Jan.

4, 1966

w. T, JONES ETAL

3,227,588

CRYSTALLINE EXPLOSIVES IN A VISCO~ELASTIC BINDER OF SHEET FORM

Filed March 11, 1964

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United States Patent 0

1

3,227,588
Patented Jan. 4, 1906

2
plasticiser. For example, it has been found that poly
isobutylene with a molecular weight of about 15,000
(Staudinger) requires the addition of about 20% of a
plasticiser before it can be readily incorporated with the

3,227,588

CRYSTALLINE EXPLOSIVES IN A VISCO

ELASTIC BINDER 0F SHEET FORM
Walter Thomas Jones, Petts Wood, Kent, and John Wilby,

Eltham, London, England, assignors to Her Britannic

explosive.

Department, London, England

Suitable plasticisers are aliphatic esters containing at

least 15 carbon atoms and the esters of dibasic acids, such
as sebacic acid and phthalic acid,.are particularly suitable.

Majestys Principal Secretary of State for the War

Filed Mar. 11, 1964, Ser. No. 351,138

Claims priority, application Great Britain, Mar. 14, 1963,

10,115/63
15 Claims. (Cl. 14918)

10

Examples of suitable plasticisers include ethyl oleate,

dibutyl phthalate and di(2-ethylhexyl) sebacate.
The presence of extremely ?ne particles (i.e. particles

of less than 1 micron in diameter) of a polymeric highly

The present invention relates to explosive compositions
?uorinated halocarbon in the binder of the explosive com
that are particularly useful for the production of explosive
position, confers the ability on explosive sheets made of
sheets, which are used, for example, to harden metal
the composition to remain in contact with a surface with
surfaces and to form, shape or demolish metal articles.
out having excessive surface stickiness and generally en
Explosive compositions in accordance with the present
hances their mechanical and ?exing properties. In par
invention provide explosive sheets that have su?icient
ticular, the resistance to tearing is increased and the
mechanical strength to retain an imposed shape without
chances of cracking during ?exing are reduced.
support and su?icient ?exibility to be bent through acute
angles without materially cracking or breaking. Further 20 Suitable ?uoro-poly-mers are aliphatic polymeric ?uoro
carbons that do not contain any hydrogen but may contain
more, these explosive sheets do not require coating either
another halogen, for example, chlorine and which are
to provide strength or to remove surface stickiness.
made by a suspension process so that they can separate in
In accordance with the present invention, an explosive
extremely ?ne particles in the composition. Such com
composition that is suitable for the production of explosive
sheets comprises between 85% and 90% by weight of a 25 pounds are exempli?ed by polytetra?uoroethylene, poly

hexa?uoropropylene and polytri?uorochloroethylene.

crystalline high explosive, such as R.D.X. (cyclo trimethyl

The preferred ?uoropolymer is polytetra?uoroethylene

ene trinitramine), H.M.X. (cyclo tetramethylene tetrani
(P.T.F.E.), which is available commercially (for example,
tramine), P.E.T.N. (pentaerythritol tetranitrate) or tetryl
grade CD3 supplied by Messrs. I.C.I. Ltd.) as a powder
(2,4,6-trinitrophenylmethylnitramine), in a ?ne particu
late form with a bimodal particle size distribution bound 30 consisting of aggregates (about 500 to 600 microns in
diameter) composed of individual particles, each about
7 in a visco-elastic binder of which between about 3 and
0.1 micron diameter, so that the aggregates can be broken
25% by weight is a highly ?uorinated polymeric halo
down in the ?nal manufactured explosive composition.
carbon. The term highly ?uorinated throughout the
If the ?uoropolymer is present in only a small propor
speci?cation and claims includes fully ?uorinated. If
there is less than 85% by weight of the explosive there is 00 U1 tion (at least 3%) of the visco-elastic binder there is some
improvement in the properties of the explosive composition
but proportions between 5 and 20% by weight, and
preferably between 7 and 15% by weight must be added

van increasing chance (particularly for thin sheets) that

the sheet will not propagate a detonation.

If there is

more than 90% of explosive the sheet is brittle and lacks

mechanical strength. The proportion of explosive is

preferably between 87% and 89% by weight.
To produce an explosive composition containing these
high proportions of explosive powder and yet having

40

to obtain the best-results.

There is no overall improvement in the properties of

the composition as the proportion of ?uoropolymer is

increased beyond 20% by Weight of the binder, and as

the mixing and rolling of the composition in manufacture

' suitable rheological properties, the explosive must be

I present as a ?ne powder (i.e. at least 95% of the particles

_ becomes increasingly ditlicult as the proportion increases

are less than 100 microns diameter) which has a bimodal

beyond 20%, the proportion should not exceed 25%.

particle size distribution so that a high degree of particle

packing can be achieved with separation of the particles
in the binder matrix. The measured particle size distribu
tion of a suitable explosive powder showed one peak

Furthermore, the ?uoropolymer sti?'ens the composi

tion so allowance should be made for this when deter

mining the viscosity of the binder, especially for additions

of more than 10% say. A suitable overall viscosity value

between 20 and 25 microns and another between 8 and 50 for the binder with the fluoropolymelr added is between

10 microns while practically all of the powder had a

40,000 and 200,000 poises determined 'by the extrusion

particle size of less than about 50 microns.

method using Mooneys equation at a rate of shear of

The visco-elastic binder used in the explosive composi- .

1tion is a Bingham material whose response to stress

conforms to the superposition of elements which obey

Hookes elastic law and elements which obey Newtons
viscosity law. Visco-elastic substances which are prefer
ably used as the main constituent (i.e. comprising more
than 50% by weight of the viscoelastic binder) are

5sec._1 at25 C.

'

Crystalline high explosives are not produced in the

form of ?ne particles as required for the explosive com
position and any treatment such as crushing the neat

high explosive to produce ?ne particles is preferably

avoided. However, in accordance with a feature of the
invention, an explosive composition as hereinbefore de

aliphatic hydrocarbon polymers, such as polyisobutylene 60 scribed may be readily manufactured by forming'a mixed
or polypropylene, having a substantially linear polymer

composition of the constituents in the required propor

chain with lower alkyl side-groups. Polyisobutylene is a

tion and then repeatedly passing the mixture through

satisfactory binder when its molecular weight is at least of

differential rollers having a separation which is less than

0.01 inch, and is preferably about 0.002 to 0.003 inch.
In accordance with the invention, therefore, a process
for the manufacture of an explosive composition com~
prises intermixing a composition containing 85 to 90%

the order of 5,000 (when measured by S'taudingers

viscosity method); too low a molecular weight results in
a sticky explosive composition that lacks mechanical
strength. When the binder has a relatively high molecular
weight it may be too viscous for ready incorporation with
the explosive even in a water slurry, in which case the

_ by weight of a crystalline high explosive in a visco-elastic

binder containing between 3 and 25% by weight of a

viscosity may be reduced by blending with a suitable 70 highly ?uorinated polymeric halocarbon as extremely ?ne
amount of either a lower molecular weight polymer or a
particles made by a suspension process, and repeatedly

3,227,588
=3

passing the mixed composition through differential rollers

having a separation less than 0.01 inch, whereby the high
explosive is ground into ?ne particles having a bimodal

23.
added and stirring continued for one hour, at the end
of which time the particles of R.D.X. are uniformly
coated. The suspension is ?itered through a oambric

size distribution and the polymeric halocarbon is dis

persed in the binder.
It is generally impractical, especially in large scale

?lter to remove excess Water and the ?ltered material con

processes, to incorporate the explosive with the binder

in the cold for one hour. The explosive composition is

taining about 20% of water is thoroughly mixed with

P.T.F.E. (1.2 lb.) in a Werner P?eiderer incorporator

then passed repeatedly through a di?erential rolling ma

after the ?uoropolymer has been added, and the explosive
chine having knurled rollers rotating at different periph
is then incorporated with the plasticized binder before
the ?uoropolymer is added. In practice a Water slurry 10 eral speeds so that there is a pronounced shearing action
on the composition as it .passes between the nip between
of the high explosive is intermixed with the binder which
the rollers.
is then drained before the addition of the ?uoropolymer.
A suitable machine is a Torrance drum feed roll set
The differential rollers in practice should be knurled
to a minimum separation between its knurled rollers of
as otherwise it is di?icult to pass the moist composition
through the narrow gap. The number of passes required 15 0.003 inch and having a 12 in. diameter roll rotating at
about 15 r.p.m. and a 15 in. diameter roll rotating at
to grind the explosive particles to the required size is

about 60 r.p.m. The peripheral speeds of the two rolls

reduced by decreasing the gap between the rollers and by

increasing the difference between the peripheral speeds

are thus about 50 and 250 ft./min. giving a differential

of the rollers which causes shearing of the particles.

speed of about 200 ft./min. Under these conditions, the

Between 10 and 30 passes should be su?cient if a gap

of about 0.002 to 0.003 inch is used with a differential

composition is repeatedly passed through the rolls by

peripheral speed of the rollers of the order of three

feet/sec. This differential rolling also breaks down the

aggregates of ?uoropolymer particles and disperses the

particles through the composition.

Explosive compositions in accordance with the inven

tion are essentially as follows:

__________________________ __

R.D.X. before mixing in the P.T.F.E., in the way already

described. However, on a smaller scale (about 2 kg.)
incorporation of R.D.X. with the complete visco-elastic

binder composition containing the P.T.F.E. is practicable.

0.5-3

Percent

P.T.F.E.

As the binder composition is made more viscous by

the addition of the P.T.F.E. it is easier to incorporate the

The differential rolling machine may then be a Torrance

By way of example, a typical general explosive com

Polyisobutylene+plasticiser

hours at 95 C. or the composition can be left as thin

sheets and simply dried in an oven.

85-90

position is:
High explosive _________________________ __

A Werner P?eiderer incorporator may

Percent
Viscose-elastic binder _____________________ __ 9.5l2
Fluoropolymer

The explosive composition is then ?nally dried in any

suitable drier.

25 be used, for example, treatment lasting for about four

The explosive composition is then dried and can be

formed into an explosive sheet simply by a ?nal rolling
between rollers separated by the desired thickness of
the sheet which may in practice be down to about 0.08
inch.

High explosive __________________________ _._

the circulating drum feed for about ?ve minutes, this

being theoretically equivalent to about 25 passes.

87-89

______________ __ 10.5-11

______________________________ __

11.5

The high explosive may be R.D.X., I~LM.X., P.E.T.N.

or tetryl.

A speci?c composition A which falls within this gen

eral composition is as follows:

Laboratory Roll through which the explosive composi

tion is given ten passes with a minimum separation of
about 0.003 inch.
The explosive sheets are made by passing the dried

explosive composition through a rolling machine, having

two smooth steel rollers of the same diameter, rotating
at identical speeds, with the gap set to give the desired
sheet thickness down to about 0.08 inch.
Vie claim:
1. A flexible explosive sheet composition which com
45 prises between 85 and 90% by weight of a crystalline

high explosive in a ?ne particulate form with a bimodal

particle size distribution which is bound in a visco-elastic

binder of which between 3 and 25% by weight consists

of extremely ?ne solid particles of a highly ?uorinated
Polyisobutylene (Oppanol B15) ______________ __ 8.4 50 polymeric halocarbon having a diameter less than 1
micron through said binder.
Di(2-ethylhexyl) sebacate ___________________ __
2.4
2. A ?exible explosive sheet composition according to
P.T.F.E.
_________________________________ __
1.2
claim 1 in which said crystalline high explosive is a ni
An alternative composition B using a less viscous grade
trarnine explosive.
3. A ?exible explosive sheet composition according to
of Polyisobutylene is as follows:
Percent
claim 1 in which the said polymeric halocarbon is poly
Percent

R.D.X.

__________________________________ __

88.0

R.D.X.

__________________________________ __

88.0

tetra?uoroethylene.

d. A ?exible explosive sheet composition according to

claim 3 in which the polytetra?uoroethylene is present in
P.T.F.E.
_________________________________ __
1.2 60 a proportion between 5 and 20% by Weight of the visco
elastic binder.
All the above percentage proportions are by weight.
5. A ?exible explosive sheet composition according to
By way of example, the manufacture of an explosive
claim 4 in which the polytetra?uoroethylene is present as

Polyisobutylene (Oppanol B8) _______________ __

9.6

Di(2-ethylhexyl) sebacate ___________________ __

1.2

composition having the speci?c composition A and the

particles of the order of 0.1 micron diameter in a propor
production of explosive sheets therefrom will now be 65 tion between 7 and 15% by weight of the visco-elastic
described. The complete manufacture is illustrated by
binder.

the accompanying diagrammatic drawing.

Polyisobutylene (70 parts by weight) is stirred and

6. A flexible explosive sheet composition according to

claim 1 in which the high explosive is cyclo trimethylene

heated in an incorporator to a temperature between about

trinitramine.

90 and 100 C. Di(2-ethylhexyl) sebacate (20 parts by

weight) is added and the mixture stirred until a mix of

uniform composition is obtained. A slurry of R.D.X.

(88 lb.) and water (500 lb.) is heated to a temperature
of about 95 C. and stirred at 200 r.p.m. in a mixing

vessel.

The plasticised polyisobutylene (10.8 lb.) is

7. A flexible explosive sheet composition according to

claim 1 in which the high explosive is cyclo tetramethylene
tetranitramine.
8. A ?exible explosive sheet composition according to
claim 1 in which the high explosive is pentaerythritol tetra
75 nitrate.

3,227,588

5
9. A ?exible explosive sheet composition according to
claim 1 in which the high explosive is 2,4,6-trinitrophenyl

methylnitramine.
10. A ?exible explosive sheet composition which com

prises between 85 and 90% by weight of a crystalline

high explosive in a ?ne particulate form having a bimodal

less than 1 micron, said polyisobutylene and plasticizer

therefor constituting between 10.5 and 11% by weight of
the composition and said polytetra?uoroethylene con
stituting 1 to 1.5% by weight of the composition.
14. In a process for the manufacture of an explosive

sheet composition the steps of intermixing a composition

containing 85 to 90% by weight of a crystalline high ex

plosive in a visco-elastic binder containing between 3 and
25 % by weight of a highly ?uorinated polymeric halo
hydrocarbon polymer having lower alkyl side chains, be
tween 3 and 25% by weight of extremely ?ne solid par 10 carbon as extremely ?ne particles made by a suspension
process, and repeatedly passing the mixed composition
ticles of a highly ?uorinated polymeric halocarbon having
through differential rollers having a separation less than
a diameter less than 1 micron, and a plasticizer for the

particle size distribution which is bound in a visco-elastic

binder comprising at least 50% by weight of an aliphatic

said hydrocarbon polymer.

0.01 inch, whereby the high explosive is ground into ?ne

particles having a bimodal size distribution and the halo
11. A ?exible explosive sheet composition according to
claim 10 in which the said hydrocarbon polymer is poly 15 carbon is dispersed throughout binder in the form of solid
particles having a diameter less than 1 micron.
isobutylene.
12. A ?exible explosive sheet composition which com

prises between 85 and 90% by weight of a crystalline high

explosive in a ?ne particulate form having a bimodal

15. A process for the manufacture of an explosive

sheet which comprises the process according to claim 14

followed by a ?nal rolling of the composition between

particle size distribution which is bound in a visco-elastic 20 rollers separated by the desired thickness of the explosive
binder comprising at least 50% by weight of polyiso
sheet.

butylene, between 3 and 25% by weight of extremely

?ne solid particles of a highly ?uorinated polymeric halo
carbon having a diameter less than 1 micron, and a plas
ticizer for the said polyisobutylene which is an ester hav 25
ing at least 15 carbon atoms.
13. A ?exible explosive sheet composition which com

References Cited by the Examiner

UNITED STATES PATENTS
2,999,743
3,102,833

9/1961
9/1963

Breza et a1. ________ __ 14919

Schulz __________ __ 14919 X.

3,117,044
1/1964 Sauer _____________ __ 149-49
prises between 87 and 89% by weight of a crystalline
3,138,501
6/1964 Wright __________ __ 14919 X
high explosive in a ?ne particulate form with a bimodal
3/1965 Wright __________ __ 149-19 X
particle size distribution which is bound in a visco-elastic 30 3,173,817
binder comprising polyisobutylene and a plasticizer for
CARL D. QUARFORTH, Primary Examiner.
said polyisobutylene and polytetra?uoroethylene in the
BENJAMIN R. PADGETT, Examiner.
form of extremely ?ne solid particles having a diameter