U.S. patent number 3,607,222 [Application Number 04/780,613] was granted by the patent office on 1971-09-21 for method for evaporating alloy.
This patent grant is currently assigned to Air Reduction Company Incorporated. Invention is credited to Kurt D. Kennedy.
United States Patent |
3,607,222 |
Kennedy |
September 21, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
METHOD FOR EVAPORATING ALLOY
Abstract
A method is described for evaporating an alloy from a single
crucible in a vacuum enclosure. A solid bar of alloy is fed
upwardly into the crucible from the bottom thereof. The alloy is
heated to form a covering pool and to produce evaporation. The feed
rate of the solid bar is regulated to maintain a substantially
constant level of molten alloy relative to the crucible.
Inventors: |
Kennedy; Kurt D. (Berkeley,
CA) |
Assignee: |
Air Reduction Company
Incorporated (New York, NY)
|
Family
ID: |
25120102 |
Appl.
No.: |
04/780,613 |
Filed: |
November 26, 1968 |
Current U.S.
Class: |
75/10.29;
118/726; 219/121.28; 219/121.15 |
Current CPC
Class: |
C23C
14/246 (20130101) |
Current International
Class: |
C23C
14/24 (20060101); C23c 013/02 (); B01d
003/10 () |
Field of
Search: |
;75/65EB ;118/49
;117/107,107.1,93.3,106 ;219/121EB |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Curtis; Allen B.
Claims
What is claimed is:
1. A method for evaporating an alloy from a single crucible in a
vacuum enclosure, said alloy, in the molten condition, including at
least two metals one of which is at least twice as volatile as the
other, comprising: feeding a solid bar of alloy of substantially
the same cross section as the crucible interior upwardly into the
crucible from the bottom thereof, heating the bar of alloy in the
crucible to form a molten pool completely covering the solid end of
the bar, heating the surface of the molten pool to produce
evaporation, and regulating the feed rate of the solid bar to
maintain a substantially constant level of molten alloy relative to
the crucible and thereby replenish the alloy at substantially the
same rate as its evaporation.
2. A method according to claim 1 wherein the crucible is
cooled.
3. A method according to claim 1 including controlling the heat
losses out of the bottom of the solid bar to maintain them
substantially constant.
4. A method according to claim 1 wherein the heating is
accomplished by means of an electron beam.
5. A method for evaporating an alloy, from a single cooled crucible
in a vacuum enclosure, said alloy, in the molten condition,
including at least two metals one of which is at least twice as
volatile as the other, comprising: cooling the crucible, feeding a
solid bar of alloy of substantially the same cross section as the
crucible interior upwardly into the crucible from the bottom
thereof, heating the surface of the bar of alloy in the crucible to
form a molten pool completely covering the solid end of the bar and
to produce evaporation, controlling the cooling rate and the heat
losses out of the bottom of the solid bar to maintain a
substantially balanced condition of heat removal to heat input, and
regulating the feed rate of the solid bar to maintain a
substantially constant level of molten alloy relative to the
crucible and thereby replenish the alloy at substantially the same
rate as its evaporation.
Description
This invention relates to vacuum evaporation of metals and, more
particularly, to a method for evaporating a molten alloy from a
single crucible in a vacuum enclosure.
Vapor deposition, that is, the evaporation of material and
subsequent condensation thereof on a substrate to be coated, has
been successfully used in a variety of manufacturing operations.
One particular vapor deposition technique which is of advantage
where high purity is desirable involves the utilization of a cooled
crucible and means for heating the surface of molten material
contained in the crucible. Surface heating may, for example be
accomplished by means of a suitably directed electron beam, plasma
beam, or laser beam. By cooling the crucible, a skull of solidified
molten material forms between the molten material and the crucible
wall, isolating the molten material from the crucible and
preventing any reaction between the molten material and the
crucible material.
Although satisfactory for many types of materials, heretofore known
methods of vapor deposition have frequently encountered difficulty
in evaporating alloys. This is particularly true for alloys having
constituent materials of widely different volatilities, such as
alloys of iron plus rare earth metals. For a given heating energy
input and beam density the the evaporation rate depends upon the
efficiency of the vapor deposition system. The efficiency of the
system, however, is affected by a wide variety of different factors
which cause changes in the heat balance of the system. Such changes
can result in variation in the amount of solid alloy that lies
between the cooled crucible walls and the molten alloy. The melting
and freezing of alloy at the skull creates segregation of the
alloy's components and thus may cause changes in the composition of
the molten alloy in the crucible. This may result in an undesired
variation in the composition of the deposit on the substrate.
Evaporation of alloy constituents from separate crucibles
simultaneously is one way of avoiding segregation problems, but
greatly increases the cost and complexity of the system. Thus,
evaporation of an alloy from a single crucible may be
preferable.
In order to replenish the molten material in the crucible for alloy
evaporated therefrom during typical vapor deposition operations,
feed stock is introduced into the crucible. One form of feeding is
by utilizing a wire fed into the path of the heating beam or
directly into the molten alloy in the crucible through the open top
of the crucible. Many important alloys are not available in wire
form, however, for lack of commercial value of the alloy in wire
form, or because of difficulty in fabricating the alloy because of
brittleness. Alloys that are commercially available in wire form
are frequently full of dissolved gas and generate a considerable
amount of undesirable spitting when melted into the molten
pool.
Cast alloy bars are sometimes preferable to wire for feeding
purposes because cast bars are generally obtainable commercially in
more pure form than wire and in a wider variety of available
alloys. Such cast bars are generally greater than one-half inch in
diameter requiring, in most instances, a relatively slow movement
of the bar into the molten pool to replenish the molten alloy at
the rate at which it is being evaporated. This may be difficult due
to variations in the heat pattern of the system which make the bar
melt back at varying rates and therefore cause significant changes
in the actual feed rate of new alloy into the molten pool. Under
such circumstances, a heat imbalance occurs in the system with the
consequent undesirable changes in alloy composition previously
pointed out.
A further difficulty encountered in vapor deposition systems,
particularly when the crucible in which the molten alloy is
contained is cooled to form a skull, is that condensate has a
tendency to form between the skull and the water cooled crucible
along the top edges thereof. During operation, such condensate
builds up and may wedge between the skull and the crucible, leading
to increased mechanical pressure and an attendant increase in the
rate at which heat is transferred from the molten material to the
cooled crucible. If the molten material is permitted to cool off,
such as between coating operations, the solidified alloy will
frequently shrink away from the supporting crucible. Upon
reheating, the same mechanical pressures mentioned above will
generally not develop, and the rate of heat transfer is therefore
not the same as that which existed during the previously described
situation. Such changes between successive operations in the ratio
of the volume of liquid to the volume of solid alloy results in
changes in the alloy composition of the molten pool for reasons
previously described, and such changes cannot easily be
predicted.
It is, therefore, an object of the invention to provide an improved
method for evaporating a molten alloy from a single crucible in a
vacuum enclosure.
Another object of the invention is to provide a method for
evaporating alloys having constituent materials of widely different
volatilities wherein improved uniformity of vapor composition is
obtainable.
It is another object of the invention to provide a method for
evaporating an alloy wherein the replenishment rate of evaporant is
closely controllable.
Other objects of the invention will become apparent to those
skilled in the art from the following description, taken in
connection with the accompanying drawing in which a vapor
deposition system for performing the method of the invention is
illustrated schematically.
Very generally, the method of the invention comprises heating the
surface 11 of a molten alloy 12 in a crucible 13 to produce
evaporation. A solid bar 14 of alloy, of substantially the same
cross section as the crucible interior, is fed upwardly into the
crucible from the bottom thereof to replenish alloy evaporated
therefrom. The feed rate of the solid bar is regulated to maintain
a substantially constant level of molten alloy relative to the
crucible.
Referring now more particularly to the drawing, the vapor
deposition system illustrated therein includes a vacuum enclosure
16, the interior of which is evacuated by a suitable vacuum pumping
system 17. A substrate 18 to be coated with a layer 19 of condensed
vapor is positioned within the enclosure 16 in the path of the
vapor by suitable supporting means, not illustrated.
The surface 11 of the molten alloy 12 contained within the crucible
13 is heated by means of an electron beam 21. The electron beam 21
is produced by an electron gun including an emissive filament or
emitter 22 disposed within a recess in a backing electrode 23. An
anode or accelerating electrode 24 is disposed adjacent the open
side of the recess in the backing electrode to accelerate electrons
out of the recess, as indicated by the dotted lines in the drawing.
The electron beam thus developed is deflected through a generally
curving path onto the surface 11 of the molten alloy 12 by means of
a magnetic field having curving lines of flux which are concave
with respect to the surface 11. The magnetic field is established
between a pair of pole pieces 26, one of which is shown. An
electromagnetic coil 27 is disposed around a low-reluctance core 28
which extends between the pole pieces 26 to establish the pole
pieces at opposite polarities. Suitable means, not illustrated, are
provided for supplying the required electrical potentials and
currents to the various times described. An electron beam gun
generally of the type described is shown and described in greater
detail in U. S. Pat. No. 3,177,535.
The crucible 13 is provided with an internal passage 29 through
which a suitable coolant, such as water, may be circulated. The
crucible is supported within the vacuum enclosure 16 by suitable
supports, not illustrated.
A large number of factors contribute to the evaporation rate. Two
factors which are of substantial importance are the overall
efficiency of the system and the size of the area of the surface to
which heat is being added by impingement of the electron beam or
other heating beam. The efficiency of a vacuum deposition system
may be defined by the expression (H.sub.t /H.sub.a).times.100 where
H.sub.t is the theoretical heat required to produce the evaporation
rate desired and H.sub.a is the actual heat input. Thus, the fewer
the heat losses in the system, the higher the efficiency will be.
Where higher temperatures are required to produce evaporation,
greater heat losses result, lowering the efficiency. For example,
cadmium, which has a relatively low evaporation temperature, may be
evaporated in many instances at efficiencies of greater than 80
percent. On the other hand, tantalum, which has a relatively high
evaporating temperature, is usually evaporable at efficiencies
which are typically less than 10 per cent.
As previously mentioned, the evaporation rate also depends upon the
sharpness of the area of impingement of the beam on the surface 11
of the alloy 12 in the crucible 13. For given material and beam
power, the larger the spot or impingement area, the lower the
evaporation rate. The relationship, however, is not linear and the
effects of variation in the impact area are much less for lower
evaporation temperature materials. Of course, the evaporation rate
becomes less if the beam is swept over the entire surface of the
molten material, rather than impinging upon a particular area
thereof. Such beam sweeping may be desirable to produce a more
uniform evaporation from the entire surface of the molten material.
Basically, however, the evaporation rate is most easily controlled
by controlling the total power input or heat input of the electron
beam or other heating beam, and by controlling the power density of
such beam.
In order to replenish alloy evaporated from the crucible, the solid
bar 14 of replenishment alloy is fed upwardly into the crucible
from the bottom thereof. The bar is of the same cross section as
the crucible interior and therefore constitutes the bottom or
support for the molten alloy 12. The region of the bar adjacent the
crucible 13 remains solid, due to cooling of the crucible, until
just below the surface of the molten pool. The beam power and
density are controlled so that the pool diameter at the surface is
equal to the inner diameter of the crucible so the pool completely
covers the solid part of the bar 14. If a fluctuation in heating
occurs, causing melting of the bar 14 earlier, the pool surface
area does not change, helping to keep the evaporation rate
constant. Moreover, the avoidance of exposure of the solid end of
the bar, and the avoidance of the formation of an exposed skull
aids in maintaining a constant pool composition. The feed rate is
controlled by the feed rollers 31 and 32 which engage the sides of
the bar and feed it upwardly into the crucible. The rate of feed
may be controlled by controlling the rate of rotation of the feed
rollers 31 and 32 by suitable means, not illustrated. For
operations which are to be continuous over an extended period of
time, relatively long length of the bar 14 may be accommodated by
feeding the bar through a suitable vacuum valve 33 in the wall of
the enclosure 16. A thermal insulation 34 may be provided at the
lower end of the bar 14 to minimize heat losses through the bar
from the crucible.
The feed bar 14 is moved upwardly at a rate which may be
appropriately adjusted by the operator through visual observation
of the liquid level in the molten pool to maintain such level as
nearly constant as possible. Examples of typical feed rates are set
out below, and the average rate of feed depends on the evaporation
rate. If an error of feed should occur, or conversely if a
fluctuation in the heat balance of the system occurs, causing the
liquid level of the pool to drop, the liquid-solid interface
between the molten pool and the solid bar also drops, tending to
keep the liquid inventory constant. This helps to maintain the
evaporation rate and the pool composition relatively constant. This
is of great advantage when evaporating alloys having constituents
of widely different volatilities, since steady state conditions aid
in maintaining constant composition in the condensate. In addition,
the constant moving of the feed stock bar upwardly produces an
abrading action which prevents condensate from accumulating between
the bar and the walls of the cooled crucible.
By feeding the replenishment stock into the crucible in the manner
described above, it is easy to maintain a constant level of the
molten pool by appropriate adjustments in the feed rate. Moreover,
the rate of heat transfer out of the crucible is generally
constant, reducing the likelihood of changes in the skull thickness
and attendant melting and freezing of metal which produces
segregation and changes in the pool composition. Since the heat
loss, when evaporating in accordance with the invention, may be
maintained substantially constant, the pool depth may also be
maintained substantially constant, creating an equilibrium
condition wherein the feed rate equals the evaporation rate.
In order to more fully illustrate the advantages of the invention,
the following examples are set forth. The invention, however, is
not intended to be limited to such examples. Typical feed rates, in
the following examples, may be about 1 or 2 inches per hour, and
typical evaporation rates may be about 1 or 2 pounds per hour. The
following examples illustrate that the invention is of particular
advantage where elements of widely differing volatilities are
present, such as with ratios of volatility of two or more to one.
The actual volatility ratio may not necessarily be consistent with
the volatilities of the elements by themselves, since compounds may
form (due to intermetallic reactions) which have different
volatilities from the elements alone.
EXAMPLE I
Evaporating an Fe 25 Cr alloy in accordance with the invention is
capable or producing a condensate on a substrate which ranges from
23 to 27 percent chromium utilizing a 2-inch-diameter feed bar and
crucible interior and utilizing 25 kilowatts of electron beam
power. In such an alloy, the ratio of volatilities is about three
to one, chromium to iron. Evaporation wherein replenishment stock
is fed into a similar size crucible from the top, using similar
beam power and an identical composition alloy, is typically only
capable of holding a .+-.5 percent variation in chromium
composition.
EXAMPLE II
Using a 2-inch-diameter crucible and a 2-inch-diameter feed stock
bar of an 80 percent nickel 20 percent iron alloy, a 10 -kilowatt
electron beam may be utilized to produce evaporation of the alloy
with a range of chromium composition in the condensate from 79.8 to
80.2 percent. In such an alloy, the ratio of volatilities is about
two to one, iron to nickel. Operations utilizing more conventional
methods may be expected to produce a range of nickel composition in
the condensate from 79.5 to 80.5 percent.
EXAMPLE III
Using a 2-inch inner diameter crucible and a 2-inch-diameter alloy
bar comprised of 25 percent chromium, 6 percent aluminum and 0.4
percent yttrium, the balance iron, a 15 -kilowatt electron beam may
be used to produce evaporation and a condensate with a composition
as follows:
Chromium: 23% to 27%
Aluminum: 5% to 7%
Yttrium: 0.2% to 0.5%
Using previously known methods, typical composition percentages
have about twice the composition spread. The yttrium is about one
twenty-fifth as volatile as the aluminum, the chromium about three
times the aluminum, and the iron about the same as the yttrium. The
ratios of volatilities are not necessarily consistent with the
volatilities of elements above because of the formation of
compounds due to intermetallic reactions.
EXAMPLE IV
An alloy containing 18 percent chromium, 8 percent nickel and the
balance iron may be evaporated in accordance with the method of the
invention, using a 2-inch-inner-diameter crucible and a
2-inch-diameter feed stock bar. The resultant condensate contains
from 16.5 to 19.5 percent chromium and from 7to 9 percent nickel.
The iron in such a situation is about twice the volatility of the
nickel, and the chromium about six times that of the nickel. Using
previously known methods, evaporation of the same alloy may result
in a condensate ranging from 14 to 23 percent chromium and from 5
to 12 percent nickel.
EXAMPLE V
An alloy containing 6 percent aluminum, 4 percent vanadium and the
balance titanium may be evaporated in accordance with the invention
using a 2-inch inner diameter crucible and a feed stock bar of
about the same diameter. The resultant condensate contains from
41/2 to 71/2 percent aluminum and 31/2 to 41/2 percent vanadium.
The aluminum is about 50 times as volatile as the titanium, and the
vanadium is about one-half the volatility of the titanium.
Previously known methods may be expected to produce twice the range
of variation in composition.
EXAMPLE VI
An alloy containing 70percent copper and 30 percent nickel may be
evaporated from a 2-inch inner diameter crucible and a feed stock
bar of about the same diameter. The resultant condensate contains
from 65 percent to 75 percent copper, the balance nickel, with the
volatility of copper being about 50 times the volatility of nickel.
Previously known methods may b expected to hold a composition range
of 50 to 90 percent copper, the balance nickel.
It may therefore be seen that the invention provides an improved
method for evaporating a molten alloy from a single crucible in a
vacuum enclosure. Improved uniformity of condensate composition is
obtainable and the replenishment rate of evaporant is closely
controllable.
Various modifications of the invention in addition to those shown
and described herein will become apparent from the foregoing
description and accompanying drawing. Such modifications are
intended to fall within the scope of the appended claims.
* * * * *