U.S. patent number 3,622,369 [Application Number 04/618,512] was granted by the patent office on 1971-11-23 for process for forming stoichiometric silicon carbide coatings and filaments.
This patent grant is currently assigned to United Aircraft Corporation. Invention is credited to Malcolm Basche, Urban E. Kuntz.
United States Patent |
3,622,369 |
Basche , et al. |
November 23, 1971 |
PROCESS FOR FORMING STOICHIOMETRIC SILICON CARBIDE COATINGS AND
FILAMENTS
Abstract
A process whereby stoichiometric silicon carbide is chemically
deposited on a resistively heated wire from a reactant gas mixture
including methyldichlorosilane and hydrogen together with a
carbonizing gas such as methane.
Inventors: |
Basche; Malcolm (West Hartford,
CT), Kuntz; Urban E. (East Hartford, CT) |
Assignee: |
United Aircraft Corporation
(East Hartford, CT)
|
Family
ID: |
24478028 |
Appl.
No.: |
04/618,512 |
Filed: |
February 24, 1967 |
Current U.S.
Class: |
427/589; 118/718;
118/724; 428/390; 427/249.3; 427/249.15; 118/733; 428/391 |
Current CPC
Class: |
C23C
16/325 (20130101); C22C 47/04 (20130101); Y10T
428/2962 (20150115); Y10T 428/296 (20150115) |
Current International
Class: |
C22C
47/00 (20060101); C23C 16/32 (20060101); C22C
47/04 (20060101); B41m 005/24 () |
Field of
Search: |
;117/16C,16A,69,107.1,46CG |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Leavitt; Alfred L.
Assistant Examiner: Batten, Jr.; J. R.
Claims
We claim:
1. A process for continuously depositing silicon carbide on a
heated wired as it is drawn through a reactor comprising the steps
of:
maintaining the wire at a temperature sufficient to effect
deposition of silicon carbide on the wire, the peak temperature of
the wire being within the range of 1,200.degree.-1,400.degree.
C.;
exposing the wire to a gaseous stream consisting essentially of
methyldichlorosilane admixed with hydrogen; and
adding methane to the gaseous stream to effect the formation of a
coating of essentially stoichiometric silicon carbide,
the methyldichlorosilane/hydrogen ratio in the reactor being
maintained within the range of about 1/1:1/3 on a molar basis and
the methane comprising 10-60 mol percent of the total gas flow.
Description
BACKGROUND OF THE INVENTION
It is known that filamentary materials may be produced by pyrolytic
techniques wherein the desired material is deposited on a
resistively heated wire which is drawn through a gaseous reactant
mixture containing the material to be deposited.
In a copending application Ser. No. 618,510 entitled Process for
Forming Filamentary Silicon Carbide by Malcolm Basche and Urban E.
Kuntz filed on Feb. 24, 1967 and now abandoned, which shares a
common assignee with the instant application, there has been
described a process wherein silicon carbide is deposited on a
resistively heated wire from a gaseous reactant mixture including
methyldichlorosilane and hydrogen. In that copending application,
there is taught a method for producing continuous filaments of
silicon carbide as well as methods for forming composite filaments
such as boron with a thin coating of silicon carbide.
Silicon carbide, because of its relative inertness and its strength
at elevated temperatures, offers excellent potential as the
reinforcement material in fiber-reinforced composites utilizing a
wide variety of matrix compositions. The strength of these silicon
carbide fibers is, however, dependent upon their composition. While
it may be desirable in some instances, as is hereinafter discussed
in greater detail, to provide a silicon carbide filament or coating
which varies from the stoichiometric composition, control of this
variation is essential. This is particularly true in those
instances wherein the silicon carbide is utilized to form a
diffusion barrier on other filaments such as boron. Silicon or
silicon-rich silicon carbide does not provide the desired substrate
or matrix compatibility to the same degree as does the
stoichiometric composition.
Using the process described in the previously mentioned copending
application, satisfactory silicon carbide filaments have been
produced in continuous lengths of 9,000 feet or more. It has been
found, however, that without very careful attention to the process
details, the silicon carbide filaments may be formed with a silicon
rich outer layer which, although it might be advantageous in some
instances, is nevertheless detrimental to the compatibility
characteristics of the filaments in usage with the metal
matrices.
SUMMARY OF THE INVENTION
The present invention relates in general to a process for
depositing stoichiometric silicon carbide on a resistively heated
wire and, more particularly, to a process for forming silicon
carbide by chemical deposition from a gaseous reactant mixture
including methyldichlorosilane to which a carbonizing gas, such as
methane has been added. It contemplates not only the production of
filaments which are predominantly silicon carbide but also the
production of composite filaments wherein the silicon carbide is
provided as a thin layer over a variety of substrates, principally
boron.
BRIEF DESCRIPTION OF THE DRAWINGS
In the detailed description which follows it will be convenient to
make reference from time to time to the drawings in which: FIG. 1
is a simple sketch, taken in elevation, of a reactor used in the
pyrolytic deposition of silicon carbide.
FIG. 2 is a schematic view of the gas system used to provide the
gaseous feed for the reactor of Fig. 1.
FIG. 3 is a graph of the pressure-temperature relationship as
related to the composition of the deposit.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring first to Fig. 1, the preferred reactor configuration for
producing the silicon carbide coating on a resistively heated wire
2 which is drawn downward through the reactor 4, may be seen to
comprise a tubular containment vessel 6, having dual gas inlets 8
and 10 at the upper end of the reactor and a single-exhaust port 12
at the lower end thereof. Cooling hydrogen is fed through the inlet
8, and the inlet 10 is used for introduction of the reactant gas
mixture including methyldichlorosilane (CH.sub.3 SiHC1.sub.2) and
methane, and in some instances, hydrogen. The containment vessel is
formed of Pyrex, although Vycor, quartz and a number of other
dielectrics are suitable. In a different configuration, various
metals are also 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 convenient means by which poser
may be supplied to the wire for resistance heating purposes.
Although the end plugs may readily be seen to differ in overall
configuration, they both incorporate a number of common features.
They are each formed to provide a well 20 and 22, respectively, 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. A variable
resistance 32 is provided in the external circuit to permit
regulation of the power supplied to the wire and, hence,
temperature control thereof. The upper end 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 further each formed with a centrally
oriented orifice 40 and 42 which is large enough to accommodate the
free passage of the wire therethrough but which, in combination
with the wire, is small enough to retain the mercury, through
surface tension forces, in the 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. The reactant gases enter
the reactant chamber in an enlarged chimney portion 50, reverse
flow therein, and enter the tubular member 6 at opening 52. In
order to maintain the methyldichlorosilane at a fixed and
controlled level, a condenser is utilized to yield a gas mixture
with a fixed dew point. Such a system is set forth schematically in
Fig. 2. It has been found that at pressures of about 4 p.s.i., a
dew point of between 12.degree. C. and 15.degree. C. produces
filaments of good quality and consistency. At a dew point of
25.degree. C. the concentration of said silane appeared too high
and resulted in filaments of reduced strength. At a dew point of
0.degree. C., said silane concentration appeared too low.
Experiments were run utilizing both hydrogen and argon as the
carrier gases and, in all cases, the hydrogen carrier produced
filaments having the higher strength. In subsequent
experimentation, tests were run utilizing methane as the carrier
gas, dispensing with the hydrogen entirely, except that, in most
instances a limited amount of hydrogen was used for cooling
purposes at the upper mercury seal. Results were perfectly
satisfactory. In general, a methyldichlorosilane molar percentage
of from 10-60 percent, based on total flow, will be preferred,
regardless of the carrier gas composition. In general, it was found
that the peak temperature of the wire must be maintained within the
range of 1,100.degree.-1,500.degree. C. and preferably within the
range of 1,200.degree.-1,400.degree. C.
In the gas system depicted in Fig. 2, hydrogen from a suitable
source is introduced through conduit 60, through pressure regulator
62, flowmeter 64, and valve 66, to the evaporator 68. Part of the
hydrogen is bubbled through the liquid methyldichlorosilane 70 in
the evaporator and the hydrogen-methyldichlorosilane mixture is
discharged therefrom through conduit 72 to the condenser 74 which
is maintained at the appropriate temperature to provide an output
having a dew point of the appropriate range, this output from the
condenser being introduced into the reactor 4 through inlet 10 as
previously described.
A portion of the hydrogen may bypass the evaporator and be
introduced through line 76 to a three-way control valve 80 for
reactor purging purposes or to further regulate the composition of
the reactant gas mixture. Cooling hydrogen is admitted to the
reactor through inlet 8 from conduit 82 through valve 84 and
flowmeter 86.
A study was made of the pressure-temperature relationship involved
in the deposition of silicon carbide. In the formation of
filamentary silicon carbide and in the formation of coatings of
silicon carbide on reactive filamentary material, such as boron, it
is extremely important that at least a substantial portion of the
deposited material is approximately stoichiometric silicon carbide
rather than silicon or silicon-rich silicon carbide. For this
reason, the carbonizing medium such as methane is also introduced
into the reactant gas mixture. The methane addition is introduced
to the system through conduit 90, valve 92 and flowmeter 94. The
reactant gas mixture may, therefore, be seen to preferentially
comprise methyldichlorosilane, hydrogen and methane, although as
previously indicated, the hydrogen may be omitted if desired.
The curve shown in Fig. 3 shows that to produce silicon carbide
without free silicon, one must work above the curve for the desired
results because at any point below the curve either silicon or a
mixture of silicon carbide and silicon will be produced. The
majority of experiments conducted were run at one atmosphere
pressure, but the data accumulated was sufficient to demonstrate
the problem.
The temperature distribution in the usual reactor operated at one
atmosphere pressure is such that only a limited portion of the
filament on which deposition is being effected, lies above the
curve. Accordingly, there is a tendency to produce a layer on the
wire which is rich in silicon. In a 30 inch reactor, a graded fiber
has been produced which is stoichiometric silicon carbide at the
surface abutting the wire and silicon-rich silicon carbide at the
outer surface of the coating. Many of the problems that researchers
have associated with silicon carbide fiber, such as reactivity with
the metal matrix materials and strength degradation at elevated
temperatures, can be explained by this high silicon content.
Similarly, many of the problems associated with the operation of
the reactors producing these fibers can be traced to this silicon
formation. The addition of a carbonaceous gas such as methane to
the reactant gas mixture, according to the present teaching,
permits the formation of stoichiometric silicon carbide without the
undesirable high silicon contents. As an obvious corollary, in
those instances where a graded coating is desired the desired
properties can be achieved by the judicious control of the methane
content and the temperature distribution in the reactor. It has
been found that satisfactory results obtain with a
methyldichlorosilane/hydrogen ratio maintained in the reactor in a
range of about 1/1:1/3 on a molar basis and with methane comprising
10-60 mol percent of the total gas flow.
In one experiment utilizing approximately 16 mol percent methane in
the reactant gas mixture consisting of methyldichlorosilane and
hydrogen, silicon carbide filaments having tensile strengths as
high as 571,000 p.s.i. were produced without difficulty, and
microprobe analysis verified the absence of free silicon in any
significant amount.
It should be pointed out that, in some applications, a filament can
be produced which is basically silicon carbide having a thin outer
layer of pure silicon. The resulting fiber, after careful oxidation
of the silicon, would then actually comprise a composite, silicon
carbide with a silica (glass) coating. This would be particularly
excellent for use with the resin matrix materials.
EXAMPLE 1
In a system of the type described utilizing a 61/2-inch long
reactor formed from 9 mm. Pyrex tubing, a silicon carbide coating
has been produced on boron fiber at a rate of 760 feet/hour. The
filamentary boron substrate was of the type produced by chemical
deposition on a resistively heated wire. At an evaporator pressure
of 2 p.s.i.g., a hydrogen flow rate through the evaporator of 483
cc./min. was maintained with no bypass hydrogen flow around the
evaporator. The condenser was maintained at 14.5.degree. C. and a
methyldichlorosilane flow rate of 231 cc./min. was effected.
Cooling hydrogen was admitted to the reactor at a rate of 114
cc./min. and the methane addition to the reactant gas mixture was
made at the rate of 150 cc./min., resulting in a total gas
composition in the reactor of 15.3 mol percent methane, 23.4 mol
percent methyldichlorosilane and 61.3 mol percent hydrogen. The
wire temperature was established at approximately 1,130.degree. C.
In this regard, it should be noted that the maximum temperature
must be below that temperature at which crystallization of the
boron occurs.
EXAMPLE II
In a test somewhat similar to that described, utilizing a 30 inch
long reactor formed from Pyrex tubing having a diameter of 9 mm.
silicon carbide filaments have been produced on a tungsten wire at
a rate of 200 feet/hour. Gas flow rates and compositions
approximated those set forth in the previous example, but the wire
temperature peak was maintained in the range of
1,200.degree.-1,400.degree. C. Over 9,000 feet of continuous
silicon carbide filament was produced having ultimate tensile
strengths as high as 571,000 p.s.i.
In general, the silicon carbide filaments were produced in the
range of 3-4 mils. As previously indicated, those produced in
processes utilizing the methane addition had strengths on the order
of 571,000 p.s.i. while those produced without the methane addition
were generally limited to ultimate tensile strengths on the order
of 345,000 p.s.i.
Boron fiber is generally produced with a diameter of 3-4 mils.
Tests on 3.8 mil boron fiber with a 0.2 mil coating of
stoichiometric silicon carbide indicated that the composite fiber
had essentially the same ultimate tensile strength as the basic
boron or about 460,000 p.s.i.
EXAMPLE III
In a similar test utilizing a reactor formed from 25 mm. tubing 8
inches long, a silicon carbide coating of 0.2 mil thickness was
produced on 4.4 mil boron fiber. Methane was utilized as the
carrier gas and introduced to the evaporator at a rate of 520
cc./min., the evaporator being held at 14.degree. C. This resulted
in a methyldichlorosilane flow rate of 193 cc./min. Cooling
hydrogen was admitted at a rate of 200 c.c./min. The total
composition of the gas in the reactor, on a molar basis, was 57
percent methane, 22 percent hydrogen and 21 percent
methyldichlorosilane A subsequent microprobe analysis revealed no
excess silicon or carbon in the deposit.
In the course of experimentation, silicon carbide was deposited on
various substrate materials including in addition to tungsten and
boron, graphite and tantalum. Further, wire temperatures and gas
compositions were varied extensively to optimize the process
conditions. Still further, the various filaments were subjected to
compatibility testing in various matrix materials, including
aluminum, magnesium and titanium. No degradation of the silicon
carbide fibers was found after heating them in aluminum at
580.degree. C. for 24 hours, and in titanium at 730.degree. C. for
24 hours. The compatibility of the boron-silicon carbide composite
filaments was similarly established in other tests for periods of
over 500 hours.
It will readily be seen that by this invention there has been
provided a process for producing silicon carbide filaments and
silicon carbide coatings whereby the character and chemistry of the
silicon carbide may be precisely regulated with the resultant
improvement in the quality of the filament produced and in the ease
by which the filament may be produced.
* * * * *