U.S. patent number 3,620,815 [Application Number 04/806,955] was granted by the patent office on 1971-11-16 for vapor collimation in vacuum deposition of coatings.
This patent grant is currently assigned to United Aircraft Corporation, East Hartford, CT. Invention is credited to Dennis J. Evans, Mitchell J. Bala, Nicholas E. Ulion, Sol S. Blecherman.
United States Patent |
3,620,815 |
|
November 16, 1971 |
VAPOR COLLIMATION IN VACUUM DEPOSITION OF COATINGS
Abstract
In the processes for forming protective coatings on metals,
particularly the nickel-base and cobalt-base superalloys, by
deposition in vacuum, an inert gas cascade surrounding the melt is
utilized to collimate the coating vapor cloud and reduce low angle
deposition.
Inventors: |
Sol S. Blecherman (Newington,
CT), Mitchell J. Bala (Hazardville, CT), Dennis J.
Evans (Rocky Hill, CT), Nicholas E. Ulion (Vernon,
CT) |
Assignee: |
United Aircraft Corporation, East
Hartford, CT (N/A)
|
Family
ID: |
25195213 |
Appl.
No.: |
04/806,955 |
Filed: |
March 13, 1969 |
Current U.S.
Class: |
427/251; 118/726;
427/597 |
Current CPC
Class: |
C23C
14/228 (20130101); C23C 14/24 (20130101) |
Current International
Class: |
C23C
14/24 (20060101); C23c 011/00 (); C23c
013/00 () |
Field of
Search: |
;117/106,107,107.1
;118/49,49.1,50,48 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Alfred L. Leavitt
Assistant Examiner: Kenneth P. Glynn
Attorney, Agent or Firm: Richard N. James
Claims
1. In the process for forming protective coatings on metals by
vacuum vapor deposition, the improvement which comprises:
establishing a cloud of coating material in vapor form moving
between a molten pool of coating material and the articles to be
coated, said article to be coated being substantially within the
line-of-sight of the molten pool; and at a plurality of locations
peripherally of the vapor cloud, injecting a high-velocity stream
of inert gas at an angle toward the vapor cloud to reduce the
extent of low-angle vapor deposition and to redirect and
2. The method according to claim 1 wherein:
3. The method according to claim 2 wherein: the vacuum in the
system is sufficiently low to prevent the generation of a
4. The method of improving the efficiency of deposition in vacuum
coating processes wherein a high-melting point alloy is to be
coated upon a metallic substrate which comprises: establishing a
moving cloud of coating material vapor between the source of
coating material and the substrate to be coated, said article to be
coated being substantially within the line of sight of the molten
pool; encircling the source of coating material with an inert gas
cascade having a plurality of exit parts angularly directed
inwardly toward and upwardly from the source; and admitting an
inert gas at high-velocity through the exit ports to collimate the
coating material vapor toward the vertical line-of-sight between
the source and
5. The method according to claim 4 wherein:
6. The method according to claim 5 wherein: the pressure in the
system is maintained at a value low enough to prevent the
generation of a plasma upon the admission of helium to the system.
Description
The present invention relates in general to metal coating processes
and apparatus therefor and, more particularly, to vacuum deposition
processes.
It is well-known that the conventional nickel-base and cobalt-base
superalloys do not in and of themselves exhibit sufficient
oxidation-erosion resistance to provide component operating lives
of reasonable duration in the dynamic oxidizing environments such
as those associated with the operation of gas turbine engines.
Accordingly, it has been the usual practice to provide these alloys
with a protective coating in such applications.
Although the aluminide coatings, such as that described in the U.S.
Pat. No. 3,102,044, to Joseph, have in the past displayed
satisfactory performance, it is well known that these coatings,
because of their dependence upon the availability of substrate
elements, often are characterized by a composition less than
optimum. Furthermore, these coatings are often achieved only at the
expense of some mechanical property loss in substrate strength.
Many of the more advanced coatings developed for the next
generation of jet engines depend in the first instance on the
deposition of a high-melting point coating alloy with a concurrent
or subsequent reaction with the substrate to attain the desired end
composition, microstructure or adherence. These new alloys
generally demand the application of special coating techniques to
provide the right species in the right amounts at the surfaces to
be protected.
Several coating compositions of current interest are described in
detail in copending applications of the present assignee. Among
these compositions is that hereinafter referred to as the FeCrA1Y
coating at a nominal composition of, by weight, 30 percent
chromium, 15 percent aluminum, 0.5 percent yttrium, balance iron,
as discussed in the copending application of Frank P. Talboon, Jr.,
et al. entitled "Iron Base Coating for the Superalloys," Ser. No.
731,650 filed May 23, 1968, now U.S. Pat. No. 3,542,530. Another
such composition is the CoCrA1Y composition at about, by weight, 21
percent chromium, 15 percent aluminum, 0.7 percent yttrium, balance
cobalt.
The basic problems associated with the deposition of these coating
alloys relates to their high-melting points and the difficulty of
providing the right amount of all of the alloy species in the
coating as applied. Satisfactory results have been attained through
the use of vacuum vapor deposition techniques, such as that
suggested in the U.S. Pat. No. 2,746,420 to Steigerwald. These
processes, which have in the past been primarily directed toward
the application of relatively low-temperature materials of
relatively simple composition, are in the present instance
characterized by extreme sensitivity to variations in the process
parameters and, accordingly, reproducibility as well as processing
expense is a problem.
The vacuum vapor deposition of electron beam melted metals in
existing low-evaporation rate, production-type systems, such as
high-cyclic speed or strip line coaters, has essentially been
limited to line-of-sight coating from the source (molten pool of
coating metal) to rotating or linearly moving substrates. Recently,
several techniques have been developed to improve the versatility
of the basic process through randomization or redirection of the
vapor cloud. In one such method, a low-velocity, controlled inert
gas leak, to a chamber pressure sufficiently low to prevent
sustaining a gas plasma but sufficiently high to substantially
decrease the mean free collision path of the metal vapor atoms in
the vicinity of the surface to be coated, has been utilized to
randomize the direction of the metal vapor atoms thus permitting
the coating of non-line-of-sight areas.
The present invention contemplates a vacuum deposition process
which utilizes controlled inert gas impingement on the vapor cloud
to collimate and densify the coating material vapor cloud. For this
purpose, an inert gas is admitted at high velocity into the vacuum
chamber through a gas cascade or multiorificed nozzle surrounding
the pool of molten coating material, the gas being introduced at an
angle to the vapor cloud to minimize low-angle vapor deposition
and, in essence, to pump the vapors into a more concentrated vapor
cone.
FIG. 1 illustrates, somewhat schematically, a vacuum deposition
chamber with an inert gas cascade surrounding the molten pool and
operating to reduce the angle of the vapor cone.
FIG. 2 is an expanded view of the molten pool area more clearly
showing the relative position of the gas cascade.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As shown most clearly in FIG. 1, the articles to be coated 2 are
mounted within a vacuum chamber 4. Inasmuch as the process is
fundamentally line-of-sight, the parts are usually mounted to
effect rotation about their individual axes, typically utilizing a
pass-through (not shown) through the vacuum chamber to an external
drive system. For minimum nonuniformity of coating between the
individual parts, they are normally mounted in a plane of vapor
isodensity 6, or roughly along an arc defining a zone of constant
vapor concentration, the parts closest to the vertical passing
through the center of the molten pool being located slightly
farther from the pool surface than those positioned at an angle
with respect to said vertical. The parts are further positioned as
close as possible to the surface of the molten pool for maximum
coating efficiency but far enough removed therefrom to prevent
coating contamination by splash from the pool. The pool height
varies with each system but for a 2 inch diameter pool and a
deposition rate of about 0.3 mils per minute with a FeCrA1Y coating
material, a mean height of about 10 inches has been found to be
satisfactory.
There are a number of heating techniques which have been employed
in the past in connection with vacuum deposition and heat
treatment. A preferred heat source and that illustrated
schematically in the drawing is an electron beam gun 8. The
arrangement of the electron beam gun within the vacuum chamber is a
function of design. In some installations, deflection magnetics
have been utilized to direct the beam onto the surface 12 of the
coating material ingot 10. A 30 kilowatt electron beam unit has
provided satisfactory deposition rates with a 2 inch diameter
ingot, the depth of the molten pool usually being 1/4-1/2 inch.
The ingot 10 is made movable with respect to the water cooled
crucible 14 and is normally continuously fed into the crucible to
maintain a constant pool height. This is important for two reasons.
First, because the electron beam is focused on the pool surface, it
is desirable to maintain the ingot level at the proper height.
Secondly, because coating efficiency, composition and uniformity
are very susceptible to pool height changes, a constant height
relationship 16 between pool and parts to be coated is
preferred.
The key to the present invention is the provision of a multiple
orifice inert gas manifold 20 around the periphery of the molten
pool, the orifices 21 being angled upwardly and inwardly toward the
vapor cloud. A high-velocity inert gas stream, preferably helium,
to reduce the incidence of a plasma gas discharge resulting in
process instability, is utilized to narrow the cone configuration
of the vapor cloud from its normal wide angle 22 to a more acute
angle 24, with a resultant densification of the vapors. In essence,
the inert gas stream reduces the scatter of the vapor cloud and
thus reduces the material loss incident to low-angle vapor emission
from the melt.
A number of tests were conducted with various coating materials and
various substrate alloys. In one series of tests, helium gas was
introduced at a line pressure of 17 p.s.i.a. through a 4 inch
diameter ring manifold oriented concentric with the 2 inch diameter
molten pool. Fifty-three evenly-spaced, 0.036 inch diameter holes
26 through the wall of a stainless steel tube, oriented at an angle
of approximately 45.degree. with respect to the vertical, were
provided for orificing purposes.
When weight measurements were made (corresponding specimens have
been coated with and without the admission of inert gas) increases
were noted in those tests utilizing inert gas admission.
Additionally, spurious deposits of the coating material in
low-angle locations on the vacuum chamber were significantly
reduced.
The results of a number of these tests are summarized in the
following table. ##SPC1##
Referring to table I, it will be noted that tests 2 and 3 were run
utilizing the inert gas cascading of the present invention and thus
should be compared with tests 1 and 4 which were run without vapor
cloud collimation. In each case, three specimens were coated
simultaneously, specimen 2 being the specimen located directly over
the centerline of the 2 inch diameter pool, specimens 1 and 3 being
located closer to the pool but offset from the vertical centerline
thereof at an angle of 70.degree. with respect to the pool
horizontal.
A vertical reference specimen located at an angle of 52.degree.
with respect to the pool horizontal was utilized to ascertain the
effect of vapor cloud collimation on the incidence of low-angle
deposition.
It will be noted that in each case specimen weight gain was
increased with inert gas admission through the cascade and
low-angle deposition was decreased.
The typical coating procedure has utilized a power setting of the
electron beam gun at 21 kilowatts for the CoCrA1Y material and at
15.5 kilowatts for the FeCrAlY coating. Control of coating
thickness to .+-. 0.0005 inch at a designed thickness of 0.005 inch
has been consistently achieved.
It has been mentioned previously that chamber pressures should be
maintained at a low-enough value to prevent the incidence of a
plasma generation in the process which results in a fundamental
instability and a loss of control of the process. In the present
process to reduce the possibility of plasma generation, helium
rather than argon is preferred for vapor cloud collimation
purposes.
The very important factor in the process, once satisfactory coating
conditions are attained, is the close maintenance of these
conditions as experience has demonstrated the relative criticality
of the process to small variations in the process parameters.
While the invention has been described in connection with
particular preferred embodiments and examples, these will be
understood to be illustrative only. Numerous modifications to the
constructional details, materials and process parameters will be
evident to those skilled in the art within the true spirit of the
invention as set forth in the appended claims.
* * * * *