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Патент USA US2411116

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2,411,116
Patented Nov. 12, .1946
' UNITED sTAT'E S PATENT OFFICE
2,411,116
, SELF-HEALING CONTAINER FORMING
'
MATERIAL
'
- Manuel Sanz, Los ' Angeles, Calif., assignor, by
mesne assignments, to Consolidated Vultee Air
craft Corporation, a corporation of Delaware
Application March 21, 1942, Serial No. 435,689
4 Claims.
(01. 1544-435)
1
2
The present invention relates generally to self
healing material. More particularly the inven
tion relates to that type of material which is
more particularly de?ned by claims at the com I
designed primarily for use in the fabrication of
a vfuel or lubricant container, automatically seals
5 .
‘ itself immediately after being punctured or torn
clusion hereof.
In the drawing which accompanies and forms
a part of this speci?cation or disclosure and in
which like numerals of reference denote corre
sponding partsthroughout the several views:
Figure l is a perspective of a piece of self
by“ a projectile or like object, and comprises a
healing container forming material embodying
self-healing intermediate layer of masticated rub-'
her having pronounced cohesiveness, an outer
the invention; and
Figure 2 is an enlarged section of the material.
layer of tough elastic material, such, for exam 10
The material which is illustrated in the draw
ple, as fully cured or vulcanized rubber, and
an inner‘ layer of synthetic rubber or like mate
ing constitutes the preferred form or embodi
rial of the type that is insoluble in, and unaf
ment‘of the invention. It is essentially of‘ the self
fected by, hydrocarbons.
1
healing variety and has special capability of use
The primary object of the invention is to pro 15 in the fabrication of a gasoline or lubricant con
vide a self healing container forming material
of this type which has certain advantages over,
tainer for an airplane or other vehicle. Gener~
ally speaking, the material is a laminated or
and is more e?icient than, previously designed
materials, especially that which is disclosed in,
and forms the subject matter of, application for 20
United States Letters Patent ?led by Scott,
Rethorst on July 29, 1940, Serial No. 348,098
(now Patent No.'2,406,903, dated September 3,
lamellated structure and is of the so-called self
_
healing variety by reason of the fact that imme
diately after being punctured or torn it seals
automatically. When the material is used to form
an airplane fuel container any bullet or pro
jectile passing ‘through it results in no loss of
fuel due to the special self healing tendencies.
1946).
'
Another object of the invention is to provide 25 or properties of the material. As its components
the material comprises an intermediate layer 3,
a self healing material‘ of the type and character
an outer layer 4 and an inner layer 5.‘ These
under consideration’in which the self healing
three layers are bonded together as hereinafter
intermediate layer is formed of partially, cured
or vulcanized masticated rubber and has an ad
described, with the result that the material is
mixture of a small amount of synthetic resin 30 essentially of unitary character.
which is insoluble in hydrocarbons.
The intermediate layer 3 is the self healing
layer and possesses its self healing attributes due
A further object of the invention is to provide
to its chemical and physical properties. It is
a composite or laminated self healing material
formed for the most part of partially cured mas—
of the aforementioned type in which the inner
layer of vulcanized synthetic rubber is vulcanized
ticated rubber and is characterized by the ‘fact
that it has an extreme or ‘pronounced degree
in situ on the inner face of the self healing
of cohesiveness. This marked degree of cohe
intermediate layer and has an admixture of a
siveness results in the layer having the desired
small amount of a synthetic resin which serves
as an e?icient plasticizer for the synthetic rub
self healing action. The layer 3 is formed by.
ber- while at the same time it does not affect 40 mixing together the following components or
ingredients 'in substantially the proportions set
in any way the resistance of the synthetic rubber
to gasoline, oil or other hydrocarbons.
forth and then subjecting them to a vulcaniz
ing temperature in order to obtain a partial cure:
A still further object of the invention is to
provide a self healing container forming material
which is generally an improvement inthe art, 45
effectively and e?iciently ful?lls its intendedpur
pose and may be manufactured at a compara
tively. low cost.
‘
‘
.
‘
,
.
‘
Parts by weight
Masticated rubber ______________________ __ 100
Zinc
_
2
Agent for producing partial cure________ __'_
oxide
‘A
‘
'
\
‘
Synthetic resin
advantages and characteristics of the present self 50 Pale‘crepe rubber'is preferably’ used as the rub
ber component- Such rubber is preferably mas
healing container forming material. will be ap
tic'ate'd to the desired degree of plasticity'by mill
parent from a consideration of the following
ing it together with the other ingredients or
detailed description.
components. The zinc oxide serves as an anti
The invention consists in the several novel
features whichare hereinafter set forth and are 55 oxidant and also as an activator for the agent
Other objects of the invention and the various
\
.
'
2,411,116
,
a
‘
-
3
by a ‘Shore durometer and in addition tensile
for effecting partial cure. For such agent tetra
methylthiuram disulphide or tetramethylthiuram
tetrasulphide is used.- Tetramethylthiuram di
strength of approximately 3500 pounds. per
square inch and an elongation of 550 per cent
at break. Vulcanized rubber of this character
. sulphide is known commercially as “Tuads” and
is relatively hard and has such elasticity that
when compressed by the passage of a projectile
therethrough it returns to its normal position
amount of the agent and the fact that the agent
and thereby closes the hole or puncture. When
. (tetramethylthiuram disulphide or tetramethyl
the material is punctured the punctured portion
thiuram tetrasulphide) possesses but a small
quantity of sulphur the rubber component of the 10 of the outer layer 4 springs together or contracts
and hence draws together the punctured por
~ composition constituting the layer 3 is only par
tion of the intermediate layer 3. As soon as the
tially cured or vulcanized when it is subjected
punctured portion of the intermediate layer is
to heat for vulcanizing purposes. Glycol-seba
drawn together by the action of the outer layer
cate is preferably used as the synthetic resin
‘ component. This particular material is insoluble 15 such portion seals, as hereinbefore pointed out,
due to cohesiveness and swelling. The outer
in, and unaffected by, hydrocarbons and has sev
layer 4 is formed by sheeting out into layer form
eral functions or purposes. In the ?rst place
a mass of rubber having sulphur or any other
it operates as a plasticizer for the pale crepe
vulcanizing agent therein together with a suit
rubber during mastication of the latter by mill
ing. In addition it tends to make-the layer‘3 20 able accelerator for the vulcanizing agent and
a small quantity of zinc oxide for activating the‘
plastic. Another function of the synthetic resin
accelerator. After sheeting of the mass to form
is to increase the strength of the partially cured
the layer 4 said layer is brought into contact with
rubber component of the layer 3. The synthetic
the layer 3‘and the two layers are subjected to
resin, although insoluble in, and unaffected by,
hydrocarbon, such as gasoline, does not change 25 heat. During the heating step the composition.
or rubber mass constituting the outer layer 4
to any great degree the normal properties _of the
tetramethylthiuram tetrasulphide is known com
merci'ally as ‘v‘Tetrone? Because of the small‘
masticated pale crepe rubber. It does, as previ
ously pointed out, give strength to the layer as
a whole. When the layer 3 is punctured by a
bullet or .other projectile the torn edges are 30
drawn together in response tovthe herein de
scribed action of the outer layer 4. As soon as
is fully vulcanized and the composition consti
tuting the intermediate layer 3 is partially vul
canized. As heretofore pointed out, atempera
ture of approximately 287° F. is employed for
vulcanizing purposes and. the material is sub
jected to such temperature for forty minutes.
During the vulcanizing operation'there is a slight
such edges are drawn into contact with one an
migration of “the sulphur or other vulcanizing
other a sealing action is effected due to‘ the
marked or pronounced degree of cohesiveness of 35 agent in the outer layer into the outer face of
the intermediate layer 3. Such migration results
the layer 3. Because a slight amount of gaso
in the outer layer becoming permanently bonded
line flows into the cut or tear a swelling action
to the intermediate layer.
takes-place and this assists in effecting auto
matic sealing. This swelling is due to the chemi
The inner layer 5 is coextensive with, and per
cal action which takes place when ‘the partially 40 manently bonded to, the irm'er face of theinter
cured rubber is contacted by the gasoline. By
mediate layer 4. It is formed of vulcaniz‘ed syn
having a small amount of synthetic resin, such
thetic rubber and an admixture of synthetic resin.
as glycol-sebacate, in the layer 3 the torn edges
“Neoprene” [chloroprene] or “'I'hiokol” [an olefin
of the punctured portion of the layer have suf?- . polysul?de reactionproductl may be used as the
cient resistance to the gasoline so that the seal 45 synthetic rubber component of the inner layer 5. ‘
obtained by cohesion and swelling is not weak
ened or dissolved by the gasoline. Glycol-seba
cate is a polymerized ester of the alkyd type and
is known commercially as “Dyal 1929.” In lieu
of glycol-sebacate, glycerol phthalate may be,
used. In producing the layer 3 the various com
ponents or ingredients are introduced into a mill
and are then milled until the composition has a
‘ plasticity of 250 as measured by a Williams par
Glycol-sebacate is preferably used as the syn
thetic resin. In practice it has been found that .
such a resin when used in an amount of from
,
so
1% to 10% by weight of the synthetic rubber pro
duces the desired results. The synthetic resin,
that is, the glycol-sebacate, serves as a plasticizer
for the synthetic rubber and makes it possible
readily and evenly to sheet the composition con
After milling to the
stituting the inner layer in connection with
formation of such layer. .In forming the inner
proper extent the composition is calendered into
layer form. It is then subjected to a tempera
ture of approximately 287° F. for forty minutes.
layer the synthetic resin is milled or otherwise
mixed with the synthetic rubber and the resultant
allel plate plastometer.
mass is then sheeted onto the inner face of the
During the high temperature period to which
intermediate layer 3 prior to the vulcanizing step.
the composition is subjected a partial cure or 60 During‘ the vulcanizing stepvulcanization of the
vulcanization of the pale crepe rubber compo
inner layer occurs and the latter becomes per
nent’isl obtained. _The ?nal product constitut
manently bonded to the inner face of the inter
mediate layer 3. The inner layer, by reason of
the fact that it is formed of synthetic rubber,
, however, plastic and possesses an extremely high 65 such as “neoprene” or “Thiokol,” and synthetic
ing the layer 3 is pronouncedly elastic but has
‘substantially no adhesiveness or tackiness. It is,
degree of cohesiveness.
The outer layer 4 serves as a reenforcing or
resin, such as glycol-sebacate, is insoluble in,
and unaffected by,‘ gasoline or other hydrocarbons
strengthening medium for the self healing inter
and hence ,when the material is used to form a
mediate layer 3 and is coextensive with the lat
fuel container the fuel is prevented from con
ter. It is permanently bonded to the outer face 70 tacting and a?ecting the intermediate layer 3
of the layer 3 and is formed of fully cured or vul
canized rubber. In practice it has been found
that desirable results are obtained when the
of partially cured masticated rubber. The inner _
layer is tough, elastic and flexible and when punc
tured the punctured portion springs back and
draws with’ it the adjacent punctured portion of
outer layeris formed of vulcanized rubber hav
ing a hardness of approximately 65 as measured 75 the intermediate layer 3. The punctured por
2,411,110
6
tion of the inner layer permits a small portion of
gasoline to ?ow into the cut or punctured por
strength of, the masticated partially cured rub
ber without inhibiting swelling of said rubber
tion of the intermediate layer and this results in
when the latter is contacted by hydrocarbons, an
swelling of the punctured portion of the inter
outer layer of tough highly elastic vulcanized rub-.
mediate layer, as heretofore pointed out. In Cl ber vulcanized in situ on the outer face of, and
practice it has been found that desirable results
serving to reenforce, the self healing layer and
are obtained when the synthetic rubber consti
adapted in connection with puncture of the mate
tuting the-inner layer 5 has a hardness of ap
rial .to have its punctured portion contract and
proximately 35 as measured by a Shore durom
draw together the punctured portion of the self
eter. Because glycol-sebacate, the material that 10 healing layer, and an inner layer of vulcanized
is used as the plasticizing agent for the syn- , synthetic rubber vulcanized in situ on the inner
thetic rubber component of the inner layer, is
insoluble in, and unaffected by, hydrocarbons, the
hydrocarbon resisting properties ofthe synthetic
face of the intermediate layer and selected from
the group consisting of Chloroprene and an olefin
polysul?de reaction product.
rubber are not affected. By having glycol-seba 15
cate or a similar synthetic resin in the inner layer .
as well as the intermediate layer an eiiicient bond
between the two layers is obtained.
‘
'
3. A container forming material comprising a
self healing intermediate layer formed of masti
cated partially cured rubber having an extremely
high degree of cohesiveness but substantially no
tackiness or adhesive tendency, and a uniformly
The thickness‘ of each layer is immaterial,
although it has been found in practice that good 20 dispersed admixture of a synthetic resin selected
resultsare obtained when the inner layer 5 is
from the group composed of glycol-sebacate and
a‘: of an inch in thickness; the intermediate layer
glycerol phthalate and in such amount that it
3 is 1A; of an inch in thickness: and the outer
serves as a plasticizer for, and to increase the
layer 4 is 1”; of an inch in thickness.
strength of, the masticated partially cured rubber
The herein described material effectively and 25 without inhibiting swelling of said rubber when
efficiently ful?lls its intended purpose and has
the latter is contacted by hydrocarbons, an outer
marked or pronounced self healing properties.
layer of tough highly elastic vulcanized rubber
Whereas the material has been described as
bonded to the outer face of, and serving to reen
being primarily for use in the manufacture of
force, the self healing layer and adapted in con
fuel containers it is to be understood that it is 30 nection with puncture of the material to have
capable of being used for'othe'r purposes. It is
its punctured portion contract and draw together
also to be understood that the invention is not
the punctured portion of the self healing layer,
to be restricted to the details set forth since these
and an inner layer bonded to the inner face of
may be modi?ed within the ‘scope of the appended
the intermediate layer and formed of vulcanized
claims without departing from the spirit and
synthetic rubber selected from the group consist
scope of the invention.
ing- of Chloroprene and an ole?n polysul?de re
Having thus described the invention what I
action product and a uniformly dispersed admix
claim as new and desire \to secure by Letters Pat
ture of glycol-sebacate in su?icient amount to
ent is:
plasticize the vulcanized synthetic rubber and
'1. A container forming material comprising a 40 also promote adhesion of the latter to said inner
self healing intermediate layer formed of masti
face of the intermediate layer.
‘
cated partially cured rubber having an extremely
4. A container forming material comprising a
high degree of cohesiveness but substantially no
self healing intermediate layer formed of masti
tackiness or adhesive tendency, and a uniformly
cated partially cured rubber having an extremely
dispersed admixture of a synthetic resin selected 45 high degree of cohesiveness but substantially no
from the group composed of glycol-sebacate and
tackiness or adhesive tendency, and a uniformly
glycerol phthalate and in such amount that it
dispersed admixture of a synthetic resin selected,
serves as a plasticizer for, and to increase the
from the group composed of glycol-sebacate and
strength of, the masticated partially cured rubber
glycerol phthalate and in such amount that it
without inhibiting swelling of said rubber when
serves as a plasticizer for, and to increase the
the latter is contacted by hydrocarbons, an outer
strength of, the masticated partially cured rubber
layer of tough highly elastic vulcanized rubber
without inhibiting swelling of said rubber when
bonded to the outer face of, and serving to re
the latter is contacted by hydrocarbons, an outer
enforce, the self healing layer and adapted in
layer of tough highly elastic vulcanized rubber
connection with puncture of the material to have 66 vulcanized in situ on the outer face of‘, and serv
its punctured portion contract and draw together
ing to reenforce, the self healing layer and
the punctured portion of the self healing layer,
adapted in connection with puncture of the ma
. and an inner layer bonded to the inner face of the
terial to ‘have its punctured portion contract and
draw together the punctured portion of the self
healing layer, and an inner layer formed of vul
canized synthetic rubber vulcanized in situ on
the inner face of the self healing layer and
selected-fromv the group composed of Chloroprene
intermediate layer and formed of vulcanized syn
thetic rubber that is insoluble in, and unaffected
by. hydrocarbons.
,
'
2. A container forming material comprising a
self healing intermediate layer formed of masti
cated partially cured rubber having an extremely '
- and an ole?n polysul?de reaction product and a
high degree of cohesiveness but substantially no 66 uniformly dispersed admixture of glycol-sebacate
tackiness or adhesive tendency, and a uniformly
'insu?icient amount to serve as a. plasticizer for
_ dispersed admixture of a synthetic resin selected
’ the vulcanized synthetic rubber and also to pro
from the group composed of glycol-sebacate and
glycerol phthalate and in such amount-that it '
mote adhesion of the latter to said inner face of
' the intermediate layer.
serves as a plasticizer for. and to increasefthe 7Q
‘
MANUEL SANZ.
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