U.S. patent number 3,565,345 [Application Number 04/744,153] was granted by the patent office on 1971-02-23 for production of an article of high purity metal oxide.
This patent grant is currently assigned to Texas Instruments Incorporated, Dallas, TX. Invention is credited to Herbert John Moltzan.
United States Patent |
3,565,345 |
|
February 23, 1971 |
PRODUCTION OF AN ARTICLE OF HIGH PURITY METAL OXIDE
Abstract
A torch is provided for decomposing a volatile metal chloride by
hydrolysis to directly form an oxide article on a mandrel. The
torch includes a nozzle which provides an output jet stream of
vaporized metal chloride. Sheath openings in the nozzle provide a
supply of gas which is relatively inert with respect to the gaseous
metal chloride for preventing reaction immediately adjacent the
nozzle face. A plurality of slanted nozzle openings are provided in
the nozzle for directing angled streams of combustible gas through
the sheath stream at a selected region for reaction with the jet
stream of gaseous metal chloride. When the gas streams are ignited,
a torch flame is provided which may be directly impinged upon a
mandrel in order to directly form an oxide article of high purity
thereon.
Inventors: |
Herbert John Moltzan (Dallas,
TX) |
Assignee: |
Texas Instruments Incorporated,
Dallas, TX (N/A)
|
Family
ID: |
24991642 |
Appl.
No.: |
04/744,153 |
Filed: |
July 11, 1968 |
Current U.S.
Class: |
239/422;
239/132.3; 239/428; 264/81; 239/419.3; 239/424; 239/543 |
Current CPC
Class: |
C03C
3/06 (20130101); C03B 19/1423 (20130101); C04B
41/5025 (20130101); C01B 33/183 (20130101); C04B
41/5025 (20130101); F23D 14/52 (20130101); C04B
41/455 (20130101); C03C 2201/02 (20130101); C03C
2203/44 (20130101); Y02P 40/57 (20151101) |
Current International
Class: |
F23D
14/48 (20060101); F23D 14/52 (20060101); C03B
19/00 (20060101); C03B 19/14 (20060101); C01B
33/00 (20060101); C04B 41/45 (20060101); C01B
33/18 (20060101); C04B 41/50 (20060101); C03C
3/06 (20060101); F23d 011/16 () |
Field of
Search: |
;239/132.3,419.3,422,428,424,543 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lloyd L. King
Attorney, Agent or Firm: Samuel M. Mims, Jr. James O. Dixon
Andrew M. Hassell Harold Levine Melvin Sharp Richards, Harris &
Hubbard
Claims
I claim:
1. A torch for decomposing a volatile metal chloride by vapor phase
hydrolysis to form an oxide article on a surface comprising: a. a
torch housing including a passage having a nozzle aperture for
providing an output jet stream of the vaporized volatile metal
chloride; b. a first chamber defined within said torch for
receiving a supply of gas which is relatively inert with respect to
said volatile metal chloride, said chamber having an opening
adjacent said nozzle aperture for providing a sheath stream of said
gas around said jet stream sufficient to prevent residue from being
formed on said nozzle aperture when the torch is ignited; and c. a
second chamber defined within said torch housing for receiving a
supply of combustible gas and including slanted nozzle openings,
each alternate nozzle opening having a substantially different
slant angle from that of adjacent openings, for directing angled
streams of combustible gas through said sheath stream for reaction
with said jet stream at a preselected region to provide efficient
deposition of said oxide article directly upon said surface.
2. The torch of claim 1 wherein said volatile metal chloride
comprises silicon tetrachloride and said combustible gas comprises
a mixture of oxygen and hydrogen.
3. The torch of claim 1 wherein said nozzle aperture is circular,
said opening in said second chamber is an annular opening
concentrically disposed about said nozzle aperture, and said
slanted nozzle openings are circular and are disposed symmetrically
about said annular opening.
4. The torch of claim 3 and further comprising at least six slanted
nozzle openings disposed in a circle about said annular opening,
each of said nozzle openings having an area no greater than said
nozzle aperture.
5. The torch of claim 1 wherein said slanted nozzle openings slope
toward the axis of said jet stream at an angle within the range of
2.degree. to 30.degree..
6. The torch of claim 1 and further comprising a chamber enclosing
said second chamber and having inlet and outlet means for
circulation of a cooling fluid therethrough.
7. The torch of claim 1 wherein said slanted nozzle openings are
defined in nozzle removable from said torch housing.
8. A torch for forming a silica article directly upon a mandrel by
hydrolysis of silicon tetrachloride entrained in a carrier gas
comprising: a. a torch housing having a central passage
therethrough with an inlet for receiving gaseous silicon
tetrachloride entrained in a carrier gas and having a nozzle
aperture to provide an output jet stream of gaseous silicon
tetrachloride entrained in a carrier gas; b. a sheath chamber
defined in said torch housing including an inlet for receiving a
relatively inert gas and having an annular opening disposed about
said nozzle aperture to provide a circular stream of said inert gas
around said jet stream; and c. a mixing chamber disposed about said
sheath chamber including inlets for combustible gases and a
plurality of outlet openings slanted toward the axis of said jet
stream, each alternate outlet opening having a substantially
different slant angle from that of adjacent openings, to penetrate
said circular stream at a selected region for reaction with said
jet stream, whereby a silica article may be formed by directly
impinging the flame resulting from ignition of said torch on the
mandrel.
9. The torch of claim 8 wherein said outlet openings from said
mixing chamber slant towards the axis of said jet stream at an
angle within the range of 2.degree. to 30.degree..
10. The torch of claim 9 comprising at least six said outlet
openings disposed in a circular configuration around said nozzle
aperture.
Description
This invention relates to a production of metal oxide by the
decomposition of volatile metal chloride, and more particularly to
a formation of an article of metal oxide by the vapor phase
hydrolysis of volatile anhydrous chlorides of metallic elements
from Groups III and IV of the periodic system, and particularly
silicon tetrachloride.
It is necessary in the formation of many semiconductor devices to
"pull" pull monocrystalline silicon from a melt of very pure
silicon. In order to prevent impurities from entering the melt of
silicon from the walls of the melt crucible, it has been found
advantageous to construct the melt crucible from very pure silica.
Further, it has been found desirable to provide the silicon melt
crucible with very uniform sidewalls and with a symmetrical
configuration in order to ensure a uniform "pull" from the silicon
melt.
Silica articles have been heretofore formed by various techniques.
For instance, U.S. Pat. No. 2,272,342, issued Feb. 10, 1942,
discloses the production of a silica article by the vaporization of
silicon tetrachloride or silicon fluoride and the decomposition of
the resulting vapor in a flame. The flame is then impinged on a
refractory core to deposit a layer of silica, after which the
silica is vitrified by the application of high temperature.
Additionally, U.S. Pat. No. 3,117,838, issued Jan. 14, 1964,
discloses the utilization of a flaming torch for oxidizing a gas
mixture including silane in a reactive gas to form molten silica
and then directing the molten silica onto a carbon form to grow a
body of transparent silica. Such previously developed techniques
have not, however, been completely satisfactory with respect to
forming an extremely pure silica article having a desired uniform
configuration and necessary strength for use as a melt
crucible.
It has also heretofore been known to produce finely divided metal
oxide from volatile metal chlorides by igniting streams of the
vaporized metal chloride and combustible gases within a reactor.
The volatile metal chloride is thus oxidized to form finely divided
oxide which is withdrawn from the bottom of the reactor. In order
to prevent obstruction of the nozzle through which the gas streams
are provided to the reactor, it has heretofore been known to
provide an intermediate layer of relatively inert gas between the
combustible gas and the gaseous metal chloride. Further, in some
instances, it has been known to slant the supply of combustible
gases toward the gaseous metallic chloride at angles from
45.degree. to 60.degree. to enhance the combustion reaction between
the gases. Examples of such systems are disclosed in U.S. Pat. No.
2,240,343, issued Apr. 29, 1941; U.S. Pat. No. 2,394,633, issued
Feb. 12, 1946; and U.S. Pat. No. 2,823,982, issued Feb. 18,
1958.
The present invention is an improvement over the torch for
providing vapor phase hydrolysis of a volatile metal chloride in a
flame which is described and claimed in the copending patent
application entitled "Method and Apparatus for Forming an Article
of High Purity Metal Oxide," by Michael A. Carrell, filed Jul. 11,
1968, Ser. No. 744,188.
In accordance with the present invention, a volatile metallic
chloride is vaporized and entrained in a carrier gas and streamed
from a jet nozzle. A stream of combustible gas is formed
symmetrically about the jet stream and directed at an angle in the
range of 2.degree. to 30.degree. to the axis of the jet stream to
provide a preselected reaction region with the jet stream. A stream
of sheath gas is provided between the streams to prevent reaction
closely adjacent the nozzle. When the gas streams are ignited at
the reaction region, a flame is formed which may be directed upon a
mandrel to form an article of high purity oxide directly
thereupon.
For a more complete understanding of the present invention and
further objects and advantages thereof, reference may now be made
to the following description taken in conjunction with the
accompanying drawings, in which:
FIG. 1 is a somewhat diagrammatic illustration of a torch
constructed in accordance with the invention;
FIG. 2 is a sectional view taken generally along the section lines
2-2 of the torch shown in FIG. 1;
FIG. 3 is an end view of the torch shown in FIG. 1;
FIG. 4 is a diagrammatic illustration of the temperature zones of a
torch flame formed in accordance with the invention;
FIG. 5 is a sectional view of another embodiment of a nozzle for
the torch shown in FIG. 1;
FIG. 6 is a cross-sectional view of yet another embodiment of a
nozzle for use with the torch shown in FIG. 1;
FIG. 7 is a front view of the nozzle shown in FIG. 6;
FIG. 8 is a view of yet another embodiment of a nozzle for use with
the torch shown in FIG. 1;
FIG. 9 is a graph illustrating variances in deposition rate with
the present torch in accordance with changes in the distance
between the torch and the mandrel;
FIG. 10 is a graphical illustration of the variance of the
deposition rate with the present torch versus variances in the
velocity of the central jet stream of the torch; and
FIG. 11 is a graphical illustration of variances in the deposition
rate of the present torch in accordance with variances in the flow
rate of a combustible gas provided to the torch.
Referring to FIG. 1, the torch designated generally by the numeral
10 emits a flame which provides vapor phase hydrolysis of a gaseous
volatile metal chloride to produce a metal oxide which is deposited
upon a rotating mandrel. The present torch may be used to decompose
any one of a number of the volatile anhydrous chlorides of metallic
elements from Groups III and IV of the periodic system, such as
titanium tetrachloride, aluminum tetrachloride, and tin
tetrachloride. However, in the preferred embodiment of the
invention, silicon tetrachloride is decomposed by the torch 10 to
form silicon dioxide according to the following equation:
SiCl.sub.4 + 2H.sub.2O -- SiO.sub.2 + 4HC1
A tube or pipe 12, preferably constructed from stainless steel,
extends through the length of the torch 10 to provide a passage for
vaporized silicon tetrachloride entrained in a carrier gas. A
T-connection, designated generally by the numeral 14, is connected
about the tube 12 and is sealed at one end to the tube 12 by a
collar member 16. A coupling member 18 fits over a stainless steel
tube 20 to provide an annular sheath chamber 22 between the tube 12
and tube 20. An inlet portion 24 of the T-connection 14 is
connected to the source of sheath gas in a manner to be later
described, which is in this instance oxygen containing gas. This
sheath gas is passed into the annular sheath chamber 22.
A mixing chamber 26 is formed by chamber walls 28. An inlet fitting
30 is adapted to be connected to the source of one combustible gas,
while the inlet 32 is connected to a source of a second combustible
gas. The combustible gases are mixed within the chamber 26 in order
to limit any possible flashback to the torch housing. An outer
annular chamber 34 is formed by annular walls 36 to define the
cooling chamber about the torch. An inlet fitting 38 is connected
to a suitable supply of cooled fluid which is circulated through
the chamber 34 and exhausted via an outlet fitting 40.
Oxygen is supplied through a conduit 42 to the inlet of three
flowmeters 44, 46 and 48. Hydrogen is supplied via a conduit 50 to
a flowmeter 52. Both the oxygen and hydrogen are dried prior to
entering the flowmeters. Suitable valves are provided at the output
of each of the flowmeters in order to allow accurate regulation of
the flow rate of the gases to the torch. Oxygen is supplied through
a conduit 54 to the inlet portion 24 of the T-connection member 14.
Oxygen from the flowmeter 46 is supplied through a conduit 56 to a
bubbler unit 58. The bubbler unit 58 comprises a container filled
with liquid silicon tetrachloride and includes a diffusing element
60 which bubbles the oxygen upwardly through the silicon
tetrachloride, thereby entraining vapors of the silicon
tetrachloride within the oxygen. While a bubbler assembly has been
shown, it will be understood that a conventional diffuser type gas
source could alternatively be utilized. The gaseous silicon
tetrachloride entrained in the carrier oxygen gas is passed
outwardly through a conduit 62 to the inlet of the pipe 12. Oxygen
is supplied from the flowmeter 48 through a conduit 64 to the inlet
30 of the mixing chamber 26. Hydrogen is supplied from the
flowmeter 52 through the conduit 66 to the inlet 32 of the mixing
chamber 26.
A nozzle assembly 68 is attached to the face of the torch 10 by
screws 70. As shown in FIG. 2, four screws 70 pass through the
nozzle assembly 68 and into portions of the walls defining chamber
34. Nozzle 68 comprises a unitary circular member having a center
opening 72 for receiving the end of pipe 12. As best shown in FIG.
1, the end of pipe 12 is closed, with the exception of a center
nozzle aperture 74 defined therein. In a practical torch, a nozzle
aperture having a diameter of about .063 inch has been found to
provide satisfactory results. Due to the difference in the
diameters of pipe 12 and pipe 20, an annular opening 76 is defined
concentrically about the nozzle aperture 74. The sheath chamber 22
opens into the opening 76. A plurality of nozzle openings 78 are
defined through the nozzle assembly 68. The diameter of these
openings is generally the same, or smaller than, the diameter of
the nozzle aperture 74.
An important aspect of the present invention is that the nozzle
openings 78 slant towards the axis of the jet stream which issues
from the nozzle aperture 74. As shown in FIG. 1, each of the nozzle
openings 78 makes an angle .phi. with the axis of the jet stream
issuing from the jet aperture 74. This angle .phi. may be varied
according to the invention for particular desired results, but in
any instance is within the range of 2.degree. 30.degree.. In the
torch shown in FIG. 1, an angle .phi. of 20.degree. has been shown.
As will be later described, the angle nozzle openings 78 provide a
very efficient torch flame for the direct deposition of metal
oxides.
In operation of the torch 10, silicon tetrachloride entrained in
oxygen is passed through the pipe 12 and out the jet aperture 74 as
a gaseous jet stream. A concentric sheath of oxygen is passed
through the annular opening 76. Eight streams of a combustible
mixture of hydrogen and oxygen are directed at an angle in the
range from 2.degree. to 30.degree. toward the axis of the jet
stream for penetration of the gas sheath and interaction with the
gaseous silicon tetrachloride. When the torch is ignited,
combustion occurs at this region and the silicon tetrachloride is
decomposed by vapor phase hydrolysis to form silicon dioxide. The
slanting of the combustible gas through the sheath into the gaseous
silicon tetrachloride is believed to provide substantially improved
results due to better contact with the reactants within the gas
streams to provide a more controlled and directed flame
reaction.
FIG. 4 diagrammatically illustrates the theoretical operation of
the present torch. The stream of reactant gas fed from the bubbler
58 is surrounded by a circular stream of sheath gas. In the
preferred embodiment, the sheath gas comprises oxygen in such
quantities as to be initially relatively inert with respect to the
silicon tetrachloride bubbler gas. Thus, silicon tetrachloride is
not allowed to react with a combustible gas and decompose
immediately adjacent the face of the nozzle to thereby cause
obstructions of the nozzle apertures. The combustible gas is
directed along the dotted lines through the oxygen sheath at a
distance below the nozzle face to react with the silicon
tetrachloride in the region designated generally by the numeral 80.
When the gas streams are ignited, this region 80 is extremely hot,
and provides temperatures of in the range of 1,500.degree. C.
A relatively narrow reaction zone is provided by the angled, or
focused, combustible gas stream shown in FIG. 4. This relatively
short reaction zone is in contrast with previously developed
torches without angled gas nozzles which provide relatively wide
reaction zones. The provision of the relatively small reaction zone
enables excellent contact with the reactant gases and insures
efficient production of silicon dioxide. On the other hand, an
excessive angle greater than about 30.degree. leads to a reaction
30.degree. too close to the torch, causing deposition on the burner
face and a lower efficiency.
The flame from the torch 10 is impinged directly upon a rotating
mandrel 82. Mandrel 82 is generally constructed from a substance
such as graphite which can withstand the high temperatures of the
torch. Improved results are usually obtained by preheating the
mandrel before deposition operations. The mandrel 82 is translated
along its axis in the direction of the arrow designated as 84 and a
layer of high purity silica, shown generally by the numeral 86, is
deposited directly upon the mandrel 82. The present torch enables a
very smooth deposition of high purity silica, with the resulting
article formed having sufficient "green strength" upon cooling to
allow the article to be removed from the mandrel 82 and further
treated. It is believed that this "green strength" results from a
slight sintering together of the silicon dioxide particles during
the deposition thereof.
FIG. 5 illustrates another embodiment of a nozzle assembly
according to the invention. Substantial advantages are provided by
the present torch in that nozzles may be easily changed on the
torch body in accordance with the desired uses of the torch. The
nozzle assembly shown in FIG. 5 includes an aperture 90 for
receiving the end of the pipe 12 and further includes holes 92 for
receiving suitable screws for attachment to the torch body.
Whereas the nozzle assembly shown in FIG. 1 included slanted
apertures directed at 20.degree. toward the axis of the jet stream,
the nozzle shown in FIG. 5 includes nozzle openings 94 which slope
at an angle of 10.degree. toward the axis of the jet stream and the
longitudinal axis of the torch.
FIGS. 6 and 7 illustrate yet another embodiment of a nozzle
assembly 96. Instead of the eight holes for combustible gas
previously shown, the nozzle assembly 96 includes 16 holes or
openings 98 arranged in a cylindrical configuration. Alternate ones
of the openings 98 slant toward the axis of the jet stream issuing
from the torch at different angles. For instance, the opening 100
slants downwardly at an angle of 10.degree., while the opening 102
slants downwardly toward the axis of the jet stream at an angle of
20.degree.. Each alternate nozzle opening slants downwardly at a
different angle than the openings directly adjacent thereto. Eight
nozzle openings will thus slant downwardly at an angle of
10.degree., .degree.while the eight remaining alternate openings
slant downwardly at an angle of 20.degree. . It will of course be
understood that various other configurations of varying nozzle
opening angles may be selected for nozzles according to the
invention to meet various operating requirements. Additionally,
various nozzle opening angles may be used in combination with
different combinations of openings for the combustible gas.
FIG. 8 illustrates an end view of an assembled torch according to
the invention which includes four nozzle apertures 106a--106d
defined in the end of the pipe 12. In the embodiment shown in FIG.
8, 16 nozzle openings 108 are shown in a symmetrical configuration
about the center jet nozzle apertures. Each of the openings 108 is
slanted toward the longitudinal axis of the torch in order to
pierce the sheath gas issuing from the annular opening 110 in the
manner previously described. It will be understood that a variety
of other configurations of nozzle openings may also be provided by
the invention, as long as the openings are suitable symmetrically
arranged.
FIG. 9 is a graphical representation of the effect of variances in
the distance between the nozzle of the torch and the mandrel upon
the deposition rate of the silicon dioxide and the efficiency of
such deposition. Curve 110 represents variances in the deposition
rate while curve 111 represents variances in efficiency. This data
was obtained from a torch having a flame temperature of in the
range of 1,400.degree. C. with a flow rate of 1.5 liters per minute
of gaseous silicon tetrachloride entrained in 1 liter per minute of
oxygen. A sheath gas flow rate of 1 liter per minute of oxygen was
provided, along with a flow of combustible gases at a flow rate of
5.2 liters per minute of oxygen and 30 liters per minute of
hydrogen being provided through apertures angled toward the jet
stream of silicon tetrachloride at 10.degree..
Inspection of FIG. 9 illustrates that both the efficiency and rate
of deposition of silicon dioxide on the mandrel increases at the
torch is pulled away from the mandrel; an optimum distance is about
31/4 inches. As this distance then increases, both the rate of
deposition and efficiency of deposition substantially decreases. It
will be understood that each torch having a different configuration
will have an optimum mandrel distance which will be different from
torches with other configurations.
FIG. 10 illustrates variations in the deposition rate and
efficiency of the torch described with respect to FIG. 9 utilizing
the same flow rates, with the exception that the velocity of the
bubbler gas is varied. As shown by curve 112, the deposition rate
substantially increases as the velocity of the gaseous silicon
tetrachloride entrained in carrier gas is increased. However, as
shown by curve 114, the efficiency of such deposition begins to
fall off at a velocity of about 6 feet per minute .times.
10.sup.3.
FIG. 11 illustrates changes in the deposition rate and efficiency
of the torch described with respect to FIG. 9 as the flow rate of
hydrogen into the torch is varied. Curve 116 illustrates that as
the hydrogen flow rate is increased, the deposition rate increases
to a maximum of about 120 grams per hour at about 30 liters per
minute flow rate. Thereafter, the deposition rate falls off.
Similarly, curve 118 illustrates that the efficiency of the
deposition by the torch increases to about 55 percent at about 30
liters per minute flow rate of hydrogen, and thereafter falls off
on further increases in flow rate. A similar effect is observed by
varying the flow rate of the oxygen fed into the combustion chamber
of the torch.
It will thus be observed from an inspection of FIGS. 9--11 that
optimum results are obtained by varying various parameters of the
flow rates of the gases fed into the torch and the distance from
the torch to the mandrel. For any particular torch configuration,
each of these parameters may be adjusted to a maximum to give
utmost performance of the torch.
The following examples will further explain the use of the present
torch, but should not serve to limit the utilization of the
torch.
EXAMPLE 1
A torch was constructed in accordance with FIG. 1 with eight
cylindrical holes each sloping at 20.degree. toward the
longitudinal axis of the torch for supplying combustible gas
through the sheath of oxygen to the gaseous silicon tetrachloride.
The torch was connected to a gas system similar to that shown in
FIG. 1 and then ignited. A nonrotating graphite mandrel was
disposed about 31/4 inches from the torch nozzle and the flame
issuing from the torch was impinged upon the graphite mandrel for
20 minutes. The temperature of the flame approximately one-fourth
inch from the mandrel was in the range of 1,500.degree. C. One
liter per minute of oxygen and 1.56 liters per minute of gaseous
silicon tetrachloride entrained in the oxygen was fed to the torch.
To provide this supply of gas, a conventional bubbler was
maintained at a temperature of approximately 50.degree. C. and at a
pressure of 5 pounds per square inch. The percentage of silicon
tetrachloride entrained in the oxygen carrier gas was about 60
percent. The diameter of the center nozzle aperture of the torch
was .063 inch. One liter per minute of oxygen was provided to the
torch for use as a sheath gas, while 5.2 liters per minute of
oxygen and 30 liters per minute of hydrogen were mixed in a torch
to provide the combustion gas. The resulting velocity of the gas
jet stream of gaseous silicon tetrachloride from the torch was
about 4.17 feet per minute .times. 10.sup.3. After 20 minutes of
deposition by the flame, the actual deposition of silicon dioxide
on the graphite mandrel was measured to be 41 grams. By comparing
this deposition with the theoretical computation of 76.8 grams, an
efficiency of deposition of 53 percent was computed. This
percentage was contrasted to a deposition efficiency of 46 percent
by the utilization of a torch with the identical parameters above
enumerated, but with eight holes which were not slanted toward the
axis of the jet stream. This increase in efficiency of deposition,
and in the rate of deposition, is thought to be because the
penetration of the sheath gas by the combustion gases increases the
uniformness of reaction of the gases and provides a more limited
and intense reaction zone.
EXAMPLE 2
The identical torch described in example 1 was utilized at the same
distance from the graphite mandrel for the same deposition time.
The same gas flow rates were provided into the torch, with the
exception that 2 liters per minute of oxygen was provided to the
torch for use as a sheath gas and 8 liters per minute of oxygen was
provided for mixture with the hydrogen within the torch. After 20
minutes of deposition with the torch, 44.2 grams of silicon dioxide
were deposited on the mandrel for a deposition efficiency of 58
percent.
EXAMPLE 3
In some instances, it has been found that a reduction in the
velocity of the sheath gas may increase the efficiency of
deposition of silicon dioxide. In this deposition example, the
identical torch previously described was utilized with the same
flow rates of the gases thereto and at the same distance from the
mandrel as that described in example 2, with the exception that 1.5
liters per minute of oxygen was provided to the torch for use as
the sheath gas. In this instance, after a 20 minute run, 53.3 grams
of silicon dioxide were deposited on the mandrel for a deposition
efficiency of 69 percent.
EXAMPLE 4
Increase in the velocity of the jet stream of gaseous silicon
tetrachloride also was found to provide good results with the torch
described in examples 1--3. The gas flows to the torch were
maintained as described in example 3, except that 2 liters per
minute of oxygen was provided to the bubbler and 2.86 liters per
minute of gaseous silicon tetrachloride was entrained in the
oxygen, with 1 liter per minute being used as a sheath gas. After
20 minutes of deposition at 3 inches from the mandrel, 72.9 grams
of silicon dioxide were deposited on the graphite mandrel to
provide an efficiency of 52 percent.
EXAMPLE 5
Effective deposition was found to be provided with the utilization
of the torch shown in FIG. 1 with a nozzle having 16 holes for the
combustion gas each slanted at 20.degree. toward the axis of the
jet stream. In this example, the torch was held 31/4 inches from
the mandrel for a period of 20 minutes, with an effective flame
temperature one-fourth inch from the mandrel of slightly over about
1,400.degree. C. One liter per minute of oxygen was fed to a
bubbler and entrained 1.56 liters per minute of silicon
tetrachloride therein. One liter per minute of oxygen was provided
to the torch for use as a sheath gas. 5.2 liters per minute of
oxygen was supplied to the torch for mixture with 30 liters per
minute of hydrogen to form a combustive mixture. The bubbler was
maintained at a temperature of 50.degree. C. and at a pressure of 5
pounds per square inch to provide 60.9 percent silicon
tetrachloride within the gaseous mixture. This mixture was passed
outwardly through a .063 inch diameter jet nozzle to provide a jet
stream having a velocity of 4.17 feet per minute .times. 10.sup.3.
The use of this torch after 20 minutes provided 39.2 grams of
silicon dioxide upon the graphite mandrel for a deposition
efficiency of 51 percent.
EXAMPLE 6
Excellent results were also obtained by the use of a torch
connected as shown in FIG. 1 with a nozzle having eight holes for
combustible gas, each hole being slanted toward the axis of the jet
stream at an angle of 10.degree.. The torch was held from the
mandrel about 3 1/4 inches and ignited for about 20 minutes. The
resulting flame of the torch one-fourth inch from the mandrel
surface was measured to be slightly under 1,400.degree. C. One
liter per minute of oxygen was fed to a bubbler to entrain 1.56
liters per minute of silicon tetrachloride therein. One liter per
minute of oxygen was fed to the torch for use as a sheath gas about
the jet stream. 5.2 liters per minute of oxygen was mixed within
the torch with 30 liters per minute of hydrogen to form the
combustible gas mixture. After 20 minutes, 55.2 grams of high
purity silicon dioxide were deposited upon the mandrel to provide
an efficiency of 72 percent. This efficiency is a marked
improvement over a torch utilizing the conventional nozzle to
provide parallel streams of combustible gas and jet stream of
reactant gas.
EXAMPLE 7
The torch described in example 6 was held the same distance from
the mandrel and was provided with the same flow of gases thereto,
with the exception that 8 liters per minute of oxygen was mixed
with 30 liters per minute of hydrogen to provide the combustible
gas mixture. A 20 minute deposition of the resulting torch flame
provided 60.5 grams of high purity silicon dioxide for an
efficiency of 78 percent.
EXAMPLE 8
A torch similar to that described with respect to example 7 was
utilized, with the exception that only 0.6 liter per minute of
oxygen was provided to the bubbler for entrainment with 2.28 liters
per minute of silicon tetrachloride to provide a relatively high
79.2 percent gaseous silicon tetrachloride. A 20 minute deposition
with the resulting torch deposited 78 grams of high purity silicon
dioxide upon the mandrel for an efficiency of 76 percent.
EXAMPLE 9
This example shows the results obtained with holes at an angle of
5.degree.. A run was made using a torch constructed similar to and
employing the same reactants as employed in Example 1 with the
following exceptions. The eight cylindrical holes sloped at an
angle of 5.degree. toward the longitudinal axis of the torch. The
nonrotating graphite mandrel was disposed 41/4 inches from the
torch nozzle. The temperature of the flame approximately one-fourth
inch from the mandrel was in the range of about 1,400.degree. C.
The gaseous silicon tetrachloride was entrained in the oxygen
stream at the rate of 1.57 liters per minute per liter of oxygen
fed to the torch. The velocity of the gas example stream of gaseous
silicon tetrachloride from the torch was about 4.19 feet per minute
.times. 10.sup.3. After 20 minutes of deposition by the flame, the
actual deposition of silicon dioxide on the graphite mandrel was
measured to be 44.9 grams. By comparing this deposition with the
theoretical computation of 77.3 grams, an efficiency of 58 percent
was computed.
EXAMPLE 10
This example shows the results obtained by employing double angled
holes of, respectively, 10.degree. and 5.degree.. The run was made
with similar torch construction and the same reactants as employed
in example 1 with the differences noted hereinafter. The torch was
constructed with the eight cylindrical holes having alternating
angles of, respectively, 10.degree. and 5.degree. toward the
horizontal axis of the torch for supplying combustible gas through
the sheath of oxygen to the gaseous silicon tetrachloride. A
nonrotating graphite mandrel was disposed 41/4 inches from the
torch nozzle. Gaseous silicon tetrachloride was entrained in the
oxygen fed to the torch in the ratio of 1.53 liters per minute per
liter of oxygen. The velocity of the gas jet stream of gaseous
silicon tetrachloride from the torch was about 4.12 feet per minute
.times. 10.sup.3. After 20 minutes of deposition by the flame, the
actual deposition of silicon dioxide on the graphite mandrel was
measured to be 45.3 grams. By comparing this deposition with the
theoretical computation of 75.4 grams, an efficiency of 60 percent
was computed.
The present invention thus provides a technique for forming high
purity metal oxides upon a mandrel by the vapor phase hydrolysis of
a volatile metallic chloride by flame which provides improved
deposition efficiency over prior techniques. While the invention
has been disclosed with respect to the deposition of high purity
silicon dioxide by the decomposition of silicon tetrachloride, it
will be understood that other volatile anhydrous chlorides of
metallic elements from Groups III and IV of the periodic system,
such as for example, titanium tetrachloride, zirconium
tetrachloride and the like, could additionally be advantageously
utilized with the present invention.
Although the specific embodiments of the present invention have
been described in some detail, it will be understood that various
modifications and changes will be suggested to one skilled in the
art, and it is intended to encompass such modifications and changes
which fall within the true scope of the invention as defined in the
appended claims.
* * * * *