U.S. patent number 3,874,901 [Application Number 05/353,660] was granted by the patent office on 1975-04-01 for coating system for superalloys.
This patent grant is currently assigned to General Electric Company. Invention is credited to John R. Rairden, III.
United States Patent |
3,874,901 |
Rairden, III |
April 1, 1975 |
Coating system for superalloys
Abstract
A protective coating system is provided for nickel-base and
cobalt-base superalloys which is capable of imparting oxidation and
corrosion resistance at elevated temperatures. The superalloy body
is first coated by physical vapor deposition with a composition
consisting essentially of chromium, aluminum and, optionally, a
member selected from the group consisting of yttrium and the rare
earth elements and at least one element selected from the group
consisting of iron, cobalt and nickel. Thereafter the body is
coated with an overlayer of aluminum by physical vapor deposition
and heat treated to cause the interdiffusion of aluminum into the
first coating layer and thereby greatly enhance the hot corrosion
and oxidation resistance of the coating system.
Inventors: |
Rairden, III; John R.
(Schenectady, NY) |
Assignee: |
General Electric Company
(Schenectady, NY)
|
Family
ID: |
23390023 |
Appl.
No.: |
05/353,660 |
Filed: |
April 23, 1973 |
Current U.S.
Class: |
427/250;
427/405 |
Current CPC
Class: |
C23C
14/5806 (20130101); C23C 14/16 (20130101); C23C
14/58 (20130101); C23C 26/00 (20130101); C23C
14/5893 (20130101) |
Current International
Class: |
C23C
14/58 (20060101); C23C 26/00 (20060101); C23C
14/16 (20060101); B44d 001/14 () |
Field of
Search: |
;117/71M,107,17.2P |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Weiffenbach; Cameron K.
Attorney, Agent or Firm: Adam; Gerhard K. Cohen; Joseph T.
Squillaro; Jerome C.
Claims
I claim:
1. A method of improving the high temperature oxidation and
corrosion resistance of a nickel-base or a cobalt-base superalloy
body comprising the steps of:
a. coating the superalloy body by physical vapor deposition with a
composition consisting essentially of chromium, aluminum, a member
selected from the group consisting of yttrium and the rare earth
elements, and at least one element selected from the group
consisting of iron, cobalt and nickel, and
b. subjecting the coated body to an overcoat of aluminum deposited
by physical vapor deposition, and
c. heat treating the duplex coating to cause the interdiffusion of
aluminum with the first coating to increase the oxidation and
corrosion resistance of the coating.
2. The method of claim 1, wherein said composition consists
essentially in weight percent of 14-35 percent chromium, 4-20
percent aluminum, 0-3 percent yttrium and the balance being a
member selected from the group consisting of iron, cobalt, nickel,
and mixtures thereof.
3. The method of claim 1, wherein said composition consists
essentially in weight percent of 25-29 percent chromium, 12-14
percent aluminum, 0-0.9 percent yttrium and the balance being
iron.
4. The method of claim 1, wherein said composition consists
essentially in weight percent of 19-24 percent chromium, 13-17
percent aluminum, 0-0.9 percent yttrium, and the balance being
cobalt.
5. The method of claim 1, wherein said composition consists
essentially in weight percent of 20-35 percent chromium, 15-20
percent aluminum, 0-0.30 percent yttrium and the balance being
nickel.
6. The method of claim 1, wherein said heat treating is at a
temperature in the range of about 950.degree. C. up to the
solutionizing heat treatment of the superalloy body.
7. The method of claim 6, wherein said body is a nickel-base
superalloy.
8. The method of claim 6, wherein said body is a cobalt-base
superalloy.
9. The method of claim 6, wherein the first coating has a thickness
of about 1-7 mils and the heat treated aluminum overcoating
penetrates into the first coating to a depth of about 1-2 mils.
Description
The superalloys are heat-resistant materials having superior
strengths at high temperatures. Many of these alloys contain iron,
nickel or cobalt alone or in combination as the principal alloying
elements together with chromium to impart surface stability and
usually contain one or more minor constituents, such as molybdenum,
tungsten, columbium, titanium and aluminum for the purpose of
effecting strengthening. The physical properties of the superalloys
make them particularly useful in the manufacture of gas turbine
engine components.
Heretofore, surface coatings have been used to protect the
superalloy articles from high temperature oxidation and corrosion.
Various coatings for superalloys have been described in the
literature and of particular interest are coating compositions
consisting essentially of chromium, aluminum and, optionally, a
member selected from the group consisting of yttrium and the rare
earth elements and a metal selected from the group consisting of
iron, cobalt and nickel. Illustrative coatings wherein the
compositions are given in weight percent are designated as
follows:
Ingredients FeCrAlY CoCrAlY NiCrAlY
______________________________________ Chromium 25-29% 19-24%
20-35% Aluminum 12-14% 13-17% 15-20% Yttrium 0.6-0.9% 0.6-0.9%
0.05-0.30% Iron balance -- -- Cobalt -- balance -- Nickel -- --
balance ______________________________________
The application of the coating composition to a variety of
substrates, such as nickel-base and cobalt-base superalloys may be
achieved by physical vapor deposition in a vacuum chamber. During
this procedure, the composition is thermally evaporated from a
source heated, for example, by an electron beam, and a thin metal
coating is condensed on the surface of the workpiece. Layers of the
coating are formed as the workpiece is rotated until the thickness
is, preferably, in the range of about 1-7 mils. Unfortunately, the
deposited coating has radially oriented defects which are the sites
of attack by oxidizing and/or corrosive atmospheres at high
temperatures. Such defects can lead to premature failure of the
coating.
Attempts to prolong the useful life of superalloys coated with a
FeCrAlY alloy are disclosed by Elam et al., U.S. Pat. No.
3,528,861. The coating effectiveness was found to be limited by the
formation of an intergranular precipitate during the coating
deposition cycle. The effect of the detrimental precipitate was
improved by shot peening or glass bead blasting to break up the
precipitate into small particles which are more easily taken into
solution by heat treatment.
In accordance with the present invention, I have invented a method
of improving the high temperature corrosion resistance of a
nickel-base or cobalt-base superalloy body by first coating the
superalloy body by physical vapor deposition with a composition
consisting essentially of chromium, aluminum, and, optionally, a
member selected from the group consisting of yttrium and the rare
earth elements, and at least one element selected from the group
consisting of iron, cobalt and nickel and thereafter depositing a
layer of aluminum, preferably 0.1 to 3.0 mil thick, onto the coated
body by physical vapor deposition and heat treating this composite
coating to increase the corrosion resistance of the body. The
effectiveness of the coating system may be explained by the fact
that the first coating layer exhibits flaws or boundaries that are
oriented in a perpendicular direction to the deposition plane. Upon
exposure to a corrosive environment, these flaws or boundaries are
preferentially attacked resulting in premature failure of the
coating. The application of an aluminum overcoat that is
subsequently suitably heat treated prevents this type of failure
and thereby substantially increases the life of the coated article.
In addition, the concentration profile of our novel coating system
indicates the presence of a high concentration of aluminum on the
outer surface of the coating which may also contribute to the
improved properties. The coated superalloy bodies prepared by our
invention are particularly useful in making gas turbine engine
components.
The invention is more clearly understood from the following
description taken in conjunction with the accompanying drawing in
which:
FIG. 1 is a photomicrograph (500X) of a Udimet 500 nickel-base
superalloy body coated with a CoCrAlY coating.
FIG. 2 is a photomicrograph (500X) of a Udimet 500 nickel-base
superalloy body coated with a first CoCrAlY coating and then an
aluminum layer and heat treated for three hours at 1160.degree. C.
in argon to form a composite coating according to the method of our
invention.
FIG. 3 is a photomicrograph (500X) illustrating the effect of
corrosion on a CoCrAlY coated superalloy body.
FIG. 4 is a photomicrograph (500X) illustrating the effect of
corrosion on a coated superalloy body coated as shown in FIG.
2.
The superalloys are strong, high temperature materials which are
particularly useful in gas turbine engines. A substantial listing
of these materials is set forth by W. F. Simmons, Compilation of
Chemical Compositions and Rupture Strengths of Superalloys, ASTM
Data Series Publication No. DS9E, and may be represented by the
nominal compositions in weight percent of the following
superalloys:
Udimet Ingredient Rene 80 Rene 100 In-738 500
______________________________________ C 0.17 0.18 0.17 0.08 Mn 0.2
0.50 0.20 0.75 Si 0.2 0.50 0.30 0.75 Cr 14.0 9.5 16.0 19.0 Ni *Bal.
*Bal. Bal. Bal. Co 9.5 15.0 8.5 18.0 Mo 4.0 3.0 1.75 4.0 W 4.0 --
2.6 -- Cb -- -- 0.9 -- Ti 5.0 4.20 3.4 2.9 Al 3.0 5.50 3.4 2.9 B
0.015 0.015 0.01 0.005 Zr 0.03 0.06 0.10 -- Fe 0.2 1.0max 0.50 4.0
Other -- 1.0V 1.75Ta -- ______________________________________
The first coating of our protective coating system is designated
herein as "MCrAlY" or "MCrAl" coating wherein M is a member
selected from the group consisting of iron, cobalt, and nickel.
This coating is broadly defined as consisting essentially in weight
percent of the following nominal compositions:
Ingredients Weight % ______________________________________
Chromium 14-35 Aluminum 4-20 Yttrium 0-3 Iron ) Cobalt ) Balance
Nickel ) ______________________________________ Included in this
formulation are the compositions designated hereinabove as FeCrAlY,
CoCrAlY, and NiCrAlY and also includes these compositions in which
yttrium is entirely absent. The MCrAlY or MCrAl coating is applied
to the substrate by a physical vapor deposition technique which is
described in considerable detail in Vapor Deposition, Edited by C.
F. Powell et al., John Wiley & Sons, New York (1966).
Accordingly, the coating is evaporated and deposited in a vacuum
chamber. Typically, the metal alloy is heated by an electron beam
focused on the metal alloy ingot to evaporate the metal to a vapor.
During evaporation, the vapor condenses as a coating, preferably
about 1-7 mils in thickness on the workpiece being coated. The
material to be applied is heated in a high vacuum to a temperature
at which its vapor pressure is about 10.sup..sup.-2 torr or greater
whereupon it emits molecular rays in all directions. During coating
the vacuum must be very high to permit the molecular rays to travel
from their source without disturbance until they hit the surface of
the object to be coated. A photomicrograph of a nickel-base
superalloy coated with a CoCrAlY coating is shown in FIG. 1.
Then, the first coating is overcoated with a layer of aluminum,
preferably 0.1 to 3.0 mils thick, by a physical vapor deposition
technique already described and referred to in Powell et al. cited
hereinabove. In a preferred embodiment, the aluminum layer is
deposited by evaporation from an electron beam heated source. This
technique is particularly useful because the aluminum layer can be
deposited in the same equipment used to deposit the MCrAl or MCrAlY
by simply substituting an aluminum source for the MCrAl or MCrAlY
source.
Thereafter, the coated body is subjected to a heat treatment to
cause interdiffusion of the aluminum overlayer into the first
coating layer. Essentially while the aluminum, which has a low
melting point of 660.2.degree. C., diffuses into the cracks and
defects of the first coating, a simultaneous interdiffusion
phenomena occurs during the heat treatment whereby the aluminum
combines with the first coating to form a higher melting alloy. The
minimum temperature for the heat treatment is about 950.degree. C.,
while the maximum temperature depends upon the superalloy substrate
since it is undesirable to heat above the solutionizing heat
treatment of the alloy involved. For nickel-base superalloys this
tends to be in the range of about 1040.degree.-1230.degree. C. The
heat treatment of cobalt-base alloys is much less complex than for
nickel-base alloys and high temperature solution heat treatments
are usually at about 1150.degree. C. The time of heat treatment is
preferably in the range of about 0.25-5 hours. To avoid premature
oxidation of the duplex coating surface prior to interdiffusion,
the heat treatment should be performed in an inert atmosphere, e.g.
helium, argon.
A photomicrograph of a nickel-base superalloy which has been coated
with a heat treated duplex coating of CoCrAlY plus aluminum is
shown in FIG. 2. The first coating of CoCrAlY exhibited flaws or
boundaries that are oriented in a perpendicular direction to the
deposition plane as shown in FIG. 1 which become sites for attack
by high temperature oxidation and corrosion as shown in FIG. 3.
Upon application of the heat treated duplex coating, any open
defects of an MCrAlY coating become filled as shown in FIG. 2. FIG.
4 shows a photomicrograph of the heat treated duplex coating of
CoCrAlY plus aluminum that has been subjected to a severe hot
corrosion and oxidation environment consisting of a fused salt at
1650.degree. F. containing Na.sub.2 SO.sub.4 and V.sub.2 O.sub.5.
It is to this unique coating system that we attribute the improved
properties of high temperature oxidation and corrosion
resistance.
Our invention is further illustrated by the following examples:
EXAMPLE I
Cast pins of Udimet 500 nickel-base superalloy 2 in. long were
ground to a diameter of 0.170 in. They were placed into a vacuum
electron beam furnace and the chamber was then evacuated to
10.sup..sup.-5 microns of mercury. The pins were rotated during
deposition and a resistance heater was used to heat the pins. When
the temperature reached 900.degree. C., the electron beam was
focused on an ingot having the following nominal composition:
Ingredient Weight % ______________________________________ Cobalt
64 Chromium 22 Aluminum 13 Yttrium 1
______________________________________
Evaporation of the metal was at a constant power of 19.0 kilovolts
and 275 milliamps for 30 minutes. A coating having a thickness of
about 3 mils was deposited on the pins. The pins were cooled to
room temperature in the vacuum. Then the chamber was filled to
atmospheric pressure with air and a pure aluminum source was
substituted for the CoCrAlY source. The chamber was again evacuated
to a pressure of 10.sup.-.sup.5 mm. Hg and the pins were overcoated
with a layer of aluminum about 1/2 mil thick by evaporation at a
constant power of 19.0 kilovolts and 80 milliamps for three
minutes. Finally, the pins coated with the duplex layer of CoCrAlY
plus aluminum were heat treated for three hours at 1160.degree. C.
in an argon atmosphere.
Upon examination of the sample it was noted that this procedure
resulted in a penetration of about 1-2 mils of aluminum into the
surface of the CoCrAlY coating and an essentially total filling of
the open boundaries of the CoCrAlY coating.
A crucible test was then performed to test resistance to oxidation
and corrosion of the samples coated only with the CoCrAlY coating
and the second group subjected to the duplex coating procedure.
Both groups of coated pins were immersed in a fused salt bath of
85.2 percent Na.sub.2 CO.sub.3, 0.5 percent NaCl, 13.0 percent
V.sub.2 O.sub.5 and 1.3 percent Na.sub.2 SO.sub.4 (by weight) at a
temperature of 900.degree. C. in an air atmosphere. After 16 hours
the samples were removed.
It was observed that the samples coated only with the CoCrAlY
coating were characterized by deep "spike" corrosion, but the pins
subjected to the aluminizing overcoating procedure were
substantially more resistant to attack by corrosion with little or
no evidence of "spike" corrosion.
EXAMPLE II
Following the procedure of Example I, test pins having a 0.170 in.
diameter were prepared from Udimet 500 nickel-base superalloy. The
pins were coated by electron beam evaporation with the following
nominal composition:
Ingredient Weight % ______________________________________ Nickel
70 Chromium 20 Aluminum 15
______________________________________
After the pins were removed from the apparatus, the coating had a
thickness of about 3 mils.
Thereafter some of the coated pins were overcoated with about 0.5
mil of aluminum by the physical evaporation technique. The samples
coated with the duplex layer of NiCrAl plus aluminum were heat
treated for three hours at 1160.degree. C. in argon.
Comparative high temperature oxidation and corrosion tests were
performed on test samples coated only with the NiCrAl alloy and on
test samples coated with a heat treated duplex layer of NiCrAl plus
aluminum. In the crucible test, the pins were partially immersed in
the fused salt mixture described in Example I for 16 hours at
900.degree. C. The samples coated only with the NiCrAl coating
after being subjected to the hot corrosion and oxidation test
showed the typical corrosion and "spike" penetration. The samples
which had been protected by the heat treated duplex coating showed
almost a complete absence of "spike" corrosion and that indicated
that the heat treated aluminum overlay coating had filled in the
defects of the initial coating.
EXAMPLE III
Following the procedure of Example I, cast pins of Udimet 500
nickel-base superalloy were coated by physical vapor deposition
with the following nominal composition:
Ingredient Weight % ______________________________________ Iron
64.0 Chromium 25.0 Aluminum 10.0 Yttrium 1.0
______________________________________
A coating having a thickness of about 3 mils was deposited on the
pins. Thereafter some of the pins were duplex coated by the
physical vapor deposition technique described in Examples I and
II.
When subjected to the corrosion tests it was observed that the pins
subjected to the duplex overcoat procedure were considerably more
resistant to corrosion than those which had been coated only with
the FeCrAlY coating.
It will be appreciated that the invention is not limited to the
specific details shown in the examples and illustrations and that
various modifications may be made within the ordinary skill in the
art without departing from the spirit and scope of the
invention.
* * * * *