U.S. patent number 3,811,920 [Application Number 05/215,593] was granted by the patent office on 1974-05-21 for silicon carbide surfaced filaments with titanium carbide coating.
This patent grant is currently assigned to United Aircraft Corporation. Invention is credited to Francis S. Galasso, Bernarr A. Jacob.
United States Patent |
3,811,920 |
Galasso , et al. |
May 21, 1974 |
SILICON CARBIDE SURFACED FILAMENTS WITH TITANIUM CARBIDE
COATING
Abstract
A composite filament suitable for use as a reinforcement in
titanium or nickel matrices comprises a filamentary substrate
having a silicon carbide surface layer and a thin, adherent outer
layer consisting essentially of titanium carbide.
Inventors: |
Galasso; Francis S.
(Manchester, CT), Jacob; Bernarr A. (Torrington, CT) |
Assignee: |
United Aircraft Corporation
(East Hartford, CT)
|
Family
ID: |
22803592 |
Appl.
No.: |
05/215,593 |
Filed: |
January 5, 1972 |
Current U.S.
Class: |
428/366;
427/249.3; 427/249.15; 428/368; 428/389 |
Current CPC
Class: |
C04B
41/4531 (20130101); C04B 14/4693 (20130101); C04B
41/5061 (20130101); C22C 47/04 (20130101); C04B
41/4584 (20130101); C04B 41/4584 (20130101); C04B
41/009 (20130101); C04B 41/009 (20130101); Y10T
428/2958 (20150115); Y10T 428/292 (20150115); Y10T
428/2916 (20150115) |
Current International
Class: |
C04B
41/45 (20060101); C22C 47/04 (20060101); C22C
47/00 (20060101); D02g 003/00 (); D02g
003/02 () |
Field of
Search: |
;161/175,172
;117/46CB,46CC,46CG,71M,75,16C,128,69,169 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lesmes; George F.
Assistant Examiner: Kendell; Lorraine T.
Attorney, Agent or Firm: Del Ponti; John D.
Claims
1. A composite filament for use as a reinforcement in matrices of
titanium and nickel comprising:
a filamentary substrate selected from the group consisting of
silicon carbide, silicon carbide coated boron and silicon carbide
coated carbon; and
a thin adherent outer layer which consists essentially of titanium
carbide.
2. A composite filament according to claim 1 wherein said
filamentary substrate is a silicon carbide coated boron filament.
Description
BACKGROUND OF THE INVENTION
It is known that silicon carbide surfaced filaments such as silicon
carbide, silicon carbide coated boron and silicon carbide coated
carbon are useful as reinforcing materials in composite structures,
particularly silicon carbide coated boron filaments such as those
taught in U.S. Pat. No. 3,622,369, commonly owned by the assignee
of the present invention. In particular, usefulness of silicon
carbide surfaced filaments as reinforcements in the resin matrices
and in certain metal matrices such as aluminum and magnesium is
recognized in the industry. While the reactivity of silicon carbide
is lower than that of, for example, boron, it has itself been
sufficiently high to necessitate the use of relatively low
temperature or short time at temperature processes during
fabrication of the filament reinforced metal composites in order to
prevent fiber degradation. In addition, it limits the choice of
metal matrix material and further, may well define the temperature
to which the structure is limited in operation.
Accordingly, in power metallurgy or other processes wherein
titanium or nickel is hot pressed with silicon carbide surfaced
filaments such as silicon carbide coated boron filaments, pressing
temperatures have been held below about 800.degree.C to prevent
fiber degradation. While temperatures below 800.degree.C can be
employed in such a hot pressing technique, they require
inordinately high pressures which are not practical for the
formation of larger pieces. As a consequence, realization of the
full potential of silicon carbide surfaced filaments is seen to be
dependent upon the development of techniques to enhance fiber
matrix compatibility as hereinbefore discussed.
SUMMARY OF THE INVENTION
The present invention relates to composite filaments and, more
particularly to silicon carbide surfaced filaments such as
filaments of silicon carbide, silicon carbide coated boron, silicon
carbide coated carbon and the like which are provided with a thin,
adherent coating of titanium carbide.
Titanium carbide has been found to be compatible with silicon
carbide surfaced substrates as well as with such metal matrix
materials as titanium and nickel. It has been found that a titanium
carbide coating on a silicon carbide surfaced filament to a
thickness of only 0.03 mil will not only impart oxidation
resistance to the filament but, in addition, will provide a
diffusion barrier between the silicon carbide surfaced substrate
and such matrix metals as titanium and nickel whereby fiber
degradation is minimized in processes wherein temperatures above
800.degree.C are employed.
Titanium carbide is advantageous in several respects. Because it
may perform its principal function as surface protection for
silicon carbide surfaced filaments, such as the high modulus, high
strength, low density silicon carbide coated boron in very thin
thicknesses, only a very small weight penalty is paid as a result
of its addition. Furthermore, while there is a coefficient of
thermal expansion mismatch in the use of titanium carbide, no
problem in this regard has been presented in actual practice,
primarily because of the thin film aspect.
BRIEF DESCRIPTION OF THE DRAWINGS
An understanding of the invention will become more apparent to
those skilled in the art by reference to the following detailed
description when viewed in light of the accompanying drawings,
wherein:
FIG. 1 is a simple sketch, taken in elevation, of apparatus used in
the production of the titanium carbide coating on the filaments of
the present invention; and
FIG. 2 is an enlarged cross-sectional view through one of the
filaments of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
As seen in FIG. 1, the titanium carbide coating is produced on a
resistively heated silicon carbide surface filament 2 which is
drawn downwardly through a reactor 4 comprising a tubular
containment vessel 6, having dual gas inlets 8 and 10 at the upper
end of the reactor and a single exhaust part 12 at the lower end
thereof. Cooling hydrogen is fed to the reactor through inlet 8,
and inlet 10 is used for the introduction of a reactant gas mixture
comprising methane and titanium chloride (TiCl.sub.4). The
containment vessel may be formed of Pyrex, although a number of
other materials including Vycor and quartz will be found
satisfactory. The gas inlets 8 and 10 and the exhaust 12 penetrate
and are electrically connected to the metallic end plugs 14 and 16
which provide the end closure for the containment vessel and, also
provide convenient means by which power may be supplied to the wire
for resistance heating purposes.
The end plugs are each respectively provided with a well 20 and 22,
for containing a suitable conductive sealant 24, such as mercury,
which serves the dual purpose of providing a gas seal around the
wire where it penetrates the end plugs, and further providing
electrical contact between the moving wire and the respective end
plugs which are in turn electrically connected through the tubes 10
and 12 and the leads 26 and 28 to a suitable DC power source 30.
The upper plug 14 is provided with a peripheral groove 34, which
communicates with the mercury well 20 through the passageway 36, to
provide peripheral sealing around the plug. Sealing between the end
plug 16 and the lower end of the containment vessel 6 is provided
by mercury contained in an annular well 38.
The respective plugs are each formed with a centrally oriented
orifice 40 and 42 which is large enough to accomodate the free
passage of the wire 2 therethrough but which, in combination with
the wire, is small enough to retain the mercury, through surface
tension forces, in their respective wells.
The hydrogen admitted through the inlet 8 enters the reactant
chamber immediately adjacent the wire inlet and is used primarily
for cooling purposes at the end plug 14. As shown in FIG. 2,
passage through the reactor results in a composite filament
comprising a silicon carbide surfaced substrate 46 having a thin
adherent coating of titanium carbide 48. Subsequent to the
formation of the titanium carbide layer, the filaments are
consolidated and bonded to the desired matrix material by hot
pressing.
Various process techniques and parameters may be utilized in
producing filaments of the present invention, as indicated by the
following examples.
EXAMPLE I
In a reactor of the type illustrated, utilizing an 8 inch long
reactor formed from 25 mm Pyrex tubing and a reactant gas mixture
of methane, hydrogen and titanium chloride, a titanium carbide
coating was produced on silicon carbide coated boron filaments
heated to 1150.degree.C and passed through the reactor at a rate of
600 ft./hour (reactor dwell time: 4 seconds). The substrate
filaments are commercially available from Hamilton Standard
Division of United Aircraft Corporation and comprised 4 mil boron
filaments having a 0.15 mil thick coating of silicon carbide and an
average UTS of 410,000 psi. The total gas flow through the reactor
was maintained at 500 cc/min. and the methane was saturated with
TiCl.sub.4 by passing CH.sub.4 through TiCl.sub.4 in a container
and holding the condenser above its container at
18.degree.-20.degree.C ambient cold water temperature with the
container pressure at 1 psig. Hydrogen was introduced separately
into the reactor and the ratio of hydrogen to methane was
maintained at 5 to 1.
The titanium carbide coating was verified by X-ray diffraction and
electrical conductivity measurements showed marked decrease in
resistance. The coating was found to be thin (0.03 mils) and
adherent with the coated filament exhibiting a UTS of 360,000
psi.
EXAMPLE II
The same apparatus and conditions were utilized as in Example I
except that substrate filament speed was 240 ft./hour (reactor
dwell time: 10 seconds), substrate temperature was 1050.degree.C
and the hydrogen/methane ratio was 15 to 1. The adherent titanium
carbide coating was approximately 0.02 mils thick and the coated
composite filament exhibited a UTS of 300,000 psi.
EXAMPLE III
The same apparatus and conditions were utilized as in Example II
except that substrate temperature was 1,100.degree.C and the
hydrogen/methane ratio was 5 to 1. Adherent titanium carbide
coatings were approximately 0.02 mils thick, were produced on ten
samples and the composite coated filament exhibited an average UTS
of 372,000 psi.
EXAMPLE IV
The same apparatus and conditions were utilized as in Example I
except that substrate filament speed was 150 ft./hour (reactor
dwell time: 16 seconds), substrate temperature was 1,100.degree.C
and the hydrogen/methane ratio was 25 to 1. The titanium carbide
coating was of similar thickness and quality as that produced in
Example I and the filament had a UTS of 325,000 psi.
EXAMPLE V
Example IV was repeated except that substrate temperature was
1,150.degree.C and the hydrogen/methane ratio was 15 to 1. The
titanium carbide coated filament had a UTS of 365,000 psi.
EXAMPLE VI
In the reactor apparatus of Example I a thin, adherent titanium
carbide coating is produced on a silicon carbide coated carbon
filament (1 mil circular cross section carbon monofilament
available from Great Lakes Carbon Corporation) heated to
1,100.degree.C and passed through a reactant gas mixture of
methane, hydrogen and titanium chloride in the reactor at a rate of
240 ft./hour (dwell time: 10 seconds). The total gas flow through
the reactor is maintained at 500 cc/min. and the hydrogen/methane
ratio is maintained at 5 to 1. The methane is saturated with
TiCl.sub.4 as in Example I.
EXAMPLE VII
Utilizing the apparatus and conditions of Example VI, a titanium
carbide coating is produced on a silicon carbide filament (100.mu.
continuous filament from Dow Corning or General Technologies
Corporation).
In the course of experimentation, wire temperatures, speeds and gas
compositions were varied. It is to be noted that in general, the
UTS of the filament increases as temperature increases, increases
as gas ratio increases and decreases as dwell time increases.
Further, no TiC coating was detected by X-ray diffraction when,
with a dwell time of 4 seconds, the wire temperature was
1050.degree.C and the gas ratio 25 to 1 or when the wire
temperature was 1100.degree.C and the ratio 15 to 1. Likewise, with
the dwell time increased to 10 seconds, no coating could be
observed when the temperature was maintained at 1150.degree.C with
a gas ratio of 25 to 1. Finally, with the dwell period at 16
seconds, no coating was observed when the temperature was
1050.degree.C with a gas ratio of 5 to 1.
As indicated in the examples above, the deposition of titanium
carbide does result in a small reduction in average strength of the
composite filament. This reduction is relatively slight, however,
when the proper process conditions are observed. The parameters set
forth in Example III, for example, show a reduction of only 7
percent (410,000 psi to 372,000 psi) in strength. This reduction is
not considered significant in view of the fact that the TiC coated
filaments allow bonding with titanium or nickel matrices which
normally, at temperatures above 800.degree.C, attack and destroy
silicon carbide surfaced filaments. In the present case, titanium
coated filaments were subjected to compatibility testing in
matrices of nickel and titanium. Composites were prepared by hot
pressing TiC coated silicon carbide surfaced filaments with Ti
powder at 900.degree.C and 5,000 psi for 30 minutes. They were also
prepared by hot pressing with Ni powder at 850.degree.C and 5,000
psi for 3 minutes. In all cases, the TiC coated filament was not
attacked by either the titanium or the nickel.
While the invention has been described in connection with specific
examples, numerous modifications to the process will be evident to
those skilled in the art. The examples will, therefore, be
understood to be illustrative only within the true spirit and scope
of the invention as set forth in the appended claims.
* * * * *