U.S. patent number 3,915,656 [Application Number 05/386,176] was granted by the patent office on 1975-10-28 for apparatus for growing crystalline bodies from the melt.
This patent grant is currently assigned to Tyco Laboratories, Inc.. Invention is credited to Abraham I. Mlavsky, Nicholas A. Pandiscio.
United States Patent |
3,915,656 |
Mlavsky , et al. |
October 28, 1975 |
Apparatus for growing crystalline bodies from the melt
Abstract
The invention is an improved apparatus for producing
monocrystalline bodies of alumina (or other materials) that are
characterized by varying cross-sections, for example, a sapphire
tube having an internal flange. The apparatus comprises a novel die
arrangement adapted to support a thin film of melt from which the
crystalline body is grown, the die being adjustable to change the
configuration of the film and thereby vary the shape of the body
being grown.
Inventors: |
Mlavsky; Abraham I. (Lincoln,
MA), Pandiscio; Nicholas A. (Wayland, MA) |
Assignee: |
Tyco Laboratories, Inc.
(Waltham, MA)
|
Family
ID: |
26845991 |
Appl.
No.: |
05/386,176 |
Filed: |
August 6, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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148589 |
Jun 1, 1971 |
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Current U.S.
Class: |
117/205; 65/188;
117/209; 117/218; 117/210; 117/902; 117/950; 117/911; 65/87 |
Current CPC
Class: |
C30B
15/005 (20130101); C30B 15/00 (20130101); C30B
15/34 (20130101); C30B 29/60 (20130101); Y10T
117/1072 (20150115); Y10T 117/104 (20150115); Y10S
117/911 (20130101); Y10T 117/1036 (20150115); Y10T
117/102 (20150115); Y10S 117/902 (20130101) |
Current International
Class: |
C30B
15/00 (20060101); C30B 15/34 (20060101); B01J
017/18 () |
Field of
Search: |
;23/273SP,31SP |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Yudkoff; Norman
Assistant Examiner: Sanders; D.
Attorney, Agent or Firm: Schiller & Pandiscio
Parent Case Text
This application is a division of our copending application, Ser.
No. 148,589 filed June 1, 1971 entitled "Method of Growing
Crystalline Bodies from the Melt" now abandoned.
Claims
What is claimed is:
1. Apparatus comprising a crucible, a die assembly extending into
said crucible having first and second concentric members each
having a substantially horizontal top end surface, said first
member having at least one passageway that terminates at one end in
an orifice in the said top end surface of said first member and
communicates at the opposite end with the interior of said
crucible, said members being mounted for relative axial movement so
that the said top end surface of one member can be moved into and
out of horizontal alignment with the said top end surface of the
other member.
2. Apparatus according to claim 1 wherein one of said members is
stationary and the other of said members is moveable axially.
3. Apparatus according to claim 1 further including means for
causing relative axial movement of said members.
4. Apparatus according to claim 1 wherein said first member
surrounds said second member.
5. Apparatus according to claim 4 wherein said first member is
locked to said crucible and said second member is mounted for axial
movement relative to said crucible and said first member.
6. Apparatus according to claim 5 wherein said second member
projects out of the bottom of said crucible, and further including
means for moving said second member.
7. Apparatus according to claim 4 wherein the said end surface of
said first member is annular.
8. Apparatus according to claim 7 wherein said end surface of said
second member is annular.
9. Apparatus according to claim 1 wherein at least part of said die
assembly is supported by said crucible.
10. Apparatus according to claim 1 wherein said second member
surrounds said first member.
11. Apparatus comprising a die assembly having first and second
members each having a substantially horizontal surface at a
corresponding end thereof, at least one passageway in one of said
members that communicates at one point with an orifice in the said
surface of said one member and has an inlet at a point below said
orifice, means for supporting said die assembly, means for holding
a supply of melt in communication with said inlet, and means for
moving one of said members relative to the other so as to move said
surfaces into and out of horizontal alignment with each other.
12. Apparatus according to claim 11 further including means for
heating said die assembly.
Description
This invention relates to monocrystalline tubular bodies and more
particularly to production of monocrystalline end walls or flanges
on monocrystalline tubes.
Various methods have been developed for growing monocrystalline
bodies from a melt. The present invention pertains to an
improvement in growing crystalline bodies from a melt according to
what is called the edge-defined, film-fed, growth technique (also
known as the EFG process). Details of this process are described in
the copending U.S. Pat. application of Harold E. LaBelle, Jr., Ser.
No. 700126, filed Jan. 24, 1968 for Method of Growing Crystalline
Materials.
In the EFG process the shape of the crystalline body is determined
by the external or edge configuration of the end surface of a
forming member which for want of a better name is called a die. An
advantage of the process is that bodies of selected shapes such as
round tubes or flat ribbons can be produced commencing with the
simplest of seed crystal geometries, namely, a round small diameter
seed crystal. The process involves growth on a seed from a liquid
film of feed material sandwiched between the growing body and the
end surface of the die, with the liquid in the film being
continuously replenished from a suitable melt reservoir via one or
more capillaries in the die member. By appropriately controlling
the pulling speed of the growing body and the temperature of the
liquid film, the film can be made to spread (under the influence of
the surface tension at its periphery) across the full expanse of
the end surface of the die until it reaches the perimeter or
perimeters thereof formed by intersection of that surface with the
side surface or surfaces of the die. The angle of intersection of
the aforesaid surfaces of the die is such relative to the contact
angle of the liquid film that the liquid's surface tension will
prevent it from overrunning the edge or edges of the die's end
surface. Preferably the angle of intersection is a right angle
which is simplest to achieve and thus most practical to have. The
growing body grows to the shape of the film which conforms to the
edge configuration of the die's end surface. Since the liquid film
has no way of discriminating between an outside edge and an inside
edge of the die's end surface, a continuous hole may be grown in
the crystalline body by providing in that surface a blind hole of
the same shape as the hole desired in the growing body, provided,
however, that any such hole in the die's end surface is made large
enough so that surface tension will not cause the film around the
hole to fill in over the hole. From the foregoing brief description
it is believed clear that the term "edge-defined, film-fed growth"
denotes the essential feature of the EFG process-the shape of the
growing crystalline body is defined by the edge configuration of
the die and growth takes place from a film of liquid which is
constantly replenished.
The primary object of the present invention is to provide an
improved method and apparatus for growing monocrystalline tubes
using the EFG technique. Another object is to provide new
monocrystalline tubular products.
In this connection it is known that the EFG process may be used to
grow monocrystalline tubes of selected ceramic materials such as
alumina and that tubes made of monocrystalline or polycrystalline
alumina have utility as envelopes for high intensity vapor lamps.
In the manufacture of such lamps the practice is to mount the
electrodes in metal end caps that are attached to the ends of the
envelopes by brazing or other suitable technique. It is recognized
that mounting of the electrodes may be facilitated by forming the
tubes with end walls each having an opening for direct mounting of
an electrode without need for an end cap. It is also desirable for
other applications to form ceramic tubes each having an imperforate
end wall at one end or tubes that are integral extensions of solid
rods of the same material or tubes having sections of different
internal or external diameters. It also is desirable to form
monocrystalline tubes on a continuous basis. Accordingly a more
specific object of this invention is to provide an improved method
and apparatus for producing monocrystalline tubes of ceramic
materials such as alpha-alumina that terminate in integral end
walls or flanges.
Another object is to provide a new and improved method of producing
tubes of varying cross-sections.
Still another object is to provide a method of growing a
monocrystalline body comprising a series of connected tubular
sections of like cross-section connected by transition sections
whereby the body may be severed at said transition sections to form
a plurality of short tubes.
Described briefly, the invention consists of providing a die or
forming member comprising a first member having a substantially
horizontal end surface adapted to be wet by and used to support a
film of melt from which a crystal is to be pulled and one or more
vertically extending capillaries that extend down from said end
surface, a second member coaxially disposed with respect to said
first member and having a correspondingly disposed end surface
adapted to be wet by a film of the same melt, and means providing
relative movement of said first and second members in an axial
direction so as to move said end surfaces into and out of
horizontal alignment with each other. A melt of the material to be
crystallized is supplied to the lower end of the capillaries and
rises to the top ends by capillary action. Then a molten film of
melt is formed on the end surface of the first member so as to
connect with the melt in the capillaries and a crystal is grown
from the film of melt. The film is caused to spread over the entire
end surface of the first member and the pulling speed of the
crystal and the temperature of the film are controlled so that the
crystal grows from the film at all points along its entire
horizontal expanse. After the crystal has grown to the desired
length, the end surface of the second member is moved into
alignment with the end surface of the first member and the film is
caused to expand laterally over the entire end surface of the
second member. The pulling speed of the crystal and the temperature
of the film are controlled so that the crystal now grows from the
film overlying both end surfaces. Subsequently the end surface of
the second member is moved out of alignment with the end surface of
the first member so that crystal growth can occur only from the
film overlying the end surface of the first member. Additional melt
is continuously supplied by the capillaries to the film on the
first end surface to replace the melt consumed by crystal
growth.
Other features and the advantages of the invention are described or
rendered obvious by the following detailed description which is to
be considered together with the accompanying drawings wherein:
FIG. 1 is an elevational view, partly in section, of apparatus for
practicing the method of this invention;
FIG. 2 is an elevational sectional view on an enlarged scale of a
portion of the apparatus of FIG. 1;
FIG. 3 is a plane view of a part of the apparatus of FIG. 2;
FIG. 4 is a view similar to FIG. 2 showing one phase of the growth
process;
FIGS. 5 and 6 are views similar to FIG. 3 showing other phases of
the growth process;
FIG. 7 illustrates one form of tube that can be produced according
to the invention; and
FIG. 8 shows apparatus for a modification of the invention.
The present invention may be used to produce monocrystalline tubes
made of any one of a variety of congruently melting materials that
solidify in identifiable crystal lattices. By way of example, the
material may be alumina, barium titanate, lithium niobate and
yttrium aluminum garnet. The invention is also applicable to other
materials, notably materials that melt congrently (i.e., compounds
that melt to a liquid of the same composition at an invariant
temperature). The following detailed description of the invention
is directed to growing tubes of sapphire, i.e., monocrystalline
alpha-alumina.
FIG. 1 shows a furnace embodying the invention. The furnace
consists of a vertically moveable horizontal bed 2 which engages a
stationary furnace enclosure consisting of two concentric-spaced
quartz tubes 4 and 6 that are supported at their opposite ends in
two annular heads 8 and 10 that seal off the space between the two
tubes. The bottom end of the inner tube 4 extends below bottom head
8 and is positioned in a gasket 12 disposed in a cavity in the bed.
The bottom head 8 is provided with an inlet port fitted with a pipe
14. The upper head 10 has an outlet port with a pipe 16. Pipes 14
and 16 are connected to a pump (not shown) that continuously
circulates cooling water through the space between the two quartz
tubes. The circulating water not only keeps the inner quartz tube
at a safe temperature but also absorbs most of the infrared energy
and thereby makes visual observation of crystal growth more
comfortable to the observer. The interior of the furnace enclosure
is connected by a pipe 18 mounted in the bed 2 to a vacuum pump or
to a regulated source (not shown) of inert gas such as argon or
helium. The furnace enclosure also is surrounded by an R.F. heating
coil 20 that is coupled to a controllable 500kc. power supply (not
shown) of conventional construction. The heating coil may be moved
up and down along the length of the furnace enclosure and means
(not shown) are provided for supporting the coil at a selected
elevation.
The head 10 is attached and supported by a conventional crystal
pulling mechanism represented schematically at 22. The crystal
pulling mechanism 22 has an elongate pulling rod 24 that extends
through the head 10 and into the furnace enclosure. It is to be
noted that the type of crystal-pulling mechanism is not critical to
the invention and that the construction thereof may be varied
substantially. Preferably, however, we prefer to employ a crystal
pulling mechanism that is hydraulically controlled since it offers
the advantage of being vibration-free and providing a uniform
pulling speed. Regardless of its exact construction which is not
required to be described in detail, it is to be understood that the
pulling mechanism 22 is adapted to move pulling rod 24 axially at a
controlled rate. Pulling rod 24 is disposed coaxially with the
quartz tubes 4 and 6 and its lower end has an extension in the form
of metal holder 26 that is adapted to releasably hold a seed on
which crystal growth is made to occur as hereafter described. By
way of example, the seed may be a monocrystalline tube 28 grown
previously by the EFG technique.
Located within the furnace enclosure is a cylindrical heat
susceptor 30 made of carbon. The top end of susceptor 30 is open
but its bottom end is closed off by an end wall. The susceptor is
secured to and supported by a plurality of tungsten rods 32 that
are anchored in bed 2. Supported within susceptor 30 on a plurality
of short tungsten rods 34 is a crucible 36 adapted to contain a
melt 38 of the material to be grown in accordance with the
invention. Rods 34 are secured to susceptor 30 and crucible 36 so
as to prevent movement of the crucible. The crucible is made of a
material that will withstand the operating temperatures and will
not react with or dissolve in the melt. With an alumina melt, the
crucible is made of molybdenum but it also may be made of tungsten,
iridium or some other material with similar properties with respect
to molten alumina. Where a molybdenum crucible is used, it must be
spaced from the susceptor since there is a eutectic reaction
between carbon and molybdenum at about 2200.degree.C. The inside of
the crucible is of suitable size and shape, preferably with a
constant diameter. To help obtain the high operating temperatures
necessary for the process, a cylindrical radiation shield 40 made
of carbon cloth may be wrapped around the carbon susceptor. The
carbon cloth greatly reduces the heat loss from the carbon
susceptor.
Referring now to FIGS. 1-3, mounted in crucible 36 is a die
assembly identified generally by the numeral 44. The die assembly
is made of molybdenum and comprises a cylindrical sleeve 46 that is
affixed (e.g. by welding or press fit) to a supporting disc 48 that
is locked to the crucible. The bottom end of sleeve 46 is welded to
the bottom wall of the crucible so as to prevent leakage of melt to
the interior of the sleeve. Sleeve 46 has a plurality of axially
extending, circumferentially spaced, circular bores 54 and radial
openings 56 near its bottom end to permit inflow of melt to the
several bores from the crucible. Bores 54 are sized to function as
capillaries for molten alumina. The upper end of sleeve 46
terminates in a flat horizontal surface 58 which intersects the
sleeve's outer surface at a right angle. It is to be noted that
sleeve 46 projects above disc 48 so as to be visible to the
operator. The length of the sleeve 46 and diameter of the
capillaries 54 are such that molten alumina can rise in and fully
fill the capillaries by action of capillary rise so long as the
level of the melt in the crucible is high enough to flow into the
openings 56. The height to which a column of melt can rise by
capillary action in one of the capillaries 54 can be approximated
by the equation h=2Tcos.theta./drg, where h is the distance in cm.
that the column will rise; T is the surface tension of the melt in
dynes/cm.; .theta. is the contact angle of the melt; d is the
density of the melt, r is the internal radius of the capillary in
cm.; and g is the gravitational constant in cm/sec.sup.2. By way of
example in a capillary of 0.75 mm. diameter in a molybdenum member,
a column of molten alumina may be expected to rise more than 11 cm.
by capillary action.
Slidably disposed with sleeve 46 is a molybdenum rod 60 of circular
cross-section. The upper end of rod 60 terminates in a flat
horizontal surface 62 having an axially extending cavity 64. The
latter has a diameter large enough so that surface tension will not
cause a film of melt on surface 62 to fill in over it. In this
connection it is to be noted that end surface 62 intersects the
outer surface of rod 60 and also the cylindrical surface forming
the side wall of cavity 64 at a right angle. Rod 60 is sized so as
to make a snug sliding fit with sleeve 46, particularly at the
temperature (about 2070.degree.C) at which the die assembly is
maintained during crystal growth. Rod 60 extends through a hole 68
in the bottom of the crucible and also through a hole 70 in the
bottom wall of susceptor 30. Hole 70 is oversized so as to prevent
reaction of the molybdenum rod and carbon susceptor.
Referring now to FIG. 1, the bottom end of rod 60 is connected by a
coupling 72 to a larger diameter rod 74 that is slidably mounted in
a sleeve bearing 76 that is secured in the bed 2. The lower end of
rod 74 is connected by a second coupling 78 to the piston rod 80 of
a hydraulic actuator 82. The latter is of the double-acting type,
having two inlet ports 84 and 86 at opposite ends of its cylinder.
Ports 84 and 86 are connected by hose lines 88 to a suitable source
of pressurized hydraulic fluid (not shown) via a suitable reversing
valve shown schematically at 90. Valve 90 is adapted to selectively
apply fluid under pressure to either of ports 84 and 86. When fluid
pressure is applied via inlet port 84, piston rod 80 retracts into
the actuator cylinder. Application of fluid pressure to inlet port
86 causes piston rod 80 to be extended. Actuator 82 is mounted on a
supporting bracket 92 that is secured to the bed 2. The bed 2 is
mounted on a pair of vertical slide rods 94 that are attached to a
supporting framework (not shown) that also supports the pulling
mechanism. Additionally the bed 2 is supported by a mechanism (not
shown) that is adapted to lower and raise the bed and hold it at a
selected height. Such bed raising and lowering mechanisms are well
known in the art of crystal growing furnaces and, therefore, need
not be shown in detail. Preferably, however, the bed raising and
lowering mechanism is hydraulically operated.
The apparatus just described is designed to permit growth of
tubular crystal bodies that are characterized by spaced internal
flanges, i.e., tubes that comprise successive tubular sections of
constant inner and outer diameters connected by shorter tubular
sections having the same outer but a different inner diameter. For
want of a better name, the latter sections may be termed
"transition sections." The same apparatus may be used to grow a
tube of one wall thickness onto a tube of a different wall
thickness. Crystal growth may be initiated using a tubular or
nontubular seed. Thus, it is possible to start with an
alpha-alumina seed in the form of a monocrystalline filament or
ribbon and grow a tube onto the seed in accordance with the EFG
technique described in copending application Ser. No. 700126 of
Harold E. LaBelle, Jr. Preferably, however, it is preferred to use
a monocrystalline tube previously grown by the EFG technique. Such
tubes are available commercially.
FIGS. 4 and 5 illustrate how a tube having a constant diameter
outer surface and a stepped inner surface may be grown according to
the invention using the apparatus of FIGS. 1 and 2. It is to be
noted that growth may be initiated with rod 60 disposed either in
lowered position (FIG. 4) or raised position (FIG. 5). Assuming for
purpose of explanation that initially rod 60 is in the lowered
position shown in FIG. 4 and the crucible and capillaries are
filled with an alumina melt, a previously grown sapphire tube 28 is
mounted in holder 26 in axial alignment with the die assembly. Tube
28 has substantially the same o.d. and i.d. as the surface 58. Then
with the power input to coil 30 adjusted so that the upper end
surface of 58 of sleeve 46 is about 10.degree.-40.degree.C higher
than the melting point of the tube 28, the tube is lowered into
contact with the surface 58 and held there long enough for a
portion of the end of the tube to melt and form a liquid film 96
that connects with the melt in one or more of the capillaries and
preferably covers all of the surface 58. It is to be noted that the
capillaries are filled with melt but are shown empty in FIGS. 4-6
in order to render the capillaries more distinct to the reader.
Further it is to be understood with reference to FIG. 4 that before
the end of tube 28 is melted to form film 96, the melt in each
capillary has a concave meniscus with the edge of the meniscus
being substantially flush with surface 58. The temperature gradient
along the length of the tube and the temperature of surface 58 are
factors influencing how much of the tube melts and the thickness of
the film 96. In this connection it is to be noted that the tube
functions as a heat sink so that its temperature is lower at
successively higher points thereon. However, the thermal gradient
along tube 28 is affected by the height of coil 29 and susceptor 30
and also the power input to the coil. In practice these parameters
are adjusted so that the initial film 96 has a thickness in the
order of 0.1mm.
Once the film 96 has connected with melt in at least one of the
capillaries, the pulling mechanism 34 is actuated to pull tube 28
upwardly away from surface 58. The pulling speed is set so that
surface tension will cause the film to adhere to the tube long
enough for crystallization to occur due to a drop in temperature at
the solid tube-liquid film interface. The drop in temperature
occurs because of movement of the tube away from the surface 58,
i.e. because the solid-liquid interface sees a lower temperature.
If the initial film does not fully cover surface 58, as tube 28 is
pulled surface tension will cause the film to spread fully over
surface 58 (see FIG. 3). Thus, as tube 28 is pulled, crystal growth
will occur at all points along the horizontal expanse of the film
with the result that a tubular monocrystalline extension is formed
on the tube which has substantially the same cross-sectional shape
and size as the tube. The film consumed by the crystal growth is
replaced by additional melt which is supplied by the capillaries
54. The process is continued until the tubular monocrystalline
extension has grown to a desired length. Then actuator 82 is
operated to raise rod 60 just enough to place its top and surface
62 flush with end surface 58. Once this has occurred, surface
tension will cause film 96 to spread radially inward over end
surface 62. Adjustment of the pulling speed and/or operating
temperature may be required in order to cause the film to spread.
In any event, as the film spreads, crystal growth will also spread
until finally it will occur at all points along the horizontal
expanse of the film with the result that the newly grown crystal
will have substantially the same outer diameter as surface 58 and
an inner diameter 98 approximately the same as that of cavity 64
(see FIG. 5). The change in inside diameter of the tube is not
sharp but tapered as shown at 99 in FIG. 5. Thereafter the growth
may be continued without further change in position of rod 60, in
which case the product will comprise a tube having a first section
with a relatively large i.d. and a second section with a relatively
small i.d., while its o.d. will be substantially constant.
It is also possible to start the growth process with tube 60
retracted but using as a seed a previously grown tube 28A having
the same o.d. as sleeve 58 and an i.d. equal to the diameter of
cavity 64. In this case the film formed by melting the seed tube
will cover only the upper surface 58 of sleeve 46. Accordingly the
crystal growth produced on the seed tube as it is being pulled as
above described forms a tubular extension having the same o.d. as
the original tube, but an i.d. as shown at 97 that is about the
same as the i.d. of sleeve 46.
It is contemplated also that rod 60 may be repetitively raised and
lowered at selected intervals during the growth process, in which
case the product will have alternately occurring sections 100 and
102 of relatively large and relatively small internal diameter
(FIG. 7). This product may be cut into shorter lengths at
convenient points along either the sections 100 or the sections
102.
In the case of providing envelopes for lamps, it is preferable to
cut the product at the transition sections 102. Accordingly the
sections 102 are made long enough so that when severed, e.g. along
line 104, to form a plurality of discrete tubes, each tube will
have an internal flange (which may also be considered as end wall
with a center hole) that is thick enough to provide the rigidity
required for it to function as a support for a lamp electrode.
It is to be noted that the pulling speed and the temperature of the
film may be varied during crystal growth. However, the pulling
speed should not be so great and the film temperature so high as to
cause the tube to pull free of the melt film. In growing
alpha-alumina, it is preferred to have an initial pulling speed of
about 0.1 in/min until it is determined that the film fully covers
the supporting end surface and to thereafter increase the speed to
about 0.2 in/min. The pulling speed and the film temperature
control the thickness of the film which also controls the rate at
which the film will spread. Within limits, the film thickness can
be increased by increasing the film temperature and the pulling
speed.
The following example illustrates a preferred mode of practicing
the invention.
EXAMPLE I
A molybdenum crucible having an internal diameter of about 1.50
inch, a wall thickness of about 0.20 inch, and an internal depth of
about 0.60 in. is positioned in the furnace in the manner shown in
FIG. 1. Disposed in the crucible is a die assembly constructed
generally as shown in FIG. 2. The sleeve 46 has four capillaries 54
spaced uniformly about its axis. The upper end surface 58 of sleeve
46 has an outside diameter of about 0.500 inch and an inside
diameter of about 0.450 inch. The length of sleeve 46 is such that
its upper end projects about 1/16 inch above the crucible. The rod
60 has an outside diameter of about 0.445 inch and its cavity 64
has a diameter of about 0.31 inch. The actuator is adapted to move
rod 60 through a stroke of about 0.30 inch between upper and lower
limit positions. In the upper limit position, its upper end surface
62 is flush with end surface 58. The four capillaries each have a
diameter of about 0.03 inch. The crucible is filled with
substantially pure polycrystalline alpha-alumina and a
monocrystalline alpha-alumina tube 28 grown previously by the EFG
technique is mounted in holder 26. Tube 28 is cylindrical and was
grown so that the c-axis of its crystal lattice extends parallel to
its geometric axis. Additionally, tube 28 has substantially the
same inside and outside diameter as surface 58 of sleeve 46. Tube
28 is mounted in holder 26 so that it is aligned with surface 58.
Access to seed holder 26 and the crucible 36 is achieved by
lowering bed 2 away from the furnace enclosure and lowering the
seed holder below the bottom end of furnace tube 4. With the bed
restored to the position of FIG. 1, rod 60 is lowered to its lower
limit position (FIG. 4). Cooling water is introduced between quartz
tubes 4 and 6 and the furnace enclosure is evacuated and filled
with argon to a pressure of about one atmosphere which is
maintained during the growth period. Then the R.F. coil 20 is
energized and operated so that alumina in the crucible is brought
to a molten condition (alumina has a melting point in the vicinity
of 2050.degree.C) and the surface 68 reaches a temperature of about
2070.degree.C. As the solid alumina is converted to the melt 38,
columns of the melt will rise in and fill capillaries 54. Each
column of melt will rise until its meniscus is substantially flush
with the top of the rod. After affording time for temperature
equilibrium to be established, the pulling mechanism is actuated
and operated so that the tube 28 is moved into contact with the
upper surface 58 of the die assembly and allowed to rest in that
position long enough to allow the bottom end of the tube to melt
and form film 96. After about 60 seconds, the tube is withdrawn
vertically at the rate of about 0.1 inch per minute. As the tube is
withdrawn, crystal growth will occur on the seed and at the same
time, if it does not already fully cover surface 58, the film 96
will spread fully over the surface 68 due to its affinity with the
newly grown material on the tube and the film's surface tension.
The latter force also causes additional melt to flow out of the
capillaries and add to the total volume of film.
As the tube 28 is pulled, the crystal growth will propagate
vertically throughout the entire horizontal expanse of the film 96,
with the result that growing crystal will conform in
cross-sectional shape to the surface 58. At this point the pulling
speed is increased to about 0.2 inch/min. and the temperature of
the surface 58 held constant at about 2070.degree.C. Growth is
continued until a monocrystalline tubular extension of about 4
inches has been produced on the seed tube. Then, as pulling
continues, actuator 82 is operated to raise rod 60 to its upper
limit position (FIG. 5) so as to place its surface 62 even with
surface 58. Once this has been done, the film 96 will begin to
spread onto surface 62. Spreading of the film is helped by raising
the temperature of surface 58 to about 2080.degree.C. As the film
begins to spread radially inward over surface 62, the crystal
growth will also expand horizontally. The film stops spreading when
it reaches the edge of cavity 64, and as pulling continues the
crystal growth will propagate vertically throughout the entire
horizontal expanse of the expanded film, with the result that the
growing crystal will now have the same o.d. as sleeve 46, but an
i.d. as shown at 98 (FIG. 5). Crystal growth is continued until
that portion of the tubular extension having the reduced diameter
98 reaches a length of 1/2 inch, whereupon the pulling speed is
increased to about 1.0 inch per minute. At this higher pulling
speed, the crystal body pulls free of the melt film. Thereafter,
the pulling mechanism is stopped and the furnace cooled. The tube
28 is retrieved from holder 26. The grown body is found to be
substantially monocrystalline and a crystallographic extension of
the crystal lattice of the seed tube 28. Its outside diameter is
substantially constant and approximately the same as the o.d. of
sleeve 46. Its inner surface comprises a long section (about 4
inches) with a diameter about the same as the i.d. of sleeve 46,
and two shorter sections, one having a diameter of about the same
as cavity 64 and the other being tapered as shown at 99. The inner
and outer surfaces are both smooth.
EXAMPLE II
In this example, the seed tube and the procedure are the same as in
Example I, except that growth is not terminated after that portion
of the tubular extension having the reduced diameter 98 has reached
a length of about 1/2 inch. Instead that portion is allowed to grow
to a length of about 3/4 inch, whereupon rod 60 is lowered to its
original position (FIG. 4). Rod 60 is lowered at a rate such that
as it drops the surface tension will cause film 96 to recede
radially away from cavity 64 until surface 62 is substantially
completely free of melt film. Rod 60 preferably is lowered at a
rate in the order of the pulling speed of tube 28. As the film
recedes from surface 62, the crystal growth also decreases
horizontally while continuing to propagate vertically from the
film, with the result that the growing body has a gradually
expanding internal diameter. Once the film has returned to the
internal edge of surface 58, it stops shrinking and now the crystal
body continues to grow vertically with substantially the same o.d.
and i.d. as sleeve 46. The crystal is allowed to grow an additional
4 inches and then rod 60 is again elevated to the position shown in
FIG. 5, whereupon the film again expands over the surface 62 and
the crystal again grows to the diameter of cavity 64. Thereafter
rod 60 is repeatedly lowered and raised to repeatedly vary the
internal diameter of the product as above described. The result is
a product having a stepped internal wall as shown in FIG. 7.
Although a monocrystalline tube has been used as the seed to
initiate crystal growth, it also is possible to start with a seed
of some other shape, e.g. a monocrystalline ribbon or filament, and
grow a tube therefrom as described in the aforesaid copending
application of Harold E. LaBelle, Jr. Once the body has reached a
tubular shape, it may be grown so as to have a stepped internal
surface as herein described.
It is to be noted that the invention may be used in growing tubular
or rod extensions (or flanges or end walls) of other
cross-sectional shapes, e.g. rectangular, square, triangular, etc.
on tubes or rods of the same or different cross-sections. Thus, for
example, by making the cross-section of rod 60 and cavity 64 and
the inner edge configuration of sleeve 46 square, it is possible to
grow a tubular extension or termination of square interior shape
and round exterior shape onto a tube of round or square
cross-section. By eliminating cavity 64 and positioning rod 60 as
in FIG. 5, it is possible to grow a solid rod onto a tube. Also, by
way of example, by making cavity 64 triangular or hexagonal and the
outer edge configuration of sleeve 46 square, it is possible to
grow a tubular extension with a cross-sectional configuration that
is triangular or hexagonal on the interior and square on the
exterior.
An important advantage of the invention is that it is applicable to
crystalline materials other than alumina. It is not limited to
congruently melting materials and encompasses growth of materials
that solidify in cubic, rhombohedral, hexagonal and tetragonal
crystal structures, including barium titanate, yttrium aluminum
garnet, and lithium niobate mentioned above. With respect to such
other materials, the process is essentially the same as that
described above for alpha-alumina, except that it requires
different operating temperatures because of different melting
points. Additionally, certain minor changes may be required in the
apparatus, e.g., different crucible materials in order to avoid
reaction between the melt and the crucible.
Laue X-ray back reflection photographs of alpha-alumina crystal
growth produced according to the foregoing invention reveals that
the crystal growth usually comprises one or two, and in some cases
three or four, crystals growing together longitudinally separated
by a low angle (usually within 4.degree. of the c-direction) grain
boundary. Therefore, for convenience and in the interest of
avoiding any suggestion that the crystal growth is polycrystalline
in character, we prefer to describe it as "substantially
monocrystalline," it being understood this term is intended to
embrace a crystalline body that is comprised of a single crystal or
two or more crystals, e.g., a bicrystal or tricrystal, growing
together longitudinally but separated by a relatively small angle
(i.e. less than about 4.degree.) grain boundary. The same term is
used to denote the crystallographic nature of the seed tube.
It also has been found that best results are achieved if the c-axis
of the crystal lattice of the seed tube extends parallel to the
tube's longitudinal axis, so that the extension forming a flange or
end wall also grows vertically along the c-axis. Growth in the
c-direction is characterized by smooth surfaces and superior
strength.
Obviously the invention is susceptible of modification and may be
practiced otherwise than as specifically described above. For
example, it is possible to grow tubular rods having a varying
external cross-sectional configuration, e.g., a tube having spaced
external flanges rather than internal flanges. This may be
accomplished by using a die assembly having a close fitting sleeve
slidably disposed around the outside of a stationary die member
having one or more capillaries, and means for raising and lowering
the sleeve in the same manner as rod 60. FIG. 8 illustrates one
possible die arrangement for growing tubular bodies with varying
external cross-sectional configurations. In this case the die
assembly consists of a cylindrical rod 108 having a flat top end
surface 110 with a cavity 112 (which serves the same purpose as
cavity 64) and a plurality of capillaries in the form of through
bores 114. The bottom end of rod 108 has side openings 116 to admit
melt to the capillaries. Rod 108 also has a large center bore 118
in which is slidably disposed a slide rod 120 that extends through
a hole in the bottom wall 122 of crucible 36. Although not shown,
it is to be understood that the bottom end of slide rod 120 is
connected to operating rod 72 so that it may be raised or lowered
by actuator 82. Rod 108 also has two diametrically opposed slots
124 in that portion thereof that defines bore 118. Slots 124 are
wide enough to slidably accommodate portions of a pin 126 that is
carried by slide rod 120. The ends of pin 126 are anchored in a
cylindrical sleeve 128 that surrounds and makes a close sliding fit
with the rod 108. The upper end of sleeve 128 has a flat annular
surface 130. The upper end of the crucible is covered by a
removeable disc 132 that functions as a radiation shield for the
melt and has a center hole to slidably accommodate sleeve 128. It
is to be understood that actuator 82 can move sleeve 128 from a
suitably lower limit position such as shown in FIG. 8 to an upper
limit position in which its annular end surface 130 is flush with
the upper annular end surface 110. When sleeve 128 is in its lower
limit position, crystal growth occurs from a film of melt supported
by the end surface 110. When sleeve 128 is in its upper limit
position, the film of melt can be made to cover its end surface 130
as well as surface 110 and crystal growth occurs from this larger
film of melt. In other words, when sleeve 128 is down, the crystal
growth will conform in crosssectional configuration to the annular
shape of surface 110, whereas when sleeve 128 is raised, the
crystal growth will have an exterior diameter close to the diameter
of cavity 112. Leakage of melt via the hole provided in the bottom
of the crucible for rod 120 is avoided by welding the bottom end of
rod 108 to the crucible's bottom wall. Initial formation of a film
of melt on the upper end surface 110 of the capillary assembly may
be achieved in a manner similar to that described above in
connection with Example I, but preferably using as a seed a
previously grown monocrystalline tube having an o.d. no greater
than the o.d. of end surface 110. If the melt and seed tube are
alumina, the operating temperature and pulling speed are the same
as in Example I and outward expansion of the melt film onto surface
130 is conducted by controlling the operating temperature and
pulling speed in the same manner as employed in Example I to
achieve inward expansion from surface 58 onto surface 62. The
apparatus of FIG. 8 may be used to grow a tubular or solid rod
extension (or an exterior flange) of a relatively large outside
diameter on a tube or rod of relatively small outside diameter and
as with the die assembly of FIG. 2, the die assembly of FIG. 8 may
be modified so as to grow bodies of round, square, rectangular or
other like cross-sectional configurations. In this connection it is
to be noted that a solid rod may be grown by omitting cavity
112.
With respect to the die assembly, it is to be understood that in
the following claims the term "surface" as it pertains to a die
member is intended to cover the effective film-supporting surface
of that die member, whether the member is made as a single piece or
as two or more pieces, and the term "capillary" is intended to
denote a passageway that can take a variety of forms. In this
connection it is to be noted that the sleeve 46 of FIG. 2 may
actually consist of two concentric spaced sleeves locked against
relative movement and spaced uniformly so as to provide a
continuous annular space therebetween that is adapted to function
as one large capillary. Thus, in the die assembly of FIG. 2, sleeve
46 may be replaced by two round sleeves locked to each other in
concentric spaced relation, with the annular space therebetween
measuring about 0.03 inch in a radial direction. Of course, since
the annular space functions as a capillary, the two sleeves need
not have bores like those shown at 54, but the outer sleeve must
have openings at its bottom end (corresponding to openings 54) to
permit inflow of melt to the annular capillary. The rod 60 would be
disposed within the inner one of the concentric sleeves. The
effective film supporting surface of a die member having one or
more capillaries is understood to be its entire end surface
considered as if the capillary orifices were not present since when
a film of melt fully overlies the end surface it covers over the
capillary orifices.
* * * * *