a specific
formulation before its physical properties can be described. Some general.
statements relevant to all HAN-based formulations can, however, be made. The
presence of the OH group in the hydroxylammonium cation will encourage
hydrogen bonding with the water present thus increasing the -structure" of the
mixture. This, in turn, should increase miscibility with water and discourage
crystallization at low temperature producing Instead, amorphous glasses, if
the temperature is low enough. A disadvantage associated with such hydrogen
bonding would be an increase in viscosity, a point to be seriously considered
if OH groups are also to be present in the aliphatic amines that comprise the
fuel.

A second, general point, is that formulations sufficiently energetic for

practical application oill have insufficient water to permit the formation of
normal hydration spheres around the ion; present and therefore result in
properties unpredictab.e from studies of the same ions in dilute solution. In
fact, salt concentrations will be high enough that a proper description of the
system will be a low temperature salt melt rather than a. solution. Since
hydrolysis of the salts is not expected, the concentration of nitric acid or
of the free amines will be vanishingly small and the vapor pressure of the
mixtures is expected to be approximately equal to the partial pressure of the
water present, a prediction that is confirmed experimentally.

V. PROPELLANT CHEMISTRY

Generally, propellant chemistry means the reactions and products of three

aspects of decomposition: ignition, combustion, and thermal stability, each
with pertinent subdivisions. Ignition is usually thi sequence of events that
makes decomposition self-bustaining. It often leads to combustion which
results in the final products observed. The majority of the energy is
released during combustion and both chemical and physical processes are
drastically different from those found during ignition. The: ignition phase
involves a liquid of chemical composition similar to that of. the, starting
material, whereas combustion involves primarily gases that contain significant
concentrations of unstable transient species. Physicaliy,,the ignition phase
involves pools, droplets, or sprays with reaction taking place at or near the
surface, since a definable surface still exists at these early stages of
reaction and heat transfer from the reaction zone back into the propellant is
an important means of reaction rate control. 'In contrast, -combustion is
probably controlled by. species, diffusion in hot gases at rather .high
pressures. When increasing pressure accelerates reaction rates, reaction
zones become smaller and the complexity of the. reacting system makes even
qualitative descriptions nebulous at best. An important part of the' ignition
process (or processes) is often reaction initiation, the stimulus that starts
an ob-servable chemical change. Initiation differs from ignition in that the
requirement for self-sustaining decomposition is absent. This seemingly small
difference is quite important from an experimental viewpoint because reaction
quenching' either by dilution or by cooling, can permit reactioa products to be
isolated and identified. Initiation studies also make possible detailed
investigation of activation energy, the minimum input stimulus required for
19
 reaction. If such stimulus is thermal, then initiation studies provide
information relating to thermal stability.

A. Experimental Studies

One fairly simple method to investigate initiation processes and study

the effects of compositional changes on the ignition of HAN mixtures'is •y use
if a small, high-pressure hydrogenation apparatus consisting of a 50 cmi ANSI
'316 stainless steel bomb, a furnace,' and associated gas handling hardware.
Propellant sample size is restricted to 2 ml or less because maximum safe
operating pressure of this bomb is approximately 69.9 MPa (10,000 psi), The
furnace is capable of heating the bomb and sample uniformly to about 25G C at
rates up to 10 C/min. Although the apparatus creates a set of experimental
conditions quite far removed from those to be found in a gun, the conditions
are highly reproducible and readily, selected, thus simplifying data cnllection
and evaluation. The bomb is normally equipped with a piezoelectric pressure
gauge which records the rate of gas evolution when the sample has been heated
to reaction initiation temperature. Reaction products, either gases, liquids,
or solid residues can be sampled for analysis, and mass accountability
obtained. The effect of reactant concentration on reaction initiation
temperature, obtained with this apparatus, is shown in Figure 2.

220-

200-
U
0j

S4 I.- 0

'La
o 160
LU.

140 -

120

100 I I I I- I I.
0 2 4 6 8 10 '12 14
'HAN CONCENTRATION (MI

Figure 2. Rention Initiation Temperature Of HAN Solutions

The Figure. presents the initiation temperature of HId-water mixtures as a

function of concentration. Although the data seem to indicate that initiation
temperature decreases Tinearly wich increasing HAN concentration, it would be
doubtful that this is the case, there being no basis in theory to support a
linear relationship. The relationship is probably exponential, linearity
20

• %..-" . ,o o °°.,.% %' - ' °' '... . a-.••. .' o. . .-o o..o .-... . o . . '. .. .. . . . . % -
 appearing as an excellent approximation over the range of con.entrations
studied. In fact, initiation temperature is a function not of HAN, hut of
nitrate concentration, since propellants containing various aliphatic ammonium
.i!rate salts begin to decompose at precisely the same temperature as does HAN
of equal nitrate content', Ignition is more complex than reaction initiation
3ince the observation of self-sustaining reaction is also dependent on a
number of physical phenomena such as droplet concentration, residence time,
heat transfer, etc.

The nitrate-nitronium equilibrium, first mentioned in equations [1] and

[2] appeairs to be the critical parameter in the initiation of HAN-based
propellants and any method whereby the nitroaium concentration is increased,
caus s initiation )f the reaction sequence. The critical No2 + concentration
is essentially independent of formulation but is dependent on the experimental
conditions employed so that extrapolation to different conditions is
difficult. Since the nitrate-nitroaium equilibrium can be shifted by a wide
variety of 'stimuli, such stimuli can be used, either singly or in' combination,
as propellant igniters. A number of materials such as NO2 , P2 0 5 , and
concentrated H2 SO 4 drive the equilibrium toward N02 + and can thus cause
ignition without thermal input. Stable nitronium salts exist and the addition
of small quantities of such salts as nitronium flouorophosphate or
fluoroborate very effectively ignites the propellant. An increase in
temperature increases the nitronium concentration and, when a critical level
is attained, decomposition becomes self-sustaining, since the decomposition is
exothermic.

A special comment regarding initiation by NO2 is called for since it

ralates directly to the storage stability of these formulations. The oxides
of nitrogen, including NO2 and NO, are decomposition products of HAN and NO is
promptly converted to NO2 in the presence of air. Thus, decomposition of
these mixtures, when stored in sealed containers, will accelerate unless some
means are provided for the removal of these gases..

rhe passage of an electrical current through these conducting mixtures.

causes, in addition to' the expected ohmic heating of the mixture, ion
migration, with NO3 - moving to the anode. In the vicinity of the anode NO
concentration increases thus causing an increase in NO + and, as might be
expected, reaction initiation is observed.28 If electrica energy is supplied
as a high-current pulse, a plasma arc forns and the interaction of propellant
with the plasma arg^ results in a variety of' rather complex physical and
chemical processes,29 a number of which are presently under 'investigation.
The plasma arc presents a high temperature, high pressure stimulus to the,
propellant in addition to the chemical changes induced by the passage of the
electrical current, and Lhe combined stimuli produce dramatically different

Z"N. Klein, F.J. Weinberg, and F.B. Cnrleton, "Ignition Phenomena in Energetic
Liquids," ARBRL-TR-02514, U.S. Army Ballistic Research Laboratory, Aberdeen
Proving Ground, MD, 1933. (AD B0?? 357L)
29
N.Ktein, "Liquid Propellant Ignititn Studiee," Proceedings of 20th JANNAF
Combustion Meeting, CPIA Pub. 383, Vol 1, p 473, 1983.

21

o. ....
oX•. - . .o2
.o.° ... . .. •. . . , ° . ,.••= . % "., , . , . , ° . ,-•.% .o , . .°., .• .•.°,. -
effects from those observed when the stimuli are delivered singly. IgnitLon
of propellant, by pulsed plasmas is currently being considered for use in a
liquid propellant gun 3 0 because it offers a number of advantages over other
techniques. Pressure, in the absence
31
of heating, does not induce reaction,
even at values greater than 700 MPa.

B. Effect of Fuel Structure on Reaction-Rate

A second set of data, obtained with the small pressure vessel, is shown
in Figure 3 which presents the rate of gas evolution from a group of HAN-,
aliphatic ammonium nitrate (AAN) mixtures that differ only in the chemical
structure of the aliphatic amine used.

35-
0 ! N .

30 - a HAN SIBAN
• o II/rJ.113AN
A HAN
0 IiHAN
HAN-!B.1AN
25- 2 -
O 11AF6'-D[AN
0 HArI-EDMIAN
S20
LU

W)

10-

0 50 100 150 200 250 300

TIMIE (nis)
Figure 3. Gas Evolution Rates For HAN-C 4 AN Mixtures

7)N. Klein, F.B. Carleton, and F.J. Weinberg, "Methods for Evaluation of
Ignition Stimuli for Liquid Propellants," Proceedings of 19th JANNAF
Combustion Meeting, CPIA Pub. 366, Vol 1, p5O5, 1982.
1
.3 C.A. Van Dijk, "Characterizationof'Hydroxylannonium Nitrate at Various
Pressures and Temperaturee," Geo- Cernters, Inc., Newton Upper Falls, MA,
'Rpt GC-TR-83-266, 1983.
22

?.

S..?':.,-:.-.
.. ..-
....-..-.:.':.
.-.'-.'-.:-':-'
.°'..--:..':. ": "i... ...-.- > --.-. •-. '. ..-.-... . .. .: .. . ,. .'. .
The mixtures used to obtain the Figure 3 data all are 11 Molar in nitrate
concentration, are stoichiometric, and consist of HAN,' water, and one of the
AAN salts that have the empirical formula C4 H1 2 N2 0 3 , of which eight exist. 3 2
The amines that produce these salts are listed in Table 4.

TABLE 4. THE C4 ALIPHATIC AMINES

Densit Boiling point

Amine (•gMcm-) (deg C)

CH 3 -Ch 2 -N-(CH 3 ) 2 (EDMA) 0.67 36-37

(CH 3 ) 3 -C-NH 2 (TBA) 0.693 44-46
(CH 3 ) 2 -CH-NH-CH 3 (MIPA) 0.703 50
(CH 3 -CH 2 ) 2 -NH (DEA) 0.704 55-56
CHZ-CH -CH 2 -NH-CH 3 (MPA) 0.720 62-64
(CH1 3 -CH 2 )(CIH3)CH-NH 2 (SBA) 0.724 63-65
(CH 3 )2-CH-CH 2 -NH 2 (IBA) 0.773 67-69
C113 -CH 2 -CH 2 -C11 2 -NH 2 (NBA) 0.740 16-78

Ethlydimethylamine (EDMA) is a tertiary amine, diethylamine (DEA),

methylpropylamine (MPA), and methylisopropylamine (MIPA) are secondary amines,
and normal (NBA), secondary (SBA), tertiary (TBA), and isobutylamine (IBA)' are
primary amines. All form stable, white, crystalline, nitrate salts that are
very soluble in water.

Reaction initiation temperature for the six mixtures shown in Figure 3 is

constant and' is the same as O.at required to initiate reaction in 11 Molar HAN
under the same conditions. Although no differences are observed for reaction
initiation, the results indicate significant differences in the ignition and
combustion chemi3try of propellants containing salts of tertiary amines
compared with that observed in mixtures contaiming either primary or secondary
amines. The fact that the AAN salt plays essentially no role in reaction
initiation but is of considerable importance in determining the rate of energy
reLease during combustion has profound consequences in designing propellant
formulation since it becomes possible to tailor the rate of energy release
without changing either the energy content of the mixture or the conditions
required for ignition.

If reaction initiation is permitted to take place under condition3 that

do not permit a significant increase in pressure, then reactions usually do
not continue to completion. The products and residues obtained indicate the
reaction 'sequences that took place., At the earliest stages of reaction,
6 aseous products ' 'e exclusively nitrogen and its oxides NO2 , NO, and N2 0. No
carbon containing products are obtained and all of the AAN salt is recovered
from the liquid residue. These results indicate that only the HAN is
undergoing decomposition, the reactions being both the internal oxidation-
reduction of the hydroxylammon.um ion, the oxidation of the ion, by nitrate and

32N. Klein, "Preparationand Characterizationof Several- Liquid Propellants,"

ARBRL-TR-02471, US Army Bat iatia Rsearch Laboratory, Aberdeen Proving
Ground, HD 1983. (AD B071-589)

23
the reduction of the NO3 - ion. The residue from these early reactions is
substantially more acidic than is the starting material, indicating formation
o~f the hydronium ion as a reaction product. This is not surprising since the
nitrate concentration originally present is sufficient for total oxidation of
thu mixture which, of course, has not yet occurred.

If reaction is permitted to proceed; the carbon containing ions become .

involved and a variety of organic products are obtained, the comnposition of
which is d'ependent on. the structure of the amines used originally. Primary
amines are deamiaat.~d, producing the appropriate carbonium ion which then
undergoes stepwise oxidation yielding first, alcohols:

R-NH3+ R+ + R-OH . [8]

If the alcohol is on a primary carbon, the corresponding carboxylit. acid is

obtained:

whereas a secondary alcohol produces the expected ketone:

RI-C-OH-R 2 + RI-CO-R2~ . [10]

,Both the acids and ketones are sufficiently unreactive that they can be
recovered as intermediate products.• When they finally become involved in the
reaction sequence, conditions are usually sufficiently severe that reaction
goes to compiezion and the only products obtained are N2 , C02 , and H2 0.
Tertiary amines cannot undergo deamination, although carbonium ions are
formed, and, early reaction products are instead the nitrosamines:

RIR 2 R3 NH+ + RIR 2 N-NO + R.3 + .. [11]

Thus, •rimethylamine produces dimethylnitrosamine, triethanolamine produces

bts (2-hydroxyethyl) nitrosamtne, and ethyldimethylamine gives 'both
iuethylethylnitrosamine and dimethylnitrosamtne. The carbonican ion, R3 ÷,
reacts according to Reaction [81. Secondary amines appear to undergo
deamination and the reac'tions observed are similar to those obtained with
primary amines. The consequences of the diLfference in reaction path for the
tertiary amines is important .in terms of the rate of gas generation during the
very early stages of .combustion.

'If the sample is contained, so that the evolved gases can cause a
significant increase in pressure or, if the origintal sample container is at
elevated pressure, the reaction sequence continues and the final'coahustion
products are obtained. The mode of transition to the combustion phase and the
rate of gas evolution are dependent on the structure of the AAN salt used in
formulating the mixture since the nitrosamines aud their oxidation products,
the nitraminee, are much less stable than are carboxylic acids and ketones and
therefore decompose more readily. No build-up of intermediate products takes
place resulting in a smoother rate of gas generation without the "steps" seen
in the primary and secondary amine mixtures. This is clearly illustrated in
Figure 3, Analysis of chamber residue and comparison of observed and
calculated peak pressure both indicate that reaction proceeded to completion
in the mixture containing the tertiary ammonium salt. This was not the case
for the other mixtures,. 2

............ ~~... . . .. . .

\~

S:" -'.'''.'''.'',...."'v
.... ''.-'...v ~ .. "...: . . '•.-: -•.'...-.. .".".": " .-" ..'- .." '.-.'."....'. .- ...':..- "" '
 A word of caution is in order regarding the use of thermodynamics for the
prediction of propellant performance. Since energy content is the same for
all of the mixtures shown in Figure. 3, thermochemical calculations predict no
difference in performance. The various thermochemical codes produce results
based only on' thermodynamics, kinetics of reaction not being considered. The
wright assigned to such results should, therefore, be kept in proper
perspective, to wit, negative findings bode badly for the system being
evaluated but favorable results give little or no indication that the system
will perform satisfactorily.

In addition to the example of the AAN isomers just presented, an example

of historic interest is a p{~pellant mixture consisting of hydrazine,
hydrazinijpntrate, and dater. This formulation received a great deal of
attention - because of its unique thermodynamic properties. The system is
compounded to achieve stoichiometry, vis.:

4N 2 H5 NO3 + N2 H4 ,+ 7N2 + 12H 2 0' [12]

water being added to control the energy content and to create more acceptable
physical properties. This propellant is unique among the monopropellants in
that it contains no carbon. Normally, at stoichiometry, the only product
gases from combustion of a propellant containing carbon would be N2 , H2 0, and
C0 2 , with CO2 having, by far, the, highest molecular weight. Since impetus is
closely related to the average molecular weight of the product gases, it would
be expected that N2 H4 -N 2 H5 N03 -H 2 0 mixtures be very efficient in transferring
energy to a projectile. In addition, calculations indicated that these
mixtures would have unusually lcw flame temperatures thus improving gun
life. Unfortunately, the same mixture presented such poor performance with
regard to the rate of energy release, in addition to poor thermal stability
and extreme toxicity, that it could not be seriously considered.

Mention has been made of the fact that the HAN-based propellants do not
reect to completion unless pressurized. Thermal initiation temperature is the
safe storage and handling limit of the mixture, which is 120 C when water
content is approximately 20%. If the mixtures are stored and shipped in

33
" R.D. Dwiggins, H.M. Sternberg, and D. Bosco, "Investigations of Mixtures of
Hydrazins, Hydrazine Nitrate and Water,," NAVOR) Report 2787, Naval Ordnance
Laboratoriy, White Oak, M), 1953.
34
t.,J. Evans, F.I. Given, and D.G. Doran, "Ignition and Combustion Properties
of Liquid Monopropeltants," Report for Contract DA 0.:-20G-Of-320, Poutter
Labs, Stanfovd Research Institute, Menio'Park, CA, 1956.
35 "NozzeZ Erosion, Burning Characteri'stics, Covotuw and Impetus of Liquid
PropeZZants, " R'port on, Contract DA 11-022-OR-1157, Armour Research
Foundation, Chicago, IL, 1955.
3 6 S. Wise, G. Beichter, and J. Dykstra, "The Vulnerability of Hydrazine Based
Liuid Monopropellants When Attacked By a 3.5 IN M28A2 Heat Round," BRLMR
1006, Ballistic Research Laboratory, Aberdeen Proving Ground, AD, 1956.
(AD 101 031)
25

.. "..'.'.,
% • %",.,'•......
• ... '." • •,.." . ,..............."............ '......................................."..........

.../--/ ... . ...................... l] . .... .- """................. I......• ' L- t- ''".............. I

containers that do not permit pressurization, then only a small portion of the
available energy would be released if accidentally initiated, and thus hazards
associated with propellant handling are greatly reduced. Numerous attempts to
obtain combustion at atmospheric pressu.., under a wide variety of conditions,
have consistently failed to achieve more than a partial decomposition of the
fuel component.

Attack by shaped charges or by hot spall fragments presents a hazard that

is related to, but not the same as, thermal initiation. The rate at which
energy is transferred to the propellant is markedly different in these cases,
a matter of major importance. Presently available data are incomplete, but
appear to indicate that the HAN-based propellants can be caused to undergo
substantial decomposition when attacked in such manner although detonation
has never been observed.

C. Effects of Impurities on Stab4 lity

Thermal stability, as discussed to this point, applies to mixtures that,

within detectable limits, are pure. An additional consideration that affecte
propellant stability is the role of impurities in initiating decomposition.
One such impuriy would be an acid since it has already been showl that the
presence of acids drives the N0 3 -- NO2+ equilibrium toward NO2 + and hence
facilitates reaction initiation. Thus, although the mixtures are somewhat
acidic, the presence of excess acid would adversely affect stability.

HAN-based propellants are ionic and contain both oxidizing and reducing
species. As would be expected, they react readily with a wide variety of
raterials many of which could find their way into the mixtures as
impurities. Of cardinal importance in this regard are the salts of the
transition metals, notably iron, copper, and nickel. The reactions of such
salts should not be confused with the reactions of the metals themselves,
although both are important. The effect of transit SQn metal ions on the
thermal stability vf HAN-AAN mixtures has been studied and, generally, the
presence of such impurities in low concentrations tends to lower the stability
of the mixture. The effects are quite complex, however, b havior being
dependent on the particular metal present. The ferric ion, Fe , acts as a
catalyst, lowering the activation energy required for initi tion of HAN
decom osition. The reactions observed are the reduction of Fe1+ to Fe2+ by
NH 3 OI, followed by oxidation of the Fe 2 + to Fe 3 + by N0 3 -. Reaction products
are N2 and N2 0 exclusively andreaction proceeds ac a constant rate until'
essentially all of the HAN is destroyed.

In the case of the cupric ion, Cu 2 +, both reaction mechanism and the
products obtained are drastically different. This transition metal ion does
not show catalytic action because, although Cu 2 + is reduced to Cu+ by NH3 OH+,
the complex iou• formed is not. reoxidized by N0 3 . Thus, reaction rate
decreases as Cu+ is depleted and decomposition would eventually stop. It
happens, however, that NO is a reaction product together with N2 and N2 0. The

67
N. Klein,. "Liquid Propellant Stability Studies," Proc. 15th IrcernationaZ
ICT Conference on Technology of P-opellants and High Explosives, 1984 (In
7,reea)
26
NO formed would be converted to NO2 by reaction with air and then 2 facilitate
decomposition of the mixture even as the adverse effect of the Cu + impurity
was decreasing by iLs removal.

The transition metal ions in question are always present in these

mixtures as complexes and the rei.ctivity of such complexes is strongly
dependent on the ligands involved. As an example of such dependence, the
tetraaquo complex of Cu+ is readily oxidized by nitrate whereas various amino
complexes are sufficiently stable to resist such oxidation, an observation
supported by the current data. The lability of the complex ions is also
strongly dependent on the ligands involved, amines generally forming rather
nonlabile complexes with the transition metal ions. This latter point would
suggest that this type of impurity would not lend itself to removal from
propellant mixtures by ion exchange or complexation techniques.

In addition to reaction with the ions of the ttansition metals, the HAN-
based propellants react readily with the metals themselves and with many of
their alloys. When exposed to copper or brass, RAN solutions turn blue and a
brown gas is evolved, indicating the presence of NO2 . Reaction becomes more
vigorous as it continues, eventually resulting in fume-off. of the sample. In
.contrast, reaction of HAN with iron and many of the carbon steels produces a
colorless gas and a yellow-brown solution. Reaction does not accelerate and
eventually stops when essentially all of the HAN is depleted. The apparent
similarity of reaction with the metals and with their respective ions could be
deceptive since reaction mechanisms might be different.

Simply stated, HAN-based propellants are sensitive to impurities and are

corrosive. Considerable care is required in selection of materials with which
they will come in contact both from the standpoint of damage to the propellant
and of damage to the materials. It is also possible that the presence of such
impurities will influence reaction sequences after initiation and thus change
the performance characteristics of the propellant in a gun. This effect,
although not yet investigated, could present major problems if it does indeed
occur.

VI. SUMMARY

The work presented is possibly best summarized by relating' it to the

characteristics required of a liquid propellant to be used in a gun..' The
*characteristics required are intimately related to the gun system in which it
is. to be' used which, for purpose of discussion, is to be a 'medium caliber,
high performance, sell-propelled cannon using caseless ammunition. *It 'is
reasonable to assume that the complete gun system will 'be substantially
improved over what is presently in use in order to warrant the expenditure of
effort for development and fielding of so radically different a system.

The concept of caseless ammunition presents a number of advantages to the

user and s-veral rather. severe constraints to the developer. The advantages
were described in Chapter I. Constraints concerning caseless ammunition
"center about the fact that the propellant will be pumped and is thus exposed
to the possibility of contamination. The possibility of exposure of operating
personnel to the propellant is increased requiring greater concern about
toxicity.

27
A. 'Impetus:

Factors influencing propellant impetus are sufficiently complex and

present ramifications to, other aspects of the overall ballistic cycle such
that no single value can usually be generated. In spite of this, a high
performance gun generally requires an impetus of approximately I ki/gin.
Bearing in mind that a liquid-will assume the shape of its container and that
the HAN-based, aqueous monopropellants have a density of approximately 1.5 gmn
cm 3, loading of propellant without void space will result in a volumetric
impetus of 1.5 kJ cm , a fairly high value compared with what is presently
available.

B. Vulnerability:

Propellants are energetic materials and are inherently dangerous, the

extent of the danger being closely related to the ease with which they can be
induced to release the energy that they contain. Attack on systems with which
the propellant is associated usually inivolves input of thermal or mechanical
energy and vulnerability is reduced when the energy required for initiation of
reaction is high. The ultimate in vulnerability reduction would *be that
reaction initiation not be possible until the propellant is properly loaded
into the gun *combustion chamber, a situation almost achieved in a non-
hypergolic bipiropellant because oxidizer and fuel are not in contact until.
that time. In the care of monopropellants, an alternative could be that the
mixture,, although capable of initiation, is not able to release the majority
of the energy available unless same relatively high pressure is maintained in
the combustion chamber, the situation that exists with the RAN-based
propellants.

C. Stability:

The distinction between vulnerability and stability in the context of

this discussion, is that stability refers to more benign circumstances over
longer times. Reactions of the propellant with its storage containers and the
role of trace impurities in accelerating decomposition must be carefully
considered. The presence, in the propellant, of components with relatively
high vapor pressure, such as hydrazine or the nitrate esters, could produce a
serious stability problem in that such components could evaporate,, if storage
conditions 'permitted, thus, changing the composition of the mixture.. A
stability problem of a special kind exists if the mixture contains components
that separate at some low temperature. The separation, or "freezing out" of
such components causes a. change in composition of the liquid and hence' a
change in propellant properties.- It is possible that such change is temporary
in that the components could redissolve as the temperature is, raised,
reforming the original mixture.

D. Toxicity:

Th 'e use of caseless ammunition increases the importance of propellant

toxicity because of the increased possibility of exposure. This requirement
'is of special importance, if the liquid 'is to contain nitrate esters of low
molecular weight. Such compounds are, without exception, physiologically
active to the extent that they would be considered toxic.. The HAN-based
propellants are possibly unique among candidate liquids as to the~ir lack bf
toxicity.
28
I

E. Viscosity:

Caseless ammunition requires that the propellant be pumped. into the

combusticn chamber, at high speed. Since the gun must be operational over a
broad cemperature range, propellant viscosity should not vary severely with
temperature. This is a rather difficult requirement to satisfy since liquids
inherently become more viscous at lower temperatures..

"The problem of propellant performance at various 'temperatures is not

jaddressed
- in this summary in part because the problem is not unique. to liquid
propellants. Although specific, temperature dependence data are not yet
available, it would not be surprising to find that performance is temperature
dependent.

F. Cost and Producibility:

Since the liquids are homogeneous, mixing and blending operations become
almost trivial and, obviously, casting or extruding is non-existent. Savings
expected from the absence of these production steps should be considerable and
should mkte than compensate for the increased handling and shipping costs
"associated with maintaining purity and compositional integrity while handling
the propellant in bulk. The HAN-based mixtures contain no critical materials
and are produced from raw materials for which a well established production
base already exists.

G. Demilitarization and Disposal:

It is reasonable to expect that not all available propellant will be

consumed by the weapon system and that demilitarization and disposal will be
required. Burning is becoming an increasingly less viable method of disposal
"as more becomes known of the impact of such disposal on the environment and
the use of a non-toxic and biodegradable propellant is certainly desirable.

H. Muzzle Flash and Blast:

Secondary muzzle flash and blast result from ignition of combustible

gases that are products of propellant combustion, a situation not present if
k-, the propellant is stoichlometric.

In conclusion, it would appear that, based on what is presently, known of

the HAN-based. propellants, they successfully address many of the requirements
presented. A number of problems, such as variation of viscosity with
.. temperature, corrosivity, and the deleterious effects of low concentrations of
iimpurities on stability seem formidable at this time, It is assumed that as
work continues and more becomes known about these interesting and rather
unique materials, improvements in properties and performance will be realized'.

29

"...................................................
 ACKNOWLEDGEMENT

Th,!rmochemical calculations using the BLAKE code, mentioned repeatedly in

the text, were performed by Dr. E. Freedman, of the Ballistic Research
Laboratory. I am deeply indebted to him both for graciously supplying the
results of these calculations and for numerous discussions and constructive
suggestions.

ii
 REFERENCES

1. W.J. Barr, E.J. Wilson, Jr., et al, "Liquid Fuel Catapult" Experimen.t
Inc., Richmond, VA,T.P.No.31, 1947.

2. J.C. Clark, Ignition Rutgers University Press, New Brunswick, NJ,

1972.

3. C.R. Newman, "Investigation of Application of Liquid Propellants to 90-

mm Tank Guns," Detroit Controls Corp., Redwood City, CA, Rpt. Nr. RC-
184, 1956.

4. B.A. Niemeier, D.L. Swanson, and H.B. Forney, "Liquid Propellant Small
Caliber Gun With Repetitive Fire," Experiment Inc., Richmond, VA, T.P.No
58, 1953.

5. W.F. Morrison, J.D. Knapton, and M.J. Bulman, "Liquid Propellant Guns,"
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6. T.M. Broxholm, L.C. Elmore, and W.H. Giedt, "Liquid Propellant Gun

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8. Chem. and Eng. News, American Chemical Society, Washington, DC, Vol.
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9. "Encyclopedia of Explosives and Related Items," PATR 2700, U.S. Army

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10. "Evaluation of New Propellants For Liquid Propellant Gun Systems,"

Redel Inc., North Hollywood, CA, contract Report N6. CPR-4, 1955.

11. "Investigation of Propellant Reactions For•Liquid Propellant Gun

Systems," Redel Inc., Anaheim, CA, Report on Contract NOrd-12148, 1956.

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Ammunition," Experimept Inc., Richmond, VA, TMH814, 1956.

13. J. Mandzy, I. Magoon, W.F. Morrison, and J.D4 Knapton, "Preliminary

Report on Test Firing of a 105 MM Regenerative Fixture," Proceedings of
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* San Francisco, CA, 1964.

15. "Lange's Handbook of Chemistry," 12th ed., J.A. Dean, ed., pp 5-15,
Mc Graw Hill Book Co., New York, 1979.

16. R.A. Robinson and V.E. Bower, J. Phys. Chem., Vol,65, p 1279, 1961.

31

• "' " " •''" "'''""7'''" ".......................................................

 17. N. Klein and E. Freedman, "A New Class of Improved Liquid Gun
Propellants,". Proceedings 1984 JANNAF Propulsion Conference, CPIA
Publication (in press).

18. "Kirk-Othmer Encyclopedia of Chemical Technology," 3rd ed., M. Grayson,

ed., Vol 2, p. 525, J.Wiley Sons, New York, 1978.

19. L.F. Audrieth and B.A. Ogg, The Chemistry of Hydrazine, J.Wiley Sons,
New York, 1951.

20. R.P. Seward, J. Am. Chem. Soc., Vol 77, p 905, 1955.

21. L. Medard, Memorial de Poudres (Paris), Vol 34, p 147, 1952.

22. M. Berthelot and B. Andre, Compt. Rendues, Vol 110, p 830, 1890.

23. W.J. Cruice, "Classification o. Liquid Gan Propellants and Raw Materials
for Transportation and Storage," ARBRL-CR-00454, U.S.Army Ballistic,
Research Laboratory, Aberdeen Proving Ground, MD, 1981. (AD A1O0 729)

24. C. Cranz, Lehrbuch der Ballistik, Vol 2, J.Springer Verlag, Berlin,

• 1926.

25. J. Corner, Theory of the Interior Ballistics of Guns, pp 85-129,

J.Wiley and Sons, New York, 1950.

26. E. Freedman, "BLAKE, A Ballistic Thermodynamic Code Based on TIGER,"

| Proceedings of International Symposium on Gun Propellants, 1973.

27. D.L. Kaplan, D.J. Emerson, P. Riley, and A.M. Kaplan, "Decomposition of
Four Ammonium Nitrate Propellants," NATICK/TR-83/045, U.S.Army Natick
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28. N. Klein, F.J. Weinberg, and F.B. Carleton,, "Ignition Phenomena in

Energetic Liquids," ARBRL-TR-02514, U.S.Army Ballistic Research
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29. N.'Klein, "Liquid Propellant Ignition Studies," Proceedings of 20th JANNAF

Combustion Meeting, CPLA Pub. 383, Vol 1, p 473, 1983.

30. N. Klein, F.B. Carleton, and F.J. Weinberg, "Methods for Evaluation of
Ignition -Stimuli for Liquid Propellants," Proceedings of 19th JANNAF
Combustion Meeting, CPIA Pub. 366, Vol 1, p505, 1982.

31. C.A. Van Dijk, "Characterization of Hydroxylammonium Nitrate at Various

* .Pressures and Temperatures," Geo- Centers, Inc., Newton Upper Falls, MA,
Rpt. GC-TR-83-266, 1983.

32. N. Klein, "Preparation and Characterization of Several Liquid

Propellants," ARBRL-TR-02471, U.S.Army Ballistic Research Laboratory,
' Aberdeen Proving Ground, MD, 1983. (AD B071 589)
3

32

*.. "* ••••• .. '.•....-.. ' . .... r ..... ,"" .• . _.. ' .. '.' ', - ' .. •..• ,..•. .:.-..,..... . .... •.... .,• . •
 33. R.D. Dwiggins, H.M. Sternberg, and D. Bosco, "Investigations of
Mixtures of Hydrazine, Hydrazine Nitrate and Water," NAVORD Report 2787,
Naval Ordnance Laboratory, White Oak, MD, 1953.

34. M.J. Evans, F.I. Given, and D.G. Doran, "Ignition and Combustion
Properties of Liquid Monopropellants," Report for Contract DA 04-200-ORD-
320, Poulter Labs, Stanford Research Institute, Menlo Park, CA, 1956.

35. "No-le Erosion, Burning Characteristics, Covolume and Impetus of Liquid

P:opellants," Report on Contract DA ll-022-ORD-1157, Armour Research
Founda .ion, Chicago, IL, 1955.

36. S. Wise, G. Beichler, and J. Dykstra, "The Vulnerability of Hydrazine

Based Liquid Monopropellants When Attacked By a 3.5 IN M28A2 Heat Round,"
BRLMR 1006, Ballistic Research Laboratory, Aberdeen Proving Ground, MD,
1956. (AD 101 031)

37. N. Klein, "Liquid Propellant Stability Studies," Proc. 15th International

[CT Confo on Technology of Propellants and High Explosives, 1984 (In
press)

33

•.o .. ... *. * ...... -%'.•....•w "%.".Z"-..-.-...-...°......,°'.. •.'.°.'.o.o.,.. .°.•.°°.

: ,, , • , , * ,...
..... •.... . °..•..°..o...... o.o.o•°.o.o.o..o°.b...
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