Feb.

15, 1966

c. v. MURPHY

3,235,420

PROCESS OF MAKING HOMOGENEOUS PARTICLES COMPRISING

NITRQCELLULOSE MIXTURES
Flled May 4, 1962

AQUEOUS SLURRY
OF EMULSIFIERS
AND SOLVENT

ADDITION OF

EXPLOSIVE MIXTURE

REFLUX

CENTRIFUGE

DRYING

INVENTOR

CHARLES V. MURPHY

BY

"Kr

ATTORNEY

United States Patent 0

C6

3,235,420
Patented Feb. 15, 1966

3,235,420

PROCESS OF MAKING HOMOGENEOUS PAR

TICLES COMPRISING NITROCELLULOSE
MIXTURES

Charles V. Murphy, Merchantville, N.J., assignor to E. I.

du Pont de Nemours and Company, Wilmington, Del.,

The solvent for nitrocellulose and the non-polymeric

explosive must not be miscible With water and preferably
less than about 5% soluble in water. It must boil below
about 100 C. or form an azeotrope with water boiling

at less than about 100 C. The preferred solvents for

practicing this invention are isopropyl acetate and butyl
acetate.

a corporation of Delaware

Filed May 4, 1962, Ser. No. 192,429

12 Claims. (Cl. 149-18)

In order to obtain the eminently satisfactory products

of this invention, emulsifying agents are included in the
reaction medium. Without them the particles do not
The present invention relates to explosive composi 10 have the spherical shape and controlled size. There
tions in the form of small, dense spheres and to a process
must be at least one anionic emulsifying agent admixed
for their manufacture.

'

Solid" propellant compositions are of considerable in

with at least one non-ionic emulsifying agent.

Anionic

emulsifying agents suitable in the practice of this inven-.

terest in the ?eld of rocketry, missiles and the like. In 15 tion are sodium dialkylsulfosuccinates such as sodium
forming solid propellant grains it is necessary to include
di(2-ethylhexyl)sulfosuccinate. Non-ionic surface active
some material to behave as a binder for the more ener
agents suitable in the practice of this invention are poly
getic compounds used. These energetic materials include
oxyethylene sorbitan monolaurate (sold as Tween 20),
ammonium perchlorate, ammonium nitrate, etc. Binders
polyoxyethylene sorbitan monopalmitate (sold as
which have been used include urethane polymers and the 20 Tween 40), polyoxyethylene sorbitan monooleate (sold
like. Binders of this type, however, dilute the energy
as Tween 80).
content of the propellant, therefore binders containing
The total emulsi?er content must be at least 2% based
energetic groups are desired. Nitrocellulose in the form
on the weight of the water present. The upper limit is
of small spheres has been used as a binder because such
based only on economics but preferably would not be
spheres have the property of being incorporated into 25 above 6%.
propellant mixes containing plasticizers easily and thor
The ratio of non-ionic emulsi?er to anionic emulsi?er
oughly to give stable ?uid dispersions followed by a
can range between about 70:30 to about 40:60. The
slow and controllable gelation as the particles of nitro
preferred range lies between about 65:35 and 55:45.
cellulose solvate. Compositions of nitrocellulose and
The .particle size of the non-polymeric explosive/nitro
higher energy materials such as cyclotetramethylene 30 cellulose spheres is in?uenced by the water:(explosive

tetranitramine (HMX) and cyclotrimethylenetrinitramine

+nitrocellulose) and the solvent:(explosive-l-nitrocellu

(RDX) have a higher heat of decomposition than nitro

lose) ratios. This average particle size ranges from

cellulose alone and thus have more energy.
about 25 microns to about 200 microns. Although I do
The present invention provides small, dense, spherical,
not wish to be bound by theory I believe that the
homogeneous particles of nitrocellulose admixed with a 35 greater the quantity of liquid (water+solvent) the more
solid, organic, water-insoluble, non-polymeric explosive.
?nely subdivided the particulate material can be with
These small, dense spheres are produced by a process
a given degree of agitation. The s0lvent:(nitrocellu
comprising mixing (a) nitrocellulose, (b) a solid, or
lose+explosive) ratio can vary from about 6/1 to about

ganic, water-insoluble, non-polymeric explosive, (c)

4/ 1. The water:(nitrocellulose+explosive) ratio can
water, (d) an organic solvent both for nitrocellulose and 40 vary from about 7/1 to about 5/1.
for non-polymeric explosive, (e) a non-ionic emulsi?er,
During the period of formation of the spherical par
and (f) an anionic emulsi?er, distilling off the organic
ticles the contents of the reaction vessel are ?rst mixed
solvent and separating said spheres from the aqueous
at room temperature and then heated to the re?ux tem
residue.
.
perature of the solvent-water azeotrope. The mixing
The nitrocellulose used in making the products of the

at room temperature serves to uniformly distribute the

present invention should have as high a nitrogen content

ingredients before heating to distill off the solvent. The

"as possible without impairing its solubility properties.

While the nitrocellulose does not go into solution during
the process of preparing the dense spheres of the present
invention, the solubility properties of the nitrocellulose
'play an important role in casting the ?nal propellant
grain because of their in?uence on the gelation time in
forming the grain and the strength and elongation proper
ties of the ?nished propellant. The nitrogen content of

length of this mixing can vary from about 20 to about

60 minutes.
After all of the solvent-Water azeotrope is distilled off
the heating is continued until the vapor temperature

reaches that of the boiling water.

This ?nal heating

serves merely to remove the last traces of organic sol

vent.

Good agitation is required for the instant process in

the nitrocellulose usable in the present invention varies 55 order to properly disperse the heterogeneous phases pres
from about 12% to about 13%. The grade of nitro
ent and to get spherical particles. The speed of agitation
needed depends on the construction of the vessel and
cellulose, known in the art as pyro nitrocellulose, and
having a nitrogen content of about 12.6% is the pre
agitator blade and on the size of the vessel and agitator

ferred grade for practicing this invention.

blade. A vessel having ba?les will require a lower speed
The solid, organic, water-insoluble, non-polymeric ex 60 of agitation than one without ba?les, for example. In
plosive used in conjunction with the nitrocellulose will
general, turbulent agitation is needed.
be one having a high-energy content. Examples are
Anti-foaming agents may optionally be added to the
reaction mixture during distillation to prevent carrying
pentaerythritol tetranitrate (PETN), HMX, RDX and
many others. The preferred explosives are HMX and
over of entrapped liquid during the distillation of the
RDX.

65 solvent-water azeotrope.

The ratio of nitrocellulose to non-polymeric explosive

can vary from about 40/60 to about 10/90.

Nitro

These antifoaming agents are

not essential to the invention but merely reduce the time
necessary for distilling off the solvent. Silicone oils are

cellulose serves as a binder for the non-polymeric ex

suitable anti-foaming agents.

plosive so that too little of it gives a fragile particle.

Too much nitrocellulose is not disadvantageous except
from the standpoint of low relative energy content, but
generally as little nitrocellulose as possible will be used.

in the formulation but play no part in obtaining the unique

physical form of the products of the instant invention.
They serve merely to prevent autocatalysis of the decom

Conventional nitrocellulose stabilizers can be included

3,235,420

position of the nitrate ester by absorbing nitrogen oxide

trifuge and the liquid separated from the solid. The solid

fumes as they are formed on standing over long periods.

Such stabilizers as diphenylamine, 2-nitro-diphenylamine,

spheres of HMX-nitrocellulose are dried at 55 C. These

spheres have an average diameter of 150 microns and a

and the centralites are useful.

particle density of 1.76. Eighty-?ve percent of the par

The propellant particles of the instant invention are

ticles are spheres, and the remaining particles are elon

gated spheres and rods.

Example 2
of the propellant are spherical with the remaining particles
The exact procedure of Example 1 is repeated using
being elongated spheres and rods. The essentially spheri
cal nature of the particles gives a product having a higher 10 the following ingredients:
Parts
bulk density than that of a product having non-spherical
Water _________________________________ __ 10,000
particles, which is easily incorporated into a plasticizer.
Tween 20 _____________________________ .._
150
The particle density of the propellant ranges from about

characterized by being essentially spherical, dense and

non-porous. At least 60% of the particles in any sample

1.6 to 1.8 g./ml. The spheres of the instant product vary

Aerosol OT ___________________________ __

150

in average diameter from 25 microns to 200 microns with 15

Isopropyl acetate ________________________ __

8,000

essentially no particles having a diameter greater than

250 microns. These particles increase the gelation time

RDX

__________________________________ __

1,420

Pyro nitrocellulose _______________________ __

580

when they are placed in a plasticizer or solvent therefor

over that obtained with more porous particles. This

2-nitrodiphenylamine

_____________________ __

30

The product is again in the form of dense spheres

increased gelation time is advantageous because it allows 20 having an average particle diameter of 125 microns.
more time for compounding a ?nished propellant before
Eighty percent of the particles are spheres and the re
the composition sets up.
mainder elongated spheres and rods.
The nitrocellulose-HMX composition of the present
When the above example is repeated using 8000 parts
invention is surprisingly less sensitive to ignition by static
of butyl acetate instead of isopropyl acetate and distilling
25
than nitrocellulose alone in the same spherical form. The
olf the butyl acetate-water azeotrope at 90.5 C., the
static sensitivity is measured in the following way. The
product is essentially identical with the one above.
sample (0.05 g.) is placed in a depression in a brass plate
Example 3
and an electrical spark of known energy is discharged
through the material from a needle electrode 5 mm. above

Polyoxyethylene sorbitan monolaurate (1.8 parts) and

the plate. The spark energy is reduced in 0.05 joule 30 sodium di(2-ethylhexyl)sulfosuccinate (1.2 parts) is dis
increments until ignition no longer occurs. This point is
solved in 20 parts of isopropyl acetate. This solution is
called the static sensitivity.
added to a mixture 100 parts of water and 100 parts of
The nitrocellulose-HMX composition described in Ex
isopropyl acetate and mixed well. HMX (7 parts) and
ample 1 has a static sensitivity of 1.93 joules Whereas
pyro nitrocellulose (3 parts) are added and the mixture
nitrocellulose alone in the same spherical form has a
agitated for about 30 minutes. The mixture is heated
static sensitivity of 1.1 joules. This means that the
to re?ux and the azeotrope of isopropyl acetate and
nitrocellulose is ignited by a spark having less energy
water is distilled off at about 76 C. while continuing
than that necessary to ignite the nitrocellulose-HMX
agitation. After the azeotrope is distilled off, the vapor
mixture.
temperature is allowed to rise to 100 C. The hot slurry
The process of the instant invention is more readily
is then centrifuged to separate the liquid from the solid.
understood by reference to the drawing which, sche
The solid consists of essentially spherical particles having

matically depicts the general process step requirements.

The aqueous slurry is formed in a reactor and comprises

water, at least one anionic and at least one non-ionic
emulsi?er and a solvent for nitrocellulose and a solid,

organic, water-insoluble, non-polymeric explosive, pref

erably RDX or HMX.

The slurry is agitated and the

nitrocellulose and the non-polymeric organic Water-solu

ble explosive, i.e. HMX or RDX are added while agitation
continues. The reactor is then heated to re?ux and the
water and the solvent are distilled off, whereupon the re
action mixture is fed into a preheated centrifuge to sepa
rate the liquids from the solids. After separation the

an average particle diameter of 32 microns. Ninety-?ve

percent of the particles are smaller than 62 microns in
diameter. Sixty percent of the particles are spheres, 30
percent are elongated spheres and 10 percent are rods.
The invention has been completely described above.
Many other modi?cations will be apparent to those skilled
in the art without departing from the inventive concept.
I claim:
1. A process for making explosive compositions in the

form of :small, dense, essentially spherical, homogeneous

particles, which comprises forming an aqueous dispersion
of a mixture of (1) nitrocellulose, (2) a member selected

solid explosive spheres of nitrocellulose and non-poly

from the group consisting of pentaerythritol tetranitrate,
meric explosive, i.e., preferably RDX and HMX, are 55 cyclotetramethylenetetranitramine and cyclotrimethylene
recovered.
trinitramine, (3) an organic solvent for nitrocellulose,
The invention is illustrated by the following examples.
said solvent being less than about 5% soluble in water,
Parts, where given, are by weight.
and being selected from the group consisting of nitrocel
lulose solvents boiling below about 100 C. and those
Example 1
60 forming azeotropes with water boiling below about 100
Polyoxyethylene sorbitan monolaurate (Tween 20)
C., (4) an anionic emulsi?er selected from the group
(220 parts) and sodium di(2-ethylhexyl)sulfosuccinate
consisting of sodium dialkylsulfosuccinates, and (5) a
(Aerosol OT) (140 parts) are dissolved in 200 parts of
non-ionic emulsi?er selected from the group consisting of
isopropyl acetate. This solution is added to 12,000 parts
of Water in a steel tank ?tted with a heating jacket and

polyoxyethylene sorbitan monolaurate, polyoxyethylene

a paddle-blade agitator and mixed brie?y. Isopropyl ace

tate (9800 parts) is added and mixed well. HMX (1420
parts), pyro nitrocellulose (580 parts) and 2-nitrodi
phenylamine (30 parts) are added and mixed for about
30 minutes with an agitator speed of 300 r.p.m. The

monooleate, the total emulsi?er content being at least 2%

reactor is then heated to re?ux and the isopropyl acetate

water azeotrope is distilled off at about 76 C. while con

sorbitan monopalmitate and polyoxyethylene sorbitan

by weight of the Water present in said dispersion, heating

said dispersion at a temperature suf?cient to distill off the

organic solvent, separating the liquid and solid phases

and recovering the solid particles.
2. The process of claim 1 wherein the solid non-poly

meric explosive is cyclotetr-amethylenetetranitramine.

tinuing agitation. After the azeotrope has been distilled

3. The process of claim 2 wherein the anionic emulsi?er
off, the vapor temperature is allowed to reach 100 C.
is sodium di(2-ethylhexyl)sulfosuccinate and the non
The hot reaction mixture is then fed into a preheated cen 75 ionic emulsi?er is polyoxyethylene sorbitan monolaurate.

3,235,420

5
4. The process of claim '1 wherein the solid non-poly

meric explosive is cyclotrimethylenetrinitramine.

5. The process of claim 1 wherein said solvent is iso

propyl acetate.
6. The process of claim 1 wherein said solvent is butyl

6
step (b) and mixing well, said nitrocellulose having a
nitrogen content of from about 12% to about 13%, (d)
distilling off said organic solvent while maintaining agita
tion, (e) separating said spherical particles from the
water present.

acetate.

'8. The process of claim 7 wherein the non-ionic emul

sifying agent and the anionic emulsifying agent are pres
sentially spherical, homogeneous particles comprised of
ent in a ratio by weight varying from about 70/30 to
nitrocellulose and an explosive selected from the group
about 40/60.
consisting of pentaerythritol tetranitrate, cyclotetrameth 10
9, The process of claim 7 wherein the non-polymeric
7. A process for the manufacture of small, dense, es

ylenetetranitramine, and cyclotrimethylenetrinitramine

which comprises: (a) dissolving a mixture of an anionic

explosive i-s cyclotetramethylenetetranitramine.

10. The process of claim 7 wherein the non-polymeric

emulsifying agent selected from the group consisting of
explosive is cyclotrimethylenetrinitramine.
sodium dialkylsulfosuccinates and a non-ionic emulsifying
1'1. The process of claim 7 wherein said solvent is iso
agent selected from the group consisting of polyoxyethyl 15 propyl acetate.
ene sorbitan monolaurate, polyoxyethylene sorbitan mon
12. The process of claim 7 wherein said solvent is butyl
opalrnitate and polyoxyethylene sorbitan monooleate in
acetate.
an organic solvent for nitrocellulose which is less than
References Cited by the Examiner
about 5% soluble in water and is selected from the group
UNITED STATES PATENTS
consisting of nitrocellulose solvents boiling below about
100 C. and those forming azeotropes with water boiling
2,027,114i
1/1936 Olsen et a1. ________ __ 1492
below about 100 C., (b) mixing the above solution with
2,425,854
8/1947 Alexander _________ __ 149-92
water and an additional quantity of said organic solvent,
2,916,996 12/1959 Coffee __________ __ 14992 X
the total emulsi?er content in the mixture thus prepared
being at least 2% by weight of the water present, (c) 25 CARL D. QUARFORTH, Primary Examiner.
adding said explosive and nitrocellulose in a ratio ranging
LEON D. ROSDOL, Examiner.
from about 60/40 to about 90/10 to the mixture from