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US005080735A
United States Patent [19]

[11]

Patent Number:

5,080,735

Wagner

[451' v,Date of Patent:

Jan. 14, 1992

[54] LOW FLAMMABILITY CAP-SENSITIVE

[56]

FLEXIBLE EXPLOSIVE COMPOSITION

,

[75]

lnvenm

3,227,588

Mam" G. Wagner, Wllmmgton, 1391-

3,703,080 11/1972

E L du Pom de Nemours and

Company

Wilmington

DeL

149/193

Longwell ..... ..

60/219

.. 526/255

3,977,923

8/1976

Yelzinan . . . . . . . . .

. . . .. 149/191

4,023,493

5/1977

Austin et al.

.... .. 102/302

4,102,428

7/1978 Kelly et a1.

. 181/116

4,289,551 9/1981 Perrault et al.

4,861,397

Man 23 1990

Jones etal. ...................... .. 149/193

3,956,233 9/1976 Fletcher

[21] App1_ No_; 500,047

[22] Filed:

1/1966

3,632,458 1/1972 Filter et a1.

[73] Assignee:

References Cited
Us PATENT DOCUMENTS

8/1989

149/194

Hillstrom ......................... .. 149/194

Primary Examiner-Edward A. Miller

Attorney, Agent, or Firm-Charles E. Krukiel

[57]
Related 1.1.8. Application Data

[63]

[51]

Connnuation-m-part ofSer. No. 318,794, Mar. 3, I989,

abandoned'

ABSTRACT
. .

. ~.

A cap-sensitive ?exlble explosive composition of re

duced ?ammability is provided by incorporating a

?nely divided, cap-sensitive explosive in a ?ame resis

tant polymeric binder system which contains a compati

Int. Cl.5 ............................................ .. C06B 45/10

ble ?ame retardant material.

[52]

US. Cl. .......................... .. 149/193; 149/191

[58]

Field of Search ................... .. 149/ 19.1, 19.3, 19.4

14 Claims, No Drawings

5,080,735

sold under the Trademark Viton by E. I. du Pont de

Nemours & Co. are particularly useful. Polymeric com

LOW FLAMMABILITY CAP-SENSITIVE

FLEXIBLE EXPLOSIVE COMPOSITION

positions having a limiting oxygen index greater than 21

are preferred.

In preparing the compositions of this invention, one

The Government of the United States of America has

rights in this invention pursuant to DOE Contract No.
DE-AC04-87AL42544, Subcontract LCRL-89913, sub

or more of the polymeric materials of the type men

tioned above are combined using known methods to

provide an explosive containing mixture which can be

formed into sheets which remain ?exible under ambient
conditions. It is preferable that no cross-linking occurs

ject to advance waiver of patent rights W(A)87-OO5.

CROSS-REFERENCE TO A RELATED
APPLICATION
This is a continuation-in-part of US. application Ser.
No. 07/318,794, ?led Mar. 3, 1989 (now abandoned).
BACKGROUND
This invention relates to a ?exible explosive composi
tion of reduced ?ammability. More particularly, the
invention relates to a cap-sensitive ?exible explosive

during normal processing or during ambient tempera

ture storage yet occurs rapidly on exposure to high
temperatures. Preferably an activator which is activat
able by heat from an ignition source is included in the
15 system. When activated, the polymeric material is fur

ther polymerized or cross-linked thereby transforming

it from its original ?exible state to a hardened or ther
moset state. Activators for various polymer systems are >

commercially available and include organophos

phonium salts such as benzyl triphenyl phosphonium

composition containing a ?nely divided, cap-sensitive

explosive admixed in a ?ame resistant polymeric binder
system which includes a compatible ?ame retardant
material. Such compositions are useful in applications
which require self-supporting units rather than loose
particles in environments in which the units may be

subjected to ignition temperatures.

chloride, aromatic dihydroxy compounds such as bis

phenol AF, and diamines or polyamines such as trieth

ylene tetramine.
Examples of cap-sensitive explosives which can be
25 used in the compositions of this invention include solid

organic nitrates such as pentaerythritol tetranitrate

(PETN) and nitromannite, organic nitramines such as

It is known in the explosives art to provide explosive

materials in ?exible sheet form. Finely divided explo
sives are typically combined with polymeric binders.
Embodiments in which the explosives are combined
with ?ourinated polymeric halocarbon polymers are
disclosed in US. Pat. Nos. 3,227,588, 3,326,731 and
4,750,887. None of these patents address the problem of
providing a ?exible sheet explosive which is useful in
environments in which the ?exible sheet explosive may

be subjected to ignition temperatures thereby destroy

tetryl, cyclo-trimethylenetrinitramine (RDX), cyclotet

ramethylene tetranitramine (HMX), nitroguanadine,
TACOT and mixtures of one or more of the foregoing

explosives.
Compatible ?ame retardant materials include boron
containing compounds such as zinc borate, boric acid
and ammonium ?uoborate; phosphorus containing com
35

pounds, especially phosphate esters such as 2-ethyl

ing the explosive before it can be detonated. Such tem

hexyl diphenyl phosphate, and isodecyl diphenyl phos

peratures may be encountered in deep oil well drilling

where the explosive is used in production stimulation

phate, and tricresyl phosphate; antimony oxide with a

chlorine or bromine donor; hydrated materials such as
alumina trihydrate, and other materials such as chlori

charges.

nated or brominated hydrocarbons. By compatible" it

SUMMARY OF THE INVENTION

In accordance with this invention, there is provided a

is meant that the ?ame retardant material does not react

cap-sensitive ?exible explosive composition of reduced

?ammability comprising a ?nely divided, cap-sensitive

heated with the composition for a period of 24 hours at

a temperature of 250 F. In addition the other ingredi

?ame resistant polymeric binder system. The composi

tions exhibit markedly reduced ?ammability both in

plosives composition.

exothermically with the explosive materials when

explosive and a compatible ?ame retardant material in a 45 ents comprising the ?exible explosive composition must
not react exothermically when incorporated in the ex
'

Other ingredients may be added to the compositions

of this invention. These include drip suppressants and
ing the compositions of this invention the cap-sensitive
explosive and ?ame retardant material are admixed with 50 /or reinforcing agents. Addition of a small amount of
terms of ignition resistance and burning rate. In prepar

Te?on polytetra?uoroethylene resin is particularly

the polymeric binder.

The polymeric binder is chosen from ?ame resistant
polymers and copolymers which provide a ?exible ex

plosive sheet when compounded with additional ingre

dients as described herein. The sheet when exposed to 55

elevated temperatures should maintain essentially its

original dimensions. The sheet may soften when heated
but should not lose its unitary structure. Among the
suitable polymeric binders are polymers and copoly

effective in suppressing dripping when the composition

is subjected to ignition temperatures.
In preparing the compositions of this invention, all of
the ingredients are mixed together. A slurry of particles
is made starting with water-wet explosive material and

adding all other ingredients in a jacketed half-sigma

mers which are capable of further polymerizing or

blade mixer. Mixing is carried out at temperatures be

tween and 150 and 240 F., and drying is done in the
mixer. Sheets of the combined ingredients are formed

cross-linking when activated by heat from an ignition

by rolling through a two-roll mill. Extrusion processes

source. Halogenated binders which can be formed into

may also be used.

?exible sheets of the chlorinated and/or fluorinated

polymer and copolymers families, such as those con

making the composition of the ?exible explosive materi

taining tetra?uoroethylene, hexa?uoropropylene, vi

The amounts of the particular ingredients used in

65 als of this invention are not critical. In general the com

among those which are useful in this invention. Fluoro

position should contain from about 30 to 65% by weight

of ?nely divided, cap-sensitive explosive. For most

elastomers of hexa?uoropropylene/vinylidene ?uoride

explosives purposes, amounts in the range from about

nylidene ?uoride, and tri?uorochloroethylene are

5,080,735

40 to 55% will produce satisfactory results. In a pre-

_cominued

ferred embodiment of the invention, the cap-sensitive

explosive is RDX in an amount of about 50.35 percent
by weight. The amount of ?ame retardant material will
S
.
.
.
ample
vary depending on the particular material used. Gener- 5
ally, between 10 and 30% by weight gives satisfactory
.

results. Sufficient polymeric binder must be present to

provide a ?exible sheet of the combined materials. Preferably, the amount used should provide a self-support-

D5222? @

17'8

473

11.4

43.3

none

500

43

527
583

_
-

30,6
29-0

none
none

2'3 _

2'6

60%
To by
further
weightillustrate
may be the
used.present invention, ?exible
- -

435

ing sheet. Amounts in the range from about 20 to about 10

-

Sam 18
"'R_

C6

Burn To Consumption (sec)

explosive compositions were prepared as indicated

above by mixing, drying and sheeting the mixed ingre2040
MM (H8O
clients. In the examples which follow, parts and percent- 15
ages are by weight unless otherwise stated. The ?ammaIn the Strip Burn Test it was observed that the Control

bility of the compositions was determined by the following tests:

sample dripped copiously, and the dripping material

ignited and burned. Samples 1 and 2 did not drip.

Hot Bar Test - A hot-plate is maintained at a

constant temperature. A single piece of the explosive 20

composition weighing 30 mg and roughly cubical in

Plate Bum Test

shape is placed in the center of the plate. The time the

6 Time Um Flam: Exingulshed ("1:92

sam le takes to i nite (in seconds) is measured and re-

corded. The testgis conducted in triplicate, and the re-

'-

' _

T'me Um] Smoke Genmuon stopped (mm)

sults are averaged. If no ignition occurs in three min- 25

utes, the results are recorded as no ignition.

Percent of Sim 1e Remainin

so

5
95

Strip Burn Test A sample 1"X6"><" is

clamped at one end and hung vertically. The bottom of

the sample is then exposed to the ?ame of an acetylene

(Detasheet C6 15 a ?exlble exploswe comammg 63%

torch. As soon as ignition is evident, the ignition source 30 PETN sold by E- L dll Pom d8 Nem0urs'8z Co. V1

is removed. The time required for ignition is recorded

alqng with the time required for the sample to b6 con_
Sumed. Any dripping behavior is noted

toll C10 and LM are fluomelaswmers; VH0"

Cu

?uoroelastomers and Te?on DR is a TFE-Fluoro

Plate Bum Test _ A Sample of explosive composi_

carbon resin all of which are sold by the E. I. du Pont

ratives 20 and 30 are activators for the Just-mentioned

tion 6><6"><" is divided into three parts by first cut- 35 de Nemours & c0)

ting out a 4_"><4" square leaving an Ip: shaped piece.

EXAMPLE 2

The square is then cut diagonally providin g two triang-

ular pieces_ The pieces are then arranged gllapan, on an

This example demonstrates the effects of the various

8"X8" steel plate having a thickness of g" in which a

tyPFs of mgredlents .wlthml the Scope of the appellded

hole one inch in diameter has been cut at the intersect- 40 clalms' The various Ingredients are added seqlfemlany

ing point of the crotch of the L" and two points the
triangle" An 8~X 8" cover plate having a thickness of g
is placed over the explosive material. The assembly is
secured and suspended diagonally with the hole at the
bottom. An acetylene torch ?ame is impinged on the 45

m a PETN based exploswe- Sample #2 m_am5_ only

PETN and Viton @ ?ame resistant polymeric binder.
Sample #3A demol'lstrated bOrlc acld as the ?ame Tatar
dam- Sample #4A mcludes Te?n__a5 a. dr 1P SPPPTCS'
sam- Sampl? #6A employs crosslmkmg mgredlenfts to

metal at the top edge of the hole for two minutes, and
the ?ame is then removed. Burning behavior is observed. After burning is complete, the assembly is taken

allow_ the bmder to harden- The hot bar est '5 as

descnbed hemmabove

apart, and a visual judgement is made of how much of 50

Sam 16

the original sample remains.

Comm]

Detasheet

EXAMPLE

Compound:

C6

3A

4A

6A

Composition
Control

sample

c6

PETN

55 M

1
45

13 2

520W
Viton @ LM

33.3

45

Boric Acid
Te?on DR

11.0
-

11.0
2.2

11.0
2.2

4.6

2.0

Viton C10

8.3

7.2

viion LM

25.0

21.7

Te?on DR

22

2.2

Viton @ Curative No. 20

Viton @ Curative No. 30
Zinc Borate
Speci?c Gravity
Detonation

1.5
7000

3.2
1.3
15.0
1.85
6390

2.7
1.2
20.0
1.86
6430

Velocity (m/sec)

60 Viton4

Curatlve N0. 20
VilOn

Curative No. 30
Speci?c
Gravity
Detonation
65 Velocity

1.5

7000

L73

6656

L73

7067

1.74

7117

(m/sec)
Hot Bar Test

Temp. SF.)

1?. 25:1
5;. 23:5
52. 52.
18:7

Hot Bar Test

Ignition Time (sec)

Temp. (F.l

Ignition Time (sec)

6711

5,080,735

-continued

-continued

Sample

Composition (wt 72)

Control

Percent Remaining

Detasheet
Compound:

C6

:33

98

5
2

3A

"2%"?
.

4A

"one

"(me

6A

I claim:

"one

none

none

none

52-,

43

14.5

none

none

554
583

_.
-

_
-

140
~

345
32.5

none
33.5

1. A cap-sensitive ?exible explosive composition of

.

reduced ?ammability comprising a ?nely divided cap

sensitive explosive in a ?ame resistant polymeric binder
10 system which comprises a ?uorinated elastomer, or

mixture of ?uorinated elastomers, admixed with from

about 10% to about 30% by weight of a compatible
?ame retardant material, a drip suppressant, and option

EXAMPLE 3

ally a cross-linking activator whereby the binder system

This example employs RDX as the base explosive and 15 when exposed to heat from an ignition source will

a mixture of boric acid and phosphate esters as ?ame

retardant.
Composition (wt %)

crosslink and harden at a rate which is faster than the

rate at which the explosive composition will burn.

2. The composition of claim 1 wherein said composi
tion contains from about 30 to about 65% by weight of
20 said explosive and the binder system comprises from

53:; C10

522

about 20 to about 60% by weight of the composition.

vim @ LM
Te?on DR

2L0
21

3. The compositlon of claim 1 wherein said explosive

is selected from pentaerythritol tetranitrate or cyclo

Viton Curative No. 20

0.8

Vim Curaive NO- 30

Q8

8? fcid

15-0

Santtctzer 141

trimethylenetrinitramine.

25

4. The composition of claim 1 wherein said ?ame

retardant material is selected from zinc borate or boric

5.0

acid.

5. A cap-sensitive ?exible explosive composition of

reduced ?ammability comprising from about 30 to
pany, St. Louis, Missouri and consists of a mixture of 30 about 65% by weight of a ?nely divided cap-sensitive
explosive and from about 10 to about 30% by weight of
Z-ethylhexyl diphenyl phosphate and triphenyl phos~
Santicizer 141 is available from Monsanto Com

a compatible ?ame retardant material admixed with a

phate.

?uoroelastomer binder, said binder being capable of

crosslinking and hardening when activated by intense

Speci?c Gravity

1.59

Detonation Velocity

35 heat from an ignition source at a rate which is faster

6350

Hot Bar Test

than the rate at which the explosive composition will

No ignition at 583 F.

Strip Burn Test -

burn.
6. The composition of claim 5 in the form of a sheet.

145 sec

Time to consumption

7. The composition of claim 5 wherein said explosive

is pentaerythritol tetranitrate, said ?ame retardant mate
rial is zinc borate, and said ?uroelastomer is hexa?uoro

Plate Burn Test -

Time to extinguish ?ame

l min 20 sec
4 min 15 see
> 99

Time for smoke to stop

Percent Sample Remaining

propylene/vinylidene ?uoride copolymer.

8. The composition of claim 7 wherein said explosive
material is present in an amount from about 40 to about

45 50% by weight and said ?ame retardant material is

present in an amount from about 10 to about 20% by
This example employs a mixture of zinc borate and
EXAMPLE 4

weight.

hydrated alumina as the ?ame retardant.

5O retardant material comprises a mixture of phosphate

Composition (wt 7:)

PETN

40

Viton @ C10
Viton LM

6.2
24.8

Viton @ Curative No. 20

Viton @ Qurative N0. 30

0.9
0.9

Zinc Borate

15.0

Hydrated Alumina

10.0

Specific Gravity
Detonation Velocity
Hot Bar Test
Strip Burn Test -

No ignition at 583 F.
280 see

l min. 30 sec.

extinguished

stopped

11. The composition of claim 5 in which said explo

sive is cyclo-trimethylenetrinitramine, said ?ame retar
dant material is boric acid, and said ?uroelastomer is
55

5 min. 45 sec

hexa?uoropropylene/vinylidene ?uoride copolymer.

12. The composition of claim 5 in which the explosive
is cyclo-trimethylenetrinitramine, said ?ame retardant
material is zinc borate, and said ?uroelastomer is hexa

1.76

Plate Burn Test -

Time until smoke generation

esters.

?uoropropylene/vinylidene ?uoride copolymer.

5614

Time to consumption
Time until ?ame

'

9. The composition of claim 7 in the form of a sheet.

10. The composition of claim 1 in which said ?ame

60

13. The composition of claim 1 in which said ?ame

retardant material comprises a mixture of boric acid and

phosphate esters.
14. The composition of claim 1 in which said ?ame
retardant material comprises a mixture of zinc borate
65 and phosphate esters.
*

it

1k