U.S. patent number 3,644,135 [Application Number 04/768,685] was granted by the patent office on 1972-02-22 for in-situ carbiding of pyrolyzed composites.
This patent grant is currently assigned to TRW Inc.. Invention is credited to Fred B. Speyer.
United States Patent |
3,644,135 |
Speyer |
February 22, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
IN-SITU CARBIDING OF PYROLYZED COMPOSITES
Abstract
Ablation-resistant compositions for use in high-temperature
environments produced by impregnating bundles of carbonaceous
filaments with an organometallic compound of a refractory metal
followed by pyrolysis and carburizing to thereby form the
refractory metal carbide in uniformly dispersed form throughout the
bundles of carbonaceous filaments.
Inventors: |
Speyer; Fred B. (Euclid,
OH) |
Assignee: |
TRW Inc. (Cleveland,
OH)
|
Family
ID: |
25083206 |
Appl.
No.: |
04/768,685 |
Filed: |
October 18, 1968 |
Current U.S.
Class: |
427/228; 423/440;
427/337; 264/625; 427/399 |
Current CPC
Class: |
C04B
35/83 (20130101) |
Current International
Class: |
C04B
35/83 (20060101); C23c 003/04 (); C23c 009/06 ();
C03c 017/20 () |
Field of
Search: |
;117/46CC,46CB,102
;156/155 ;161/88,170 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Burnett; Robert F.
Assistant Examiner: Litman; Mark A.
Claims
I claim as my invention:
1. The method of making an erosion-resistant composite which
comprises impregnating a fabric of carbonaceous filament bundles
with a solution of a refractory metal halide in an organic hydroxy
solvent, reacting said halide with said solvent to form a
metalloxane polymer, and thereafter pyrolyzing and carburizing the
metalloxane polymer to provide a dispersion of refractory metal
carbide throughout said fabric.
2. The method of claim 1 in which said organic hydroxy solvent is
an alcohol containing one to five carbon atoms per molecule.
3. The method of claim 1 in which said organic hydroxy solvent is a
polyol containing from two to five carbon atoms per molecule.
4. The method of claim 1 in which said carbonaceous filament
bundles are in the form of a woven cloth.
5. The method of claim 1 in which said halide is a halide of a
metal selected from the group consisting of tantalum, titanium,
tungsten, molybdenum, vanadium, hafnium, zirconium, thorium and
niobium.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is in the field of ablation-resistant compositions
of the type used, for example, in rocket nozzle cones and involves
the impregnation of carbonaceous filament bundles with a
decomposable compound of a refractory metal in liquid form.
Upon high-temperature treatment, the refractory metal compound
decomposes and forms a carbide in situ within the filament bundles
to provide a carbide coating around the individual filaments.
2. Description of the Prior Art
Silica and carbon have been shown to be inadequate in withstanding
the conditions existing in rocket thrust chambers because of the
combination of high temperatures, high gas pressures, and highly
oxidizing environments.
In recent years, many techniques have been developed for providing
carbonaceous composites which resist ablation. These techniques
have involved various modes of filament winding and layup and
depend upon fiber orientation, the creation of boundary layer
flows, refractory metal inserts, and the like, to resist ablation.
In some cases, the finished nozzles have been coated with
refractory metal slurries to extend the life of the composites.
However, none of these composites has had a uniformly dispersed
carbide because of the difficulty in depositing carbide particles
in the intersticies of the carbonaceous filament bundles.
Carbide materials would be very useful because of their very high
melting points and their resistance to oxidation. Even when the
carbide becomes oxidized, a nonvolatile product is formed which can
provide a protective barrier layer in the form of a solid oxide or
a viscous molten layer.
Integral refractory metal carbide structures cannot be readily used
in rocket propulsion systems because of their extreme brittleness
and sensitivity to thermal shock. Furthermore, there is a
limitation in size to which the carbides can be fabricated by arc
melting, powder metallurgy methods, or other fabrication
techniques.
SUMMARY OF THE INVENTION
In the present invention, carbonaceous filaments, preferably in the
form of a carbon or graphite cloth, are impregnated with a solution
of a refractory metal halide in an organic hydroxy solvent. As the
solvent is evaporated or otherwise driven off, the halide reacts
with the solvent to form a metalloxane polymer or a solvated
metalloxyhalide. Upon treatment of the impregnated cloth at
elevated temperatures, the polymer is decomposed, and the
refractory metal is capable of reacting to form a carbide with the
decomposition products of the polymer or with the carbonaceous
filament bundles or strands in which it has become impregnated.
The process described provides several advantages in producing this
type of product. For one thing, complete penetration throughout the
cloth fibers can be secured prior to carbiding. The polymers which
form within the cloth provide flexibility and improve the
handleability of the cloth. A further advantage of this improvement
in handleability is evidenced if the filament bundles are
preimpregnated with the metalloxane prior to weaving.
Because of the control that is inherently possible in the
impregnation step, the process of the present invention makes it
possible to predetermine the amount of carbide quite accurately by
control of the amount of the organometallic compound used in
impregnation.
The metalloxane polymer when dried and powdered can be used, per
se, in dispersed form in high-temperature bonding resins such as
phenolic or epoxy resins which are used to bond laminates of the
cloth together.
Another advantage stems from the fact that the impregnation
technique makes it possible to incorporate more than one refractory
metal carbide into the carbonaceous filament by a single
operation.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a somewhat schematic view of a continuous web treating
apparatus for impregnating the carbonaceous filament bundles;
FIG. 2 is a greatly enlarged cross-sectional view of the bundle
after deposition of a metalloxane polymer thereon;
FIG. 3 illustrates the structure of FIG. 2 after coating with a
resin; and
FIG. 4 is a cross-sectional view on an enlarged scale of the
filament bundle after carburization.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 1, reference numeral 10 indicates generally a supply reel
from which a woven web 11 composed of carbonaceous filament
bundles, either carbon or graphite, is continuously unrolled. The
web 11 is first trained around the periphery of the roll 12 which
is partly immersed in an impregnating solution 13 contained with a
trough 14.
The impregnating solution 13 consists of a solution of a refractory
metal halide which may be the chloride, bromide, or iodide of
refractory metals such as titanium, tantalum, molybdenum, tungsten,
vanadium, hafnium, zirconium, niobium, or the like. The
impregnating solution also contains an organic hydroxy solvent
which, in the preferred form of the invention, is either an
aliphatic alcohol containing from one to five carbon atoms per
molecule, or is a polyol containing from two to five carbon atoms
per molecule. Typical among the impregnating solutions which can be
used is the reaction product between tantalum pentachloride and
methyl alcohol which produces an alkoxide according to the
equation:
TaCl.sub.5 +3CH.sub.3 OH.fwdarw.TaCl.sub.2 (OCH.sub.3).sub.3
+3HCl.
A halide-free alkoxide product can also be prepared by reacting a
halide with the alcohol and anhydrous ammonia according to the
equation:
ZrCl.sub.4 +4CH.sub.3 OH+4NH.sub.3 .fwdarw.Zr(OCH.sub.3).sub.4
+4NH.sub.4 Cl.
The alkoxide product in this case does not remain as such but
apparently rearranges with a polymeric structure.
Graphite or carbon cloth when treated with solutions of this type
is very readily saturated. The highly acidic nature of the solution
provides excellent fiber wetting. The hydrogen chloride which is
generated as part of the reaction evaporates from the cloth leaving
a thermosetting metalloxane polymer in the form of particles which
envelop each fiber and act to give a much improved handleability to
the normally fragile graphite or carbon cloth.
After impregnation, the web 11 passes over a roll 15 where the
volatiles and acid are removed by heating with the metalloxane
remaining impregnated in the web 11. Next, the web passes around
roll 16 partly immersed in a resin-impregnant solution 17 contained
within a trough 18. Various high-temperature bonding resins,
usually phenolic or epoxy resins are known and commercially
available in the field. The chemistry of these resins, therefore,
does not form a feature of the present invention. However, the
powdered metalloxane may be dispersed into the resin solution to
provide additional refractory metal for carbiding with the
pyrolyzed resin.
After impregnation with the bonding resin, the web 11 passes over a
second drying area roll 19 and then is wound up on a takeup roll
20.
Normally, the metalloxane-saturated resin-impregnated cloth will be
used in the form of a laminate. In this type of operation, the web
may be trained about a mandrel or cut into shaped pieces and
subjected to pressure and heat in a mold to consolidate the plies
of the laminate and to cure the phenolic or other bonding resin.
Upon removal from the mold, after curing, the laminate can then be
pyrolyzed at temperatures ranging from about 1,500.degree. to
2,000.degree. F., in an inert atmosphere such as argon.
Temperatures of about 1,600.degree. are typical for phenolic
resins. Then, the pyrolyzed laminate can be resaturated with the
refractory metal solution or resin-metalloxane solution of the type
identified at reference numerals 13 and 18. This impregnation can
then be followed by another dry pyrolysis step typically at
1,600.degree. F. in an argon atmosphere.
The next step in the procedure consists in carburizing the
pyrolyzed material at temperatures of about 2,500.degree. to
3,500.degree. F. in vacuum or in the presence of an inert gas such
as argon. During carburization, the refractory metal remaining
after pyrolysis combines with carbon present from the decomposition
of the organometallics or resinous impregnant or with the
surrounding carbonaceous material of the filament bundles in which
it is embedded to form carbides. The final step of the process may
consist of a graphitizing treatment at about
4,500.degree.-5,500.degree. F. under vacuum conditions or inert gas
to form a substantially high-temperature, oxidation-resistant
composite.
FIG. 2 illustrates a fiber bundle 21 after impregnation with the
metalloxane polymer particles 22 resulting from the reaction of the
refractory metal halide with the organic hydroxy compound. FIG. 3
shows the bundle after coating with a phenolic resin coating
23.
After carburizing, a structure such as that shown in FIG. 4
results. The metalloxane particles react with the carbon present
from the decomposition of the polymer, or with the carbonaceous
strands to form carbide deposits 24 which envelop the individual
strands of the bundle 21. Decomposition of the phenolic resin
coating 23 results in the formation of adherent carbon particles
25. If the metalloxane polymer was included in the phenolic resin
additional amounts of the metal carbide will appear interspersed
with the carbon particles.
While the amount of the refractory metal carbides which appear in
the carbonaceous filament bundles can be varied at will depending
upon the ultimate use to which the composition if to be put,
typically the refractory metal carbide particles constitute about
40 to 80 percent by weight of the carbide-loaded laminate.
Additional benefits can be achieved by adding a refractory metal or
its hydride into the metalloxane solution or the phenolic resin
solution. This increases the amount of refractory metal available
for the carburization reactions.
The following formulations are typical of those which can be used
to impregnate carbonaceous filament bundles with a refractory
metal:
A. Ethylene glycol 30% by weight Zirconium tetra chloride 45% by
weight Water or alcohol 25% by weight B. Ethylene glycol 20% by
weight Methanol 20% by weight Dimethyl formamide 10% by weight
Tantalum penta chloride 50% by weight
A composition as recited in Example A was used to impregnate a
graphite fabric. After pyrolysis at 1,600.degree. F. in an argon
atmosphere, and carburization at 3,500.degree. F. in vacuum, the
composite consisted of 22 percent by weight of the graphite fabric
and 78 percent by weight of zirconium carbide. It had a specific
gravity of 1.83.
A composition of the type indicated in Example B was used to
impregnate a graphite fabric under the same conditions as in the
previous example to provide a fabric containing 35 percent graphite
by weight, 60 percent by weight tantalum carbide, and 4 percent
carbon by weight.
From the foregoing, it will be understood that the present
invention provides a means for penetrating throughout the fibers of
carbonaceous materials to provide a relatively uniform dispersion
of refractory carbides therein. The products which result have the
high-temperature, oxidation-resistance properties characteristic of
carbide materials without the brittleness which has prohibited the
use of monolithic carbide structures for high temperature use.
It should be obvious that various modifications can be made to the
described embodiments without departing from the scope of the
present invention.
* * * * *