U.S. patent number 3,854,984 [Application Number 05/419,285] was granted by the patent office on 1974-12-17 for vacuum deposition of multi-element coatings and films with a single source.
This patent grant is currently assigned to General Electric Company. Invention is credited to John R. Rairden, III, Harvey W. Schadler.
United States Patent |
3,854,984 |
Schadler , et al. |
December 17, 1974 |
VACUUM DEPOSITION OF MULTI-ELEMENT COATINGS AND FILMS WITH A SINGLE
SOURCE
Abstract
Multi-element coatings and films having a composition
substantially the same as that of a precast ingot of source
material are prepared by continuously and rapidly sweeping a high
intensity electron beam over the source surface so that only a
small volume is heated at any one instant, completely evaporated
and vacuum deposited on a desired substrate as a coating of great
uniformity in volume and thickness.
Inventors: |
Schadler; Harvey W. (Scotia,
NY), Rairden, III; John R. (Schenectady, NY) |
Assignee: |
General Electric Company
(Schenectady, NY)
|
Family
ID: |
26904099 |
Appl.
No.: |
05/419,285 |
Filed: |
November 27, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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209359 |
Dec 17, 1971 |
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Current U.S.
Class: |
427/293;
219/121.15; 118/726 |
Current CPC
Class: |
C23C
14/30 (20130101); C23C 14/16 (20130101) |
Current International
Class: |
C23C
14/30 (20060101); C23C 14/28 (20060101); C23C
14/16 (20060101); C23c 013/02 () |
Field of
Search: |
;117/93.3,16R,107,131
;118/49.1,49.5 ;219/121EB |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Martin; William D.
Assistant Examiner: Newsome; John H.
Attorney, Agent or Firm: Watts; Charles T. Cohen; Joseph T.
Squillaro; Jerome C.
Parent Case Text
This is a continuation-in-part of our copending patent application
Ser. No. 209,359 filed Dec. 17, 1971, assigned to the assignee
hereof and now abandoned.
Claims
What we claim as new and desire to secure by Letters Patent of the
United States is:
1. The method of vacuum evaporating and depositing on the surface
of a turbine engine metal part a multi-element protective coating
of substantially the composition of a single metallic alloy source,
which comprises the steps of cutting a section from an ingot of
said alloy and placing the ingot section in a chamber evacuated to
a pressure of 10.sup.-.sup.3 to 10.sup.-.sup.4 torr, sweeping a
focused electron beam of power density from 10.sup.4 to 10.sup.10
watts per square inch back and forth across the surface of the
ingot section at 60 cycles per second along a line on the ingot
section surface one-half inch long, and exposing the turbine engine
part to the combined evaporated components.
2. The method of claim 1 in which the alloy source has a nominal
composition of 70Co-25Cr-4Al-1Y, and in which the electron beam is
operated at an intensity of about 10.sup.7 watts per square
inch.
3. The method of vacuum evaporating and depositing on the surface
of a turbine engine part a multi-element protective coating of
substantially the composition of a single metallic alloy source
which comprises the steps of providing a bulk body of said alloy in
a chamber evacuated to a pressure less than 10.sup.-.sup.3 torr,
continuously heating and evaporating alloy from the bulk body by
sweeping an electron beam across the surface of the body at a rate
such that the residence interval of the beam at each successive
point of impingement of the beam on the body surface is less than
one-three hundredth of a second and causing at each said successive
impingement point the melting of a superficial portion of the bulk
body and the evaporation of part of the resulting melt under the
electron beam followed by freezing of melt residue of that
superficial portion as the beam moves to the next successive points
of impingement with the bulk body surface, and exposing the turbine
engine part to the combined evaporated components of the said
alloy.
4. The method of claim 3 in which the power density of the electron
beam is from 10.sup.4 to 10.sup.10 watts per square inch.
5. The method of claim 3 in which the alloy of the bulk is of at
least two elements selected from the group consisting of iron,
cobalt, nickel, chromium, aluminum, yttrium and silicon.
6. The method of claim 3 in which the diameter of the electron beam
at the bulk body surface is between 0.002 and 0.005 inch.
7. The method of claim 3 in which the electron beam is swept across
the bulk body surface in a raster-like pattern.
8. The method of claim 3 in which the residence interval of the
electron beam is from one-three hundredth second to one-twelve
thousandth second.
Description
This invention relates to a method of forming multi-element
coatings and films from a single source, and to a product produced
thereby, and in more particular relates to the formation of
coatings by vacuum deposition of predictable compositions
essentially identical to that of the source material.
Coatings according to the invention find utility, for example, as
applied to parts of gas turbine engines.
BACKGROUND OF THE INVENTION
The electron beam heating of source materials for vacuum deposition
of coatings and films is a well established processing technique.
Commercially available types of equipment for this processing
generally employ a maximum electron accelerating voltage of 10-20
KV. This type of equipment has proven to be excellent for
depositing single element layers. However, when multi-element
layers are required, control of deposit composition is difficult
because of the differing vapor pressures of the elements at any
given temperature. If a single source is used, the element or
elements having the higher vapor pressure are distilled
preferentially from a molten pool of the source material, giving
rise to deposits of substantially different composition than that
of the source. Additionally, the rates at which elements diffuse
into such a melt can differ considerably with the result that the
melt composition rapidly shifts away from that of the original
source material which leads to further disproportion in the
deposited coating.
SUMMARY OF THE INVENTION
In accordance with the present invention, a small, high energy
intensity electron beam during operation is continuously and
rapidly swept over a surface of the source material so that
evaporation takes place under highly nonequilibrium conditions. As
a consequence, at any instant only a small volume (a few cubic
milli-inches) will be heated and evaporated without forming a
persisting melt, thus overcoming the problem of the varying vapor
pressures of the elemental components as well as that of different
diffusion rates.
The coating produced is highly uniform throughout its thickness and
volume as a result of control of the power density and beam sweep
rate, which together determine the temperature of the incremental
surface volume at the point of impact of the electron beam such as
to achieve a vapor pressure for the least volatile constituent of
the alloy of at least 10.sup.-.sup.2 torr.
Accordingly, an object of the invention is to provide a uniform
thin film coating which is economical to apply and durable in
use.
Another object of the invention is to provide a coated turbine
blade which will resist hot corrosive conditions longer than coated
blades heretofore known.
Still another object of the invention is to provide a coating on a
turbine engine part which will resist attack under severe
conditions of operation to which it is subjected including severe
oxidation and hot corrosion.
DESCRIPTION OF PREFERRED EMBODIMENTS
In accordance with the invention, a multiple component source
contains at least two elements, preferably selected from the group
iron, cobalt, nickel, chromium, aluminum, yttrium and silicon. The
power density of the electron beam is controlled within the limits
of 10.sup.4 to 10.sup.10 watts/sq. inch for these preferred alloys.
The sweep rate of the electron beam across the surface of the
source material must be fast enough to avoid spattering and the
formation of persisting liquid phase, but slow enough to effect the
evaporation from the source. The sweep rate can range from about
100 to 3,600 linear inches/min. A preferred range of power density
and sweep rate for multiple alloy sources of the above named
preferred group of metals is within the range of 10.sup.8 to
10.sup.9 watts/sq. inch power density, and when the power density
is 2 .times. 10.sup.8 watts/sq. inch, the sweep rate should be
about 100 linear inches per minute. Stated in terms of exposure
time or electron beam residence interval, the travel of the beam
will be such that the beam will impinge upon any given point on the
source material surface from about one three-hundredth second to
about one twelve-thousandth second. Thus the beam may be moved back
and forth along a line across the source material surface impinging
upon a given point tens or even hundreds of times every second and
each time cause heating, melting, evaporation and refreezing of the
melt residue. Alternatively, the beam may be moved to define a
raster-like pattern across the source material surface so that the
interval between beam exposures at any given point on that surface
is considerably longer.
In general, the multiple element source in the from of an ingot or
similar bulk body is placed in a vacuum chamber within the path of
an electron beam and the chamber is evacuated to a pressure between
2 .times. 10.sup.-.sup.3 to 4 .times. 10.sup.-.sup.3 torr in order
to avoid electric arcing in the beam gun. It is preferable to
evaporate in a chamber where the pressure is below 10.sup.-.sup.4
torr in order to minimize gas phase collisions between the
evaporating atoms from the source and the residual gas atoms in the
chamber. Thus, the lower the pressure in the chamber, the better,
but for reasons of economy a vacuum of 1 .times. 10.sup.-.sup.6
torr is preferred.
According to the invention, a uniform coating is produced wherein
the variation in composition of the resulting film at any point
throughout its volume is less than .+-. 5 percent from that of the
nominal composition of the source.
By other methods of the prior art such as conventional evaporation
using a stationary source, variations in nominal composition as
high as .+-. 50 percent are frequently observed, and in no case can
one achieve, reproducibly over extended periods of time, a
variation of less than .+-. 10 percent by such prior art methods.
Likewise, the traveling beam technique of the prior art has not
proven to be the answer to the problem solved by this invention,
the molten pool or residue formed and maintained in such an
operation resulting in variations in nominal composition of the
order of at least .+-. 10 percent.
The following typical examples demonstrate the beneficial results
of the method of the present invention.
EXAMPLE 1
A vacuum melted ingot was prepared containing (nominally, by
weight) 70Co-25Cr-4Al-1Y. A section cut from the ingot and serving
as the source was placed in a water-cooled copper crucible in a
vacuum chamber exhausted to a vacuum between 10.sup.-.sup.3 torr
and 10.sup.-.sup.4 torr. An electron beam of about 0.005 inch
diameter giving an energy intensity of about 10.sup.7
watts/in..sup.2 was employed, using a Hamilton Standard electron
beam welder, model Wl-1 provided with GE beam deflection coils for
controlling the beam sweep in X and Y directions in various desired
sweep patterns to permit concentrated focusing. A beam power of
about 120 KV and about 2ma was used, and the beam was swept back
and forth across the source of 60 cycles/sec. along a line on the
surface about one-half inch long. A film of about 2000 A. thick was
deposited in about 20 seconds on a glass coupon three-fourths inch
by three-fourths inch which was positioned about 4 inches from the
alloy source. The alloy source was one-half inch by three-fourths
inch by one-eighth inch, cut from the above described vacuum-melted
ingot. The relative chemical composition of the resulting film
deposited was measured by X-ray fluorescence technique and is
listed in Table I. Also listed for comparison purposes, is the
X-ray fluorescence analysis of a sample of the bulk material which
was cut from the original ingot, as well as the analysis of a film
deposited by "conventional" electron beam evaporation from a source
cut from the same original ingot. The conventional evaporation was
performed using a stationary beam of somewhat lower intensity,
namely at a power of 17 KV and 110 ma, giving an estimated energy
intensity 10.sup.5 watts/in..sup.2.
TABLE I ______________________________________ Comparison of
Relative Compositions of Deposited Films from 70Co-25Cr-4Al-lY
Source Method Co Cr Al Y ______________________________________ 1.
Hi Power Moving Beam (10.sup.7 watts/in..sup.2) .778 .194 .00474
.023 2. Bulk Source Alloy .740 .225 .00038 .034 3. Conventional
evapora- tion (10.sup.5 watts/in..sup.2) .678 .317 .00092 .0038
______________________________________
The comparative analyses in Table I above, as well as in Table II,
was by X-ray fluorescence analysis, expressed as:
Counts per sec/2cm.sup.2 of element/Total counts per
sec/2cm.sup.2
and is used as a relative comparison, not equivalent to weight
percent nor an absolute quantitative analysis, but does give an
indication for comparison purposes.
From the above data in Table I, it is seen that the films deposited
by method 1 are relatively closer in composition to the bulk source
alloy. It is particularly relevant that the highly volatile element
chromium in the films deposited in accordance with the invention
are much closer to the composition of the original bulk source
alloy than was the film deposited by conventional technique using a
stationary beam for the evaporation.
EXAMPLE II
A section of a cast ingot (about one-fourth inch thick by 2 1/16
inch diameter), containing, by weight, 80 percent Ni and 20 percent
Cr was mounted on a water-cooled copper pedestal. A beam power of
0.67 KW (122 KV, 5.5 ma) was used to evaporate the material from
the source. The moving beam was swept across the surface of the
specimen in a moving circle about three-fourths inch diameter at a
rate of 40 rpm instead of along a straight line, as in Example I.
Initially the beam spot size was about one-eighth inch diameter,
which made the beam intensity 5.5 .times. 10.sup.4 watts/in..sup.2.
At seven minutes into the run, the spot size was focused to about
0.002 inches diameter, making the beam intensity about 2 .times.
10.sup.8 watts/in..sup.2. A series of films were deposited on glass
coupons at intervals, ranging from about 2,000A to about 8,000A in
film thickness. The composition of these films was analyzed, using
the X-ray fluorescence technique, as in Table I, to give a relative
indication. A comparison of the results shows that the high power
density moving beam achieved a deposited film much closer in
composition to the bulk source alloy.
TABLE II ______________________________________ Comparison of
Relative Compositions of Deposited Films from 20Cr-80Ni Source
Method Power Density Element watts/in..sup.2 Cr Ni
______________________________________ Low power 5.5 .times.
10.sup.4 .0679 .932 (moving beam) High power 2 .times. 10.sup.8
.0850 .915 (moving beam) Bulk Source -- .115 .885 Conventional 4.4
.times. 10.sup.4 .187 .813 (stationary beam)
______________________________________
It will be noted that Table II as well as Table I shows that the
high powered intensity moving beam causes a film to be deposited
which is closer in composition to that of the bulk source alloys
than the film deposited by the conventional evaporation process
using a stationary electron beam. In both Example I and Example II,
the highly volatile constituent occurs in the film at a composition
which deviates much less from the desired bulk composition as
compared to the film produced by the conventional evaporation
method.
Thus, the two compared methods of evaporation in each example
demonstrate clearly that the composition of the deposit made from
the high intensity evaporation and moving electron beam conforms
more nearly to that of the bulk source alloy than a comparable film
deposited by conventional evaporation with a stationary beam.
Those skilled in the art will understand that the concept of this
invention constitutes a basic departure from prior art practice,
particularly in respect to the fact that no lasting or persisting
liquid phase is produced or established at any time during the
vacuum evaporating and depositing operations. As indicated above
the diameter of the focussed electron beam on the bulk body source
material surface is relatively small, being from about two mils to
five mils (i.e., 0.002 - 0.005 inch) so that only a very small
fraction of the beam travel course over the bulk body surface is
exposed to the beam at any one time. Heating, melting and
evaporation, as well as refreezing of any unevaporated melt, are a
sequence of virtually milli-second events which take place at each
point of impingement of the beam with the bulk body surface. Thus,
at each successive point of impingement, a superficial portion of
the bulk body is melted and part (possibly one-half) of the melt is
evaporated before the beam moves to the next successive points of
impingement. Refreezing of the melt residue is virtually
instantaneous and in any event so rapid as to preclude diffusion of
source material constituents into the melt. Surprisingly, such
melting and evaporating and refreezing can be caused to occur in
the same small area of the bulk body surface over 100 times per
second so that there is no persisting melt but evaporation is
continuous throughout the deposition process.
* * * * *