U.S. patent number 3,714,047 [Application Number 05/020,431] was granted by the patent office on 1973-01-30 for insulating material.
This patent grant is currently assigned to Universal Propulsion Co.. Invention is credited to Frank A. Marion, Hugh J. McSpadden.
United States Patent |
3,714,047 |
Marion , et al. |
January 30, 1973 |
INSULATING MATERIAL
Abstract
This invention relates to self-extinguishing insulating
compositions containing coolants which undergo endothermic
decomposition when subjected to elevated temperature. The coolants
are incorporated in various types of binder: One is combustible
without leaving any solid residue. Another has the property of
forming a foamed char to facilitate transpirational cooling at the
heat-exposed surface. A third is incombustible. Various other
substances, such as catalysts, oxidizers and plasticizers, may also
be included.
Inventors: |
Marion; Frank A. (Riverside,
CA), McSpadden; Hugh J. (Riverside, CA) |
Assignee: |
Universal Propulsion Co.
(Riverside, CA)
|
Family
ID: |
21798590 |
Appl.
No.: |
05/020,431 |
Filed: |
March 17, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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802198 |
Feb 25, 1969 |
|
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Current U.S.
Class: |
252/62; 102/704;
252/4; 252/601; 428/480; 521/123; 521/159; 102/290; 252/3; 252/7;
428/421; 428/921; 521/128 |
Current CPC
Class: |
C08L
81/00 (20130101); C04B 26/02 (20130101); C08J
9/06 (20130101); F16L 59/00 (20130101); C04B
26/02 (20130101); C09D 5/18 (20130101); C04B
24/04 (20130101); C04B 24/045 (20130101); C04B
22/08 (20130101); Y10S 102/704 (20130101); Y10T
428/31786 (20150401); Y10T 428/3154 (20150401); Y10S
428/921 (20130101) |
Current International
Class: |
C09D
5/18 (20060101); F16L 59/00 (20060101); C08J
9/00 (20060101); C08J 9/06 (20060101); C08L
81/00 (20060101); C09k 003/28 (); C04b
043/00 () |
Field of
Search: |
;252/8.1,7,62,3,4
;260/2.5AJ ;161/190,187,184,231,403 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Ansher; Harold
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of application Ser. No.
802,198 filed Feb. 25, 1969 now abandoned.
Claims
What is claimed is:
1. An insulating composition constituting a polymerizable liquid
capable of being cured to form a solid matrix and comprising a
binder having uniformly dispersed therein a coolant substance
capable of substantially complete endothermic decomposition at
elevated temperatures above room temperatures to form gaseous
products.
2. The composition of claim 1 wherein said binder is combustible to
form gaseous products.
3. The composition of claim 1 additionally containing an oxidizing
agent capable of decomposition at elevated temperatures above room
temperatures to facilitate the oxidation of said binder.
4. The composition of claim 1 additionally containing a plasticizer
for said binder, said plasticizer being combustible to form gaseous
products.
5. The composition of claim 1 wherein said binder is a
polymerizable liquid capable of being cured to form a solid
matrix.
6. The composition of claim 5 wherein the content of said coolant
substance is in the range of above 0.5 to 4 parts by weight to 1
part by weight of said binder.
7. A self-extinguishing insulating composition, comprising an
initially liquid polymerizable binder capable of being cured to
form a solid matrix, a curing agent to polymerize said binder to
the solid state, and a coolant substance capable of substantially
complete endothermic decomposition at elevated temperatures above
room temperatures to form gaseous products, said binder being
combustible to form gaseous products without leaving a residue.
8. The composition of claim 7 wherein the content of said coolant
substance is in the range of from about 0.5 to 4 parts per part by
weight of said binder.
9. The composition of claim 7 wherein said coolant substance is
selected from the group consisting of ammonium oxalate, oxalic acid
and fumaric acid.
10. The composition of claim 9 wherein said binder is selected from
the group consisting of polysulfides, polyurethanes and epoxide
resins.
11. A self-extinguishing insulating composition comprising a
combustible binder constituting a polymerizable liquid capable of
being cured to form a solid matrix and having ammonium oxalate
uniformly dispersed therein at a level of from about 0.5 to 4 parts
per part by weight of said binder.
12. The composition of claim 11 additionally containing a
plasticizer for said binder, said plasticizer being combustible to
form gaseous products without leaving a residue.
13. The composition of claim 11 wherein said binder is selected
from the group consisting of polysulfides, polyurethanes and
epoxide resins.
14. The composition of claim 13 additionally containing ammonium
perchlorate to facilitate the oxidation of said binder.
15. An insulator, including the following substances:
a binder having properties of combusting at elevated temperatures
and forming gases and constituting a polymerizable liquid capable
of being cured to form a solid matrix;
a plasticizer having properties of combusting at elevated
temperatures above room temperatures and forming gases;
a catalyst having properties of facilitating the curing of the
binder and the combustion of the binder and the plasticizer;
and
a coolant capable of substantially complete decomposition at
elevated temperatures above room temperatures into gases in
endothermic reaction when subjected to heat.
16. The insulator set forth in claim 15 wherein the coolant
decomposes into gases which remain at the surface of the insulator
to prevent the binder and the plasticizer from combusting after the
application of heat to the insulator.
17. The insulator set forth in claim 16, further including an
oxidizer having properties of decomposing to provide an oxidation
of the binder and the plasticizer and to form gases in providing
such decomposing.
18. An insulator including the following substances:
a binder constituting a polymerizable liquid and having a
hydrocarbon chain and capable of being processed as a liquid and of
being cured to form a solid and having properties of combusting at
elevated temperatures without providing any residue;
a plasticizer constituting an ester and having properties of
combusting at elevated temperatures above room temperatures without
providing any residue;
a catalyst having properties of facilitating the curing of the
binder and the oxidation of the binder and the plasticizer at the
elevated temperatures; and
a coolant capable of substantially complete decomposition at the
elevated temperatures above room temperatures and of providing
endothermic reactions in such decomposition.
19. An insulator as set forth in claim 18, further including an
oxidizer having properties of decomposing at the elevated
temperatures to provide an oxidation of the binder and the
plasticizer and to form gases in providing such decomposing.
20. The insulator set forth in claim 18 wherein
the binder constitutes a material formed from a group consisting of
polysulfides, polyurethanes, polybutadienes, polyester resins, and
epoxides;
the plasticizer constitutes a material formed from a group
consisting of triacetin, dibutyl phthalate, and high-boiling esters
of polyfunctional alcohols; and
the coolant is formed from chemical groups consisting of oxalates,
oxalic acid, fumaric acid, oxamide, carbamide and hydrazine
compounds and carbamates.
21. An insulator including the following substances:
a binder constituting a polymerizable liquid and having a
hydrocarbon chain and capable of being processed as a liquid and of
being cured to form a solid and of combusting at elevated
temperatures above room temperatures without providing any
residue;
an oxidizer having properties of substantially complete
decomposition at the elevated temperatures to provide an oxidation
of the binder and to form gases in providing such decomposing;
and
a coolant dispersed in the binder and capable of substantially
complete decomposition at the elevated temperatures and of
providing endothermic reactions in such decomposition.
22. An insulator including the following substances and having
properties of decomposing and combusting only during the
application of heat to the insulator;
a binder having a hydrocarbon chain and capable of being processed
as a liquid and of being cured to form a solid and of combusting at
elevated temperatures without providing any residue;
an oxidizer having properties of decomposing at the elevated
temperatures to provide an oxidation of the binder and to form
gases in providing such decomposing; and
a coolant dispersed in the binder and having properties of
decomposing at the elevated temperatures and of providing
endothermic reactions in such decomposition, the binder being a
polysulfide, the oxidizer being ammonium perchlorate and the
coolant being ammonium oxalate.
23. The insulator set forth in claim 22 wherein the polysulfide,
the ammonium perchlorate and the ammonium oxalate respectively have
approximate relative parts by weight of 1, one-half and 3.
24. The insulator set forth in claim 22 wherein the ammonium
perchlorate has a range up to approximately 4 parts by weight to 1
part by weight of binder and the ammonium oxalate has a range of
approximately one-half to 4 parts by weight to 1 part by weight of
binder.
25. An insulator, including the following substances:
a binder constituting a polymerizable liquid and having properties
of becoming cured from a liquid to a solid and of combusting at
elevated temperatures above room temperatures without forming a
liquid; and
a coolant dispersed in the binder and capable of substantially
complete decomposition into gases at the elevated temperatures in
an endothermic reaction.
26. The insulator set forth in claim 25, including, a curing agent
for the binder.
27. The insulator set forth in claim 25, further including an
oxidizer capable of substantially complete decomposition at the
elevated temperatures above room temperatures to provide an
oxidation of the binder and to form gases in such
decomposition.
28. The insulator set forth in claim 25 wherein the binder
constitutes a material formed from a group consisting of
polysulfides, polyurethanes, polybutadienes and epoxides;
the coolant is formed from chemical groups consisting of oxalates,
oxamide, oxalic acid, fumaric acid, carbamide and hydrazine
compounds and carbamates.
29. The insulator set forth in claim 28 wherein oxidizer formed
from a group consisting of perchlorates and nitrates is included in
the insulator and is provided with properties of substantially
complete decomposition at the elevated temperatures to provide an
oxidation of the binder and to form gases in such
decomposition.
30. An insulator for materials including the following
substances;
a binder formed from a polymerizable liquid group consisting of
polysulfides, polyurethanes, polybutadienes, polyester resins, and
epoxides and having properties of combusting at elevated
temperatures above room temperatures without forming any residues,
the binder constituting approximately one (1) part by weight;
an oxidizer formed from a group consisting of chlorates,
perchlorates, and nitrates and having properties of substantially
complete decomposition at the elevated temperatures to provide an
oxidizing of the binder and to form gases in providing such
decomposing, the oxidizer constituting up to approximately four (4)
parts by weight;
a coolant formed from a group consisting of oxalates, oxamides,
oxalic acid, fumaric acid, carbamide and hydrazine compounds and
carbamates and capable of substantially complete decomposition at
the elevated temperatures and of providing endothermic reactions in
such decomposition, the coolant constituting approximately one-half
to four parts by weight; and
a plasticizer formed from a group consisting of triacetin, dibutyl
phthalate, and high boiling esters of polyhydric alcohols and
having a weight up to approximately 30 percent of the binder by
weight.
31. In an insulator including the following substances:
a binder formed from a polymerizable liquid group consisting of
polysulfides, polyurethanes, polybutadienes, polyester resins, and
epoxides having properties of combusting at elevated temperatures
above room temperatures without forming any residues, the binder
constituting approximately one (1) part by weight;
a coolant formed from a group consisting of ammonium oxalates,
oxamides, carbamates, oxalic acid, fumaric acid, carbamide and
hydrazine compounds and capable of substantially complete
decomposition at the elevated temperatures above room temperatures
and of providing endothermic reactions in such decomposition, the
coolant constituting approximately three (3) parts by weight;
and
a plasticizer formed from a group consisting of triacetin, dibutyl
phthalate, and high boiling esters of polyhydric alcohols and
having a weight up to approximately thirty percent (30%) of the
binder by weight.
32. In the insulator set forth in claim 31, an oxidizer formed from
a group consisting of chlorates, perchlorates and nitrates and
having properties of substantially complete decomposition at the
elevated temperatures above room temperatures to provide an
oxidizing of the binder and to form gases in providing such
decomposing, the oxidizer constituting approximately one part by
weight.
Description
BACKGROUND OF THE INVENTION
This invention relates to heat-insulating materials and more
particularly to materials which decompose during the application of
heat at elevated temperatures and which discontinue such
decomposition immediately after the application of heat has been
terminated. Considerable work has been performed to provide
materials which are able to serve as heat insulators when subjected
to elevated temperatures as high as 5,000.degree.F. In spite of
such work, satisfactory materials have not been available. One
difficulty has been that the materials continue to burn even after
the application of heat has been terminated. Another difficulty in
some uses has been that the materials liquify when subjected to
heat or deposit undesirable residues upon the application of
heat.
SUMMARY OF THE INVENTION
This invention provides materials which overcome the above
disadvantages. The materials include a coolant, preferably ammonium
oxalate, capable of endothermic decomposition at elevated
temperatures to form gaseous products. The compositions of this
invention are self-extinguishing, and the heat-exposed surfaces can
be touched comfortably immediately or almost immediately after the
application of heat has been terminated.
The compositions included in this invention have further
advantages. For example, during exposure to heat at elevated
temperatures certain of the materials included within this
invention decompose and produce gases without becoming liquified.
The gases serve as a heat barrier to minimize further exposure to
heat. The gases also allow the passage of radio frequency signals.
This is important when the compositions included in this invention
provide insulation in or around electronic equipment.
The compositions of this invention have other important advantages.
They can be formulated for paint consistency or with a consistency
suitable for casting. Viscosity can also be increased so that they
can be extruded, troweled, pressure-cast or molded.
In various embodiments of the invention, the coolants are uniformly
dispersed in binders having different properties. One type of
binder is combustible when subjected to heat, without leaving any
solid residue. Another has the property of forming a porous char
structure which permits passage of the gases resulting from the
application of heat to provide a transpirational cooling. A third
is incombustible.
Various substances can be included in the insulating compositions
of this invention with the binders and the coolants. For example,
catalysts or curatives are included to cure the binder. In the
embodiments in which the binder is combustible without leaving a
residue, a catalyst is preferably used which supplies oxygen to
facilitate the combustion of the binder.
An oxidizer may also be included in the insulating composition,
particularly when the binder is combustible without leaving any
residue. A plasticizer may additionally be included to render the
insulating composition flexible and to facilitate its
combustion.
DETAILED DESCRIPTION OF THE INVENTION
In some embodiments of the invention, the binder is combustible at
elevated temperatures, e.g., 3,000.degree.F. to 5,000.degree.F. to
form gases without first liquifying and without producing any solid
or liquid residue. A preferred binder is polysulfide resin.
The polysulfides, sometimes termed polyalkylene polysulfide
prepolymers, are mercapto-terminated polymers of the general
formula
HS(R--SS).sub.n RSH
where R is a polyvalent organic radical containing at least one
methylene group and n is an integer of from about 3 to 100, and
preferably from about 3 to 25. Preferred polysulfides include those
in which R is
--C.sub.2 H.sub.4 OCH.sub.2 OC.sub.2 H.sub.4 --
The polysulfides may be prepared by condensation of an alkali metal
polysulfide, e.g., sodium polysulfide, with an organic dihalide
such as dichlorodiethyl formal, ethylene dichloride, or
dichloroethyl ether, as described in Industrial and Engineering
Chemistry, Volume 43, pp. 324-8 (1951). Small proportions, e.g.,
0.5-2 percent, of trichloropropane or other polyhalides are often
included with the dihalide. The polysulfides range in property from
mobile to viscous liquids to solids at room temperature, depending
on molecular weight. Those of liquid form are ordinarily
preferred.
Other binders, including polyurethanes, polybutadienes and epoxide
resins, can be used in place of or with the polysulfides. These
binders are advantageous because they can be compounded in liquid
form and cured to a solid matrix at relatively low temperatures
below approximately 250.degree.F. In fact, any organic binder
capable of being compounded as a liquid and cured to a solid at
relatively low temperature can be used.
The epoxides, also referred to as glycidyl polyether resins, are
epoxy-terminated polymers of the general formula
where R' is the divalent organic radical of a dihydric alcohol or a
dihydric phenol and n usually has a value of from about 1 to
20.
Preferred epoxides include those in which R' is ##SPC1##
The epoxides may be prepared by condensation of epichlorhydrin in
alkaline medium with a dihydric alcohol or a dihydric phenol such
as Bisphenol A. The epoxides range in property from viscous liquids
to low melting solids, depending on molecular weight or degree of
condensation. The degree of condensation is indicated by the
epoxide equivalent, defined as the grams of resin per one gram
equivalent of epoxy. Epoxides are prepared with epoxide equivalents
ranging from about 140 to 4000, but those of about 185 to about 300
are usually preferred since these are in liquid form at room
temperature.
A catalyst is generally included to cure the binder. For example,
lead peroxide (PbO.sub.2) may be used as a catalyst when the binder
is a polysulfide. This catalyst is preferably employed at a level
of approximately seven per cent by weight of the binder, and may be
used in a range of approximately six to ten per cent by weight of
the binder. In addition to serving as a curing agent, a catalyst
such as lead peroxide also furnishes oxygen to facilitate the
combustion of the binder.
Paraquinonedioxime (HON:C.sub.6 H.sub.4 :NOH) may be used as a
catalyst instead of lead oxide when the binder is polysulfide.
Paraquinonedioxime is advantageous because it decomposes completely
into gaseous products.
When polyurethane constitutes the binder, glycerine or other
hydroxyl-containing substances can serve as catalyst or curative.
The hydroxyl groups react with the isocyanate groups of the
polyurethane to cure the binder. Castor oil and amines are other
examples of curing agents used with polyurethane binders.
Alternatively, a polyol binder containing free hydroxyl groups can
be condensed with an isocyanate such as tolylene diisocyanate to
form the polyurethane.
When epoxide resins are employed as binders, either alone or in
combination with polysulfides, appropriate accelerators are the
aliphatic and aromatic primary, secondary and tertiary amines,
generally employed at levels up to about 15 parts per 100 parts
epoxide. Preferred polyfunctional amines include
2,4,6-tri(dimethylaminomethyl)phenol, diethylenetriamine, and
dimethylaminopropylamine. Other suitable amines include
dimethylaminomethyl phenol and benzyldimethylamine. Polyamide
curing agents may also be employed with the epoxides. Preferred
polyamides are the reaction products of polymeric fatty acids with
polyamines. The polymeric fatty acids may, for example, be
dimerized and trimerized unsaturated fatty acids derived from
drying oils such as soybean oil, linseed oil, tung oil and the
like. The polyamines employed for the preparation of polyamide
curatives include ethylenediamine, diethylenetriamine and the
like.
A coolant, preferably ammonium oxalate (NH.sub.4).sub.2 C.sub.2
O.sub.4.sup.. H.sub.2 O, is included in the insulating composition
in all embodiments and is one of the principal features of the
invention. The ammonium oxalate may be anhydrous or hydrated. The
coolant is capable of undergoing endothermic decomposition to form
gases at the elevated temperatures so that it absorbs heat in such
decomposition. For example, when ammonium oxalate is used as the
coolant, it decomposes with the absorption of approximately 73
kilocalories per mole:
(NH.sub.4).sub.2 C.sub.2 O.sub.4.sup. . H.sub.2 O.fwdarw. 2NH.sub.3
+ 2CO.sub.2 + H.sub.2 O + H.sub.2
When ammonium oxalate is used as the coolant, it is preferably
employed at a level of approximately three parts by weight to each
part by weight of binder, particularly when the binder is
polysulfide. The relative proportion of the coolant can range from
approximately one half to four parts by weight for each part by
weight of binder. Although various ammonium salts have been known
as coolants, ammonium oxalate has apparently not been known as a
coolant, as may be seen from an article entitled "Sublimation
Pressures and Latent Heats of Ammonium Salts" by N.W. Luft in the
October, 1955 issue of "The Industrial Chemist".
Although ammonium oxalate is the preferred coolant, other materials
may be and have been used. For example, oxalic acid (C.sub.2
H.sub.2 O.sub.4) and fumaric acid (C.sub.4 H.sub.4 O.sub.4) have
been used as coolants and are effective. However, they are more
difficult to handle than ammonium oxalate since they constitute
acids, and as such, should be used over an acid-resistant primer or
base. The acid resistant furan resins are suitable binders for use
with these coolants. The furan resins are formed by the
acid-catalyzed condensation of furfuryl alcohol. The condensation
is halted at an intermediate stage by neutralization, and curing of
the resultant prepolymer may be completed by addition of a strong
acid catalyst after the coolant and any other desired ingredients
have been incorporated. The unsaturated polyester resins are also
appropriate binders for use with these coolants. The polyesters are
prepared by the condensation of a glycol, such as ethylene or
propylene glycol, with an unsaturated dicarboxylic acid such as
fumaric acid or maleic anhydride. Physical properties may be varied
as desired by employing a proportion of saturated dicarboxylic acid
or aromatic dicarboxylic acid, e.g., adipic acid or phthalic
anhydride, along with the unsaturated acid, for example, by
employing a 50:50 mole proportion of saturated and unsaturated
acid. The polyesters are generally blended with about 10 to 40 per
cent by weight of low molecular weight monomer, e.g., styrene, and
cured to solid products by addition of about 0.5 to 5 percent of an
organic peroxide catalyst, e.g., benzoyl peroxide, ter. butyl
peroxide, or methyl ethyl ketone peroxide.
Oxamide (CONH.sub.2).sub.2 and carbamide (urea) (NH.sub.2
(CONH.sub.2) are also theoretically advantageous as coolants
because they decompose endothermically. However, the gases produced
are combustible to generate heat, which neutralizes the endothermic
effect of the decomposition in some applications. Urea oxalate
(2CO(NH.sub.2).sub.2.sup.. C.sub.2 H.sub.2 O.sub.4) is also
theoretically advantageous, as are hydrazine compounds such as
hydrazine formate (N.sub.2 H.sub.4.sup.. 2HCO.sub.2 H).
A coolant such as ammonium oxalate has been used in a binder such
as polysulfide or a polyurethane without any additional material
other than a catalyst such as lead oxide for curing the binder. In
such materials, a portion of the binder may remain as a liquid film
when subjected to heat at temperatures as high as 5000.degree.F.
This is not objectionable in some applications, such as aerodynamic
heat shields, where the liquid film is swept away by aerodynamic
flow.
In some applications a completely gaseous end product is desired.
For example, in the insulation of combustion chambers of gas
generators, hot gas ducts or hot gas holding chambers, it is
preferable that the insulating material, particularly the binder,
produce no solid char or liquid products which might interfere with
the functioning of valves or control devices. A completely gaseous
end product also provides increased working fluid, enabling the gas
generator system to work at increased efficiency. Similarly, in
rocket motors, the gases produced from the insulating material
facilitate the production of increased thrust.
Where it is desired to insure that the binder will be completely
converted to gases, a limited amount of an oxidizing compound
capable of decomposition at elevated temperature is preferably
incorporated in the insulating composition. This oxidizer is
preferably ammonium perchlorate (NH.sub.4 ClO.sub.4), usually
employed at a level of approximately one part by weight to each
part by weight of binder. The proportion of oxidizer may range from
zero up to approximately 1.5 parts by weight to each part by weight
of binder. If the proportion of oxidizer exceeds about 1.5 parts by
weight, the material no longer serves as efficiently as an
insulator.
Oxidizers other than ammonium perchlorate may also be used.
Ammonium nitrate (NH.sub.4 NO.sub.3), for example, has also been
found to be advantageous. In fact, almost any chlorate, perchlorate
or nitrate may be used, urea nitrate and hydrazine nitrate being
other examples. It is preferable to use chlorates, perchlorates, or
nitrates which are free of metal cations where no residue is
desired upon decomposition.
A plasticizer may also be included in the insulating material
constituting this invention to render the material pliable.
Glycerol triacetate C.sub.3 H.sub.5 (OCOCH.sub.3).sub.3, commonly
designated as triacetin, is a preferred plasticizer when the binder
is a polysulfide. Glycerol triacetate is advantageous since it
contains a high proportion of oxygen relative to carbon.
Furthermore, it reduces viscosity so that higher coolant levels can
be incorporated in the compositions. When subjected to heat,
glycerol triacetate is combustible to form gases in substantially
the same manner as the binder. The combustion of the glycerol
triacetate is facilitated by the oxygen resulting from the
decomposition of the ammonium perchlorate. The plasticizer is
usually employed at levels of up to approximately thirty per cent
by weight based on the binder. Glycerol triacetate levels of
approximately twenty per cent by weight are preferred.
Other plasticizers may be used in place of glycerol triacetate. For
example, dibutyl phthalate may also be used. This material is
advantageous for substantially the same reasons as glycerol
triacetate, since its high oxygen content facilitates combustion,
although glycerol triacetate has the higher oxygen content. Other
plasticizers, such as high boiling esters of polyfunctional
alcohols, may be also used.
The insulating compositions constituting this invention are formed
by first combining all ingredients except the catalyst or curative.
When it is desired to form the insulating material, the curative is
added to the mixture, whereupon the composition cures to a solid in
approximately one to twelve hours. Curing can occur at ambient
temperature when the preferred binder, catalyst, coolant, oxidizer
and plasticizer specified above are employed. Alternatively, the
coolant may be mixed initially with the catalyst and oxidizer,
since they are usually all in the form of solids. This mixture may
then be added to the liquid binder or binder-plasticizer mixture
when it is desired to produce the insulating composition. Whichever
method is used, the mixtures produced prior to the mixing of the
binder and the catalyst may be stored for indefinite periods
without affecting the characteristics of the insulating material
produced.
The insulating compositions included within this invention have
important advantages. When heat is applied, as from an acetylene
torch at a temperature of approximately 5,000.degree.F., various
decomposition and combustion reactions ensure such that the net
effect is endothermic. In effect, the decomposition of the coolant,
binder, plasticizer and catalyst acts as a heat sponge which more
than offsets the heat released by the combustion. Tests have shown
that the insulating material absorbs approximately 5,000 BTU per
pound. This is comparable to the material used for the Gemini
re-entry heat shield.
The compositions are self-extinguishing immediately after the heat
is removed from the surface of the insulating material, at which
time the temperature of this surface is sufficiently low that it
can be touched without discomfort, indicating that relatively
little heat is passing through the insulating material. In this
way, members insulated by the compositions constituting this
invention are protected against substantial rise in
temperature.
In view of these properties, the insulating compositions can be
used with a pulsed source of heat to control the combustion and
decomposition of the insulating material. They can also be used
with a pyrotechnic heat source which does not produce any gas in
itself, particularly since the insulating compositions produce
gases when subjected to heat.
The insulating compositions constituting this invention have other
important advantages. For example, when used in a gas generator,
they add to efficiency by producing gases as the insulating
material is consumed. This property is especially important in
rocket motors since the gases generated from the insulating
material impart additional thrust.
Since the compositions of the invention are consumed in providing
the insulating action, a somewhat greater thickness may be applied
initially than the average thickness which may be desired. This is
particularly appropriate when the insulating material is used as
the external skin on rocket engines and missiles, where it provides
a cool external layer as it is consumed, causing the weight of the
rocket engine or missile to decrease.
The insulating compositions constituting this invention are further
advantageous in that the gaseous decomposition products produced
are incombustible without additional oxygen. This may be seen from
the fact that, when the flame from an air-acetylene torch is
applied to the insulating material, the torch must be disposed
up-wind of the effluent gases or they will extinguish the torch. If
the gases were combustible, the endothermic effect would be at
least partially offset by the combustion of the gases.
The insulating materials constituting this invention can be
advantageously used as a coolant around hot gases. The gases
produced from the insulating material are relatively cool in view
of the essentially endothermic nature of reaction, and they mix
with the gases to be cooled and receive heat from such gases.
The insulating compositions constituting this invention have
another important advantage, viz. they allow communication at radio
frequencies through the gases which are produced and which envelop
the insulating material. This is important when the insulating
materials are used to protect electronic systems from heat near
rocket engines and within missiles. The gases produced from other
insulating materials create impenetrable barriers to the passage of
energy at radio frequencies. For example, energy at radio
frequencies is generally blocked by insulators which carbonize or
char or which decompose into metal ions. The radio frequency
transparency of the insulating materials constituting this
invention has been proven in flight tests of Loki darts containing
a transponder and coated with a preferred embodiment of the
insulating material in a thickness of approximately 0.030 inches.
This coating was consumed by aerodynamic heating during the first
30 seconds of the flight. During this period of time,
communications were maintained at radio frequencies with the
transponder.
The materials constituting this invention can be formulated with a
paint consistency or with suitable consistency for casting
operations. Viscosity can also be increased so that the materials
may be extruded, troweled, pressure-cast or molded.
A coolant such as ammonium oxalate may be used with a binder such
as a polyurethane to produce an insulating material which produces
an intumescent or foaming char. For example, sugar or aluminum
hydroxide (Al(OH).sub.3) may be used as a catalyst to cure the
polyurethane binder at somewhat elevated temperature on the order
of approximately 200.degree.F. The hydroxide may be included in the
insulating materials in a ratio of approximately five to 25 parts
by weight per hundred parts by weight of binder, and preferably in
a ratio of approximately ten parts by weight per hundred parts by
weight of binder. In addition to aluminum hydroxide, the hydroxides
of other metals such as iron (ferric and ferrous), chromium
(chromic and chromous), calcium, zirconium, platinum and magnesium
may be used.
The insulating compositions described in the previous paragraph
have foaming characteristics that are produced as the binder and
catalysts react, yielding carbon dioxide as a by-product which
creates an insulation having pores. When such compositions are
subjected to heat, the gases produced by decomposition and
combustion move through the porous char structure to produce a
transpirational cooling of the insulating material. The movement of
the gases through the char structure facilitates the production of
a gaseous interface between the char and the heat source. The ratio
of binder to coolant can be varied to provide any desired
combination of char strength and density and cooling gases for a
given application.
Insulating materials with foaming characteristics have relatively
low density, and they have good resistance to vibration and
withstand physical loads well. The amount of material required to
fill a given space is also minimized. The aluminum hydroxide or
other hydroxide may deposit a residue of metal oxide, a possible
disadvantage in certain applications. However, for ablative
coatings, such metal oxides will contribute to the char
structure.
Insulating compositions having foaming characteristics have been
provided with flexible as well as rigid properties. In these, the
binders have included polyurethanes and the preferred coolant has
been ammonium oxalate. When insulating materials having flexible
properties and foaming characteristics have been produced, a
preferred mixture has been formed from 2,4- and 2,6- tolylene
diisocyanates, in approximately 80/20 ratio by weight, and
polyhydroxyl compounds. The polyhydroxyl compounds may be polyether
or polyester polyols, or a combination of polyether and polyester
polyols.
When the insulating materials have been provided with foaming
characteristics and rigid properties, polyethers have been used
which are primarily propylene oxide adducts of such substances as
sorbitol, sucrose, pentaeythritol, methyl glucoside and diamines.
These materials have ranged in functionality from triols to octols
and in equivalent weight from 75 to 160.
Coolants, and particularly ammonium oxalate, have also been
incorporated into incombustible binders such as asbestos, Portland
cement and plaster of Paris. With such insulating compositions, the
back surface opposite the heat-exposed surface has been maintained
at a temperature below the decomposition temperature of the
ammonium oxalate until the insulating composition has been
completely consumed by the application of heat.
EXAMPLES 1-3
Parts by Weight 1 2 3 32.0 20.75 19.0 liquid polysulfide resin
(binder) (a) 8.0 5.19 4.7 dibutyl phthalate (plasticizer) 2.2 1.56
1.3 lead dioxide (curing agent) 19.3 23.5 24.0 ammonium
perchlorate, 200 micron (oxidizer) 38.5 49.0 51.0 ammonium oxalate
(coolant) (a) Thiokol LP-2, dithiol of molecular weight 4000,
derived from 98 mol % dichloroethyl formal and 2 mol %
trichloroprop ane (Ind. Eng. Chem. Vol. 43, p. 324, 1951)
Formulations 2 and 3 are relatively stiff in compounding;
formulation 1 is more readily workable and is compounded with
greater ease. The cured coatings are exposed 3 inches from an
acetylene torch at an oxygen pressure of 5 pounds per square inch.
Under these conditions, formulation 1 exhibits an ablation rate of
approximately 0.0024 inches per second. Ablation rates of about
0.0020 and 0.0018 inches per second are obtained with formulations
2 and 3, respectively.
The following coating compositions upon curing exhibit comparable
insulating and ablation properties.
EXAMPLE 4
100 p. by wt. Liquid polysulfide resin (a) 25 Dibutyl phthalate
(plasticizer) 7.5 Lead dioxide (curing agent) 50 Ammonium oxalate
(coolant) 0-0.3 aluminum distearate (retarder)
EXAMPLE 5
100 p. by wt. Liquid polyurethane (b) 7.3 Amine curing agent (c)
13.2 Amine curing agent (d) 100. Ammonium oxalate, through 60 mesh
(b) Thiokol Solithane 113 tolylene diisocyanate-urethane prepolymer
having an equivalent weight of 389-404 and an isocyanate content of
10.6% (c) Thiokol C-113-300 (d) Thiokol C-113-328
examples 6-9
parts by Weight 6 7 8 9 100 100 100 100 Liquid polyurethane (b) 50
Castor Oil (curing agent) 6.5 Aluminum hydroxide (curing agent) 9.5
Calcium hydroxide (curing agent) 7.25 Magnesium hydroxide (curing
agent 150 50 50 50 Ammonium oxalate (coolant)
EXAMPLES 10-11
Parts by Weight 10 11 100 Epoxide resin (e) 100 Epoxide resin (f)
10 10 2,4,6-tri(dimethyl- aminomethyl)phenol (g) 100 100 Ammonium
oxalate (e) Shell Epon 828, the condensation product of
epichlorhydrin and bisphenol A, having a molecular weight of 350,
an epoxy value of 0.5 equivalent per 100 grams, a hydroxyl value of
0.1 equivalent per 100 g., and an epoxide equivalent of 190-210
grams per gram mole of epoxide. (f) Ciba Araldite 6020 resin,
having an epoxy equivalent of 208 grams per gram mole of epoxide
(g) Rohm & Haas DMP-30 (curing agent)
EXAMPLE 12
Parts by Wt. 60 Liquid polysulfide resin (h) 40 Epoxy resin (f) 4
2,4,6-tri(dimethyl- aminomethyl)phenol (g) 200 Ammonium oxalate (h)
Thiokol LP-33, dithiol of molecular weight 1000, derived from 99.5
mol % dichloroethyl formal and 0.5 mol % trichloropropane (Ind.
Eng. Chem. Vol. 43, p. 324, 1951)
EXAMPLE 13
100 Parts by Wt. Furan resin (j) 1.0 Acid catalyst (k) 150 Oxalic
acid (j) Resin X-2, a room-setting furfuryl alcohol condensation
polymer available from Furane Plastics Inc., of Glendale,
California. (k) Z-1A, available from Furane Plastics Inc.
EXAMPLE 14
Parts by Wt. 100 Unsaturated polyester casting resin (l) 1.0 Methyl
ethyl ketone peroxide 105 Fumaric acid (l) Copolymer of styrene and
propylene glycol maleate-phthalate
Although this invention has been disclosed and illustrated with
reference to particular applications, the principles involved are
susceptible of numerous other applications which will be apparent
to persons skilled in the art. The invention is, therefore, to be
limited only as indicated by the scope of the appended claims.
* * * * *