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Ba 1969 0088.ch001
Ba 1969 0088.ch001
The early work was done with single-base casting powder i n pro-
ducing cartridge grains for such applications as aircraft JATO's, sounding
rockets, and guided missiles. The success of the cast double-base ap-
proach was attributed in great part to the development of a ballistically
attractive family of "plateau" propellants (8, 9) which utilized various
lead salts of organic acids (e.g., lead stearate) to create low temperature
coefficients and low sensitivity of burning rate to pressure.
As the need for higher energy became pressing, double-base casting
powders were developed which maintained the excellent ballistic prop-
erties of the earlier propellants. Moreover, since these compositions were
more heavily plasticized, they were more suitable for case-bonded appli-
cations in which the propellant is cast directly into the motor and bonded
to the wall; such applications demand a low modulus of elasticity and a
high strain capability in preference to high strength. Case-bonded double-
base propellants were first used i n space launch vehicles—e.g., Project
Vanguard and Scout.
Another substantial increase i n delivered energy was obtained b y
incorporating substantial amounts of solid oxidizer (e.g., ammonium
perchlorate) and metallic fuel (e.g., aluminum) i n the casting powder.
The resulting family of composite-modified double-base ( C M D B ) pro-
pellants has found widespread use i n ballistic missiles and space motors.
Accompanying the development of propellants has been an evolution
of more complex grain designs demanding ever-increasing sophistication
in tooling and casting techniques. Early examples of cast double-base
propellants were straight cylindrical charges cast into cellulose acetate
inhibitors and featuring star-shaped perforations for maintaining a con-
stant burning surface (Figure 1). T o accommodate the requirement for
high thrusts and short burning times of larger charges with propellants
having low burning rates, the multiperforated charge design evolved. In
principle, this consisted of concentric rings of propellant connected by
struts; i n practice, it involved a complex array of arc-shaped mold cores
held in place by appropriate base plates and spiders, still inside a cylin-
drical inhibitor tube. A t the same time, the slotted tube design was
introduced for longer burning applications.
The straight cylindrical configuration was appropriate for cartridge-
loaded motors—i.e., motors which permit the separate manufacture of
propellant grains and subsequent loading into the chambers. More
efficient designs, i n terms of volumetric loading and mass fraction of
propellant, are possible i n case-bonded motors. This approach was first
used with cast double-base propellants i n the Altair motor for Project
Vanguard, Scout, Delta, and other space missions. I n such designs, it
became appropriate to fill both domes of the motor with propellant and
to work through relatively small openings at either end of the motor case
The mixer serves three purposes. First, it blends all the ingredients
to provide uniform distribution in the final propellant. Second, it provides
time, heat, and contact for solvation of all or part of the nitrocellulose
by the volatile solvent and plasticizer. Third, it provides mechanical
energy to disrupt nitrocellulose fibers and expose them to solvation.
Solvated nitrocellulose is the matrix which bonds the rest of the material
together and eventually gives strength and elasticity to the finished
propellant.
A t this stage many parameters control the uniformity and subsequent
extrusion and handling characteristics of the product—e.g.,
(1) Solvent composition. Mixtures of ether or acetone and alcohol
are commonly used as solvents.
(2) Solvent amount. The amount is largely determined by the
amount of nitrocellulose i n the composition. Figure 3 provides an example
of the effect of solvent composition and amount on density.
SOLVENT LEVELS , %
X 26.1 (STANDARD)
O 29.1
A 32.1
£ 1.910
! 1.900
1.890
50:50 60 : 40 70 : 30 80:20
(STANDARD)
ACETONE-to-ALCOHOL RATIO
Z30
<
o
z
O 25
5 5
60 90 120 150
MIXING TIME (AFTER THE ADDITION OF
THE OXIDIZER) , MINUTES
I-
II
\
\
\
\
\
\
r A >.... —
y
y
y
\r< y ^
) y
y
y
y
40 60 80 100
PERCENT OF LOT A IN BLEND
30 60 90 120 150 1 80
BLENDING A N D G L A Z I N G TIME, MINUTES
1.60
1.40
80%
u? 1.20
60% •
>
^ 0.80
O
40%
0.60
[ 20%
0.40
0.20
0 0
<
1
- '
2
—
3 4 5 6 7
TIME,
8
DAYS
9 10 11 12
— H
13
0%
14
>
15
500
COMPCDSITION # 1 a r
6*2 7
400
• *\
O »3
jE 300
O yt
z
3 200
z 7*
1.200 1.300
SCREEN L O A D I N G DENSITY, g/cc
FINISHED
PROPELLANT GRAIN
POWDER HOPPER
Pouring 88.5
Screen load 101.0
Screen load (vibration) 101.6
Air load 101.9
Airload (vibration) 102.2
full-scale units are successfully cast with the powder bed kept at atmos-
pheric pressure during casting.
REGULATED
RAM PRESSURE
dt 18(V \ l - t ) \ h ) y
'
where:
(2)
where:
<
)
Q——^gf^
0
o
/
CAST N G PRESSUR E - 25 PSIG
CAST N G TEMP. - 7 1 ° F
OEXPEF IMENTAL
— C A L C J L AT ED VIA EQUATION (2)
20
0
0 /
0 100 200 300 400 500 600 700 800 900
CONTACT TIME, SECONDS
porous media, like wet soil or gravel. After this stage the propellant
enters a precure stage during which it may be considered a quasi-con-
tinuum; casting powder granules have been markedly softened, and the
interstices are approaching the viscosity of the softened granules. Finally,
the macroscopic mechanical properties exhibit no further change, and
the propellant has entered the cured stage.
In the past, specifications for cast double-base propellant charge
manufacture had been selected on the basis of experience and trial-and-
error. If grain defects such as fissures, separations, porosity, or soft spots
were encountered during the early stages of a motor development pro-
gram, process parameters (solvent and ram pressure, ambient rest peri-
ods, etc.) were varied until defect-free charges were produced consis-
tently. During the past two years, a mathematical model of casting and
curing double-base propellant has been under development to place the
process on a sound engineering basis.
The mathematical model attempts to describe the deformations and
stresses in a grain during all stages of its manufacture. In principle,
deformations and stresses calculated with the aid of the model together
with useful failure or defect criteria would permit a prediction of grain
integrity through the entire process. Such calculations would provide
direct guidance in the specification of optimum manufacturing conditions
for defect-free grains.
Established methods for the structural analysis of cured propellant
charges can be applied to the precured stage provided the material prop-
erties during the last stages of cure are available. Recently, a structural
analysis approach has been developed (10) for the post-cast stage of the
process when the grain is a two-phase powder-solvent mixture. Since
linear viscoelasticity theory is not sufficiently general to predict the effect
of solvent and ram pressure, Biot's theory (4, 5) of porous media has
been used. To handle the complex geometry of a solid propellant grain,
the theory of porous media was combined with an existing finite element
computer program (1) for the stress analysis of cured propellant charges.
The mathematical model used thus far has not included the effects of
viscoelasticity or irreversible deformations.
To predict the mechanical integrity of any body, three things must
be known i n addition to an adequate analytical technique:
(1) The loads sustained by the body
(2) The mechanical properties of the system
(3) A useful definition of failure (loss of integrity)
The loads on a propellant charge are generally known and recorded as
the process variables (pressures), or they can be calculated from tem-
perature and thermal and mechanical properties of the system. U n t i l
recently, the required mechanical properties and failure criteria were
not known for a propellant charge during the post-cast or the precure
stages of cure.
M A T E R I A L PROPERTIES. The elementary form of the analysis used
requires the following properties of propellant during cure: tensile modu-
lus, effective bulk modulus, and propellant volume change. Each of these
properties changes with temperature and time elapsed since casting. Be-
cause of the unusual nature of the material (sticky, wet, explosive,
"gravel"), special tests, equipment, and techniques were developed for
these measurements.
80
the propellant possesses only a small fraction of the strength of the fully
cured material. A fully cured specimen of the same propellant would
yield a tensile strength of 110 p.s.i.g. at the indicated strain rate.
The effective bulk modulus and volume changes during cure are
determined in a specially designed dual dilatometer apparatus (see
Figure 18). To make these measurements, a 1-inch-diameter casting of
propellant is made in a flexible polyethylene septum held in a rigid-walled
vessel containing a fixed quantity of water. A capillary tube is connected
to the casting solvent phase to monitor the solvent which enters or leaves
the bed during cure. The corresponding volume change is termed the
bed sorption. Volume changes of the casting powder bed are monitored
with the aid of a second capillary tube connected to the water phase.
The algebraic sum of the volume changes indicated by these two capil-
laries is the total volume change of the system.
VENT
FLEXIBLE SEPTUM
SAMPLE CHAMBER
(CASTING POWDER &
CASTING SOLVENT)
KJ—
"trr
r^
z
A
\
||
0 2 4 6 8 10 12 14 16 18 20 22 24 26
DAYS @ 80 ° F
Figure 21 shows that the relatively large bed volume change observed
for 30-p.s.i.g. ram pressure are accounted for by solvent expressed from
the bed, and the total volume change is actually much less than the bed
volume change.
At first sight the above results might suggest that enormous inward
travel of rams would be observed in full-scale units using 30 p.s.i.g. or
more ram pressure during cure. Such is not the case. During the early
stages of cure, ram pressure is rapidly dissipated a relatively short dis-
tance from the end of the ram piston face. Consequently, compaction of
the powder bed owing to ram pressure is confined to the immediate
vicinity of the ram face—i.e., in the powder column and just inside the
a \ i
a V
a >
\
5
Literature Cited
(5) Biot, M. A., Willis, D. G., J. Appl. Mech., 594-601 (Dec. 1957).
(6) Foust, A. S., et al., "Principles of Unit Operations," p. 473, Wiley, New
York, 1960.
(7) W. A. Noyes, Jr., ed., "Science in World War II—Chemistry," pp. 178-8,
Little, Brown, Boston, 1948.
(8) Preckel, R. F., ARS J. 31, 1286 (1961).
(9) Preckel, R. F., AIAA J. 3, 346 (1965).
(10) Thacher, J. H., CPIAPubl.119, 1, 457 (1966).
RECEIVED April 10, 1967.