U.S. patent number 3,647,517 [Application Number 05/048,515] was granted by the patent office on 1972-03-07 for impact resistant coatings for cobalt-base superalloys and the like.
This patent grant is currently assigned to Chromalloy American Corporation. Invention is credited to Harry W. Brill-Edwards, Thomas Milidantri.
United States Patent |
3,647,517 |
Milidantri , et al. |
March 7, 1972 |
IMPACT RESISTANT COATINGS FOR COBALT-BASE SUPERALLOYS AND THE
LIKE
Abstract
In the production of impact and oxidation resistant metal
coatings on superalloy substrates, e.g., cobalt-base superalloys,
by pack cementation, such as a nickel aluminide coating, the
improvement wherein nickel is first diffusion coated onto the
substrate from a pack containing a small but effective amount of
sulfur as a metal transfer agent, following which the nickel coated
substrate is then coated with another metal, such as aluminum.
Inventors: |
Milidantri; Thomas (Spring
Valley, NY), Brill-Edwards; Harry W. (New York, NY) |
Assignee: |
Chromalloy American Corporation
(Orangeburg, NY)
|
Family
ID: |
21954994 |
Appl.
No.: |
05/048,515 |
Filed: |
June 22, 1970 |
Current U.S.
Class: |
428/656; 148/527;
427/250; 428/667; 428/680; 428/941; 75/252; 148/537; 427/327;
428/678; 428/938 |
Current CPC
Class: |
C23C
10/34 (20130101); C22C 19/053 (20130101); C22C
19/07 (20130101); Y10T 428/12854 (20150115); Y10T
428/12944 (20150115); Y10T 428/12778 (20150115); Y10S
428/938 (20130101); Y10S 428/941 (20130101); Y10T
428/12931 (20150115) |
Current International
Class: |
C23C
10/00 (20060101); C23C 10/34 (20060101); C22C
19/07 (20060101); C22C 19/05 (20060101); C23c
009/02 () |
Field of
Search: |
;117/17.2P,71M,131
;29/197,196.6 ;106/1 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Kendall; Ralph S.
Claims
What is claimed is:
1. In a method of producing a highly impact resistant coating by
pack cementation on a substrate of a heat resistant superalloy
article in which nickel is diffused into the substrate as a first
step in the ultimate formation of said impact resistant coating,
the improvement which comprises,
providing a chromium-containing superalloy article, embedding said
article in a particulate cementation pack consisting essentially of
nickel powder mixed with an inert refractory material, the bed
containing a small but effective amount of sulfur for effecting the
transfer of said nickel to the substrate of said article at an
elevated diffusion coating temperature, and
then heating said pack and the embedded article to an elevated
diffusion coating temperature whereby to effect diffusion coating
of said article with nickel, said coating being carried out while
maintaining the oxygen in said pack at a partial pressure below
which oxidation of sulfur to sulfur oxide compounds is
substantially inhibited.
2. The method of claim 1, wherein the oxygen is maintained at the
desired partial pressure by mixing with said pack a small but
effective amount of an oxygen-scavenging metal whose free energy of
formation of the oxide is at least about 115,000 calories per gram
atom of oxygen at about 250.degree. C.
3. The method of claim 2, wherein the oxygen-scavenging metal is
titanium.
4. The method of claim 3, wherein the pack cementation bed has a
composition ranging from about 5 to 60% Ni, about 1/8 to 1% Ti,
about 0.002 to 0.1% S and the balance essentially the inert
refractory material.
5. The method of claim 4, wherein the bed comprises approximately
40% nickel, approximately 0.2Ti, approximately 0.02% S and the
balance essentially aluminum oxide.
6. The method of claim 4, wherein following the production of the
diffusion-bonded nickel coating, the substrate of the article is
cleaned, and the coated surface then aluminized, whereby a highly
impact and spall resistant coating containing nickel aluminide is
produced.
7. The method of claim 6, wherein the nickel-coated article is
aluminized by embedding it in a cementation pack containing by
weight about 10 to 30% Cr, about 1 to 5% Al, a small but effective
amount of a halide energizer and the balance a particulate inert
refractory material, said article being then aluminized at a
temperature of about 1,750.degree. to 2,050.degree. F. for 1 to 30
hours.
8. The method of claim 4, wherein the superalloy is selected from
the group consisting of cobalt-base alloys containing by weight
about 10 to 30% Cr, up to about 15% Ni, up to about 15% Fe, up to
about 5% Cb, up to about 15% percent W, up to about 5% Ti and/or
Al, up to about 1% Zr, up to about 1.5% C, up to about 1 to 2% Si,
up to about 2% Mn and the balance essentially 45% Co; and
nickel-base alloys containing by weight about 10 to 30% Cr, up to
about 20 percent of a metal from the group consisting of Mo and W,
up to about 10 percent of a metal from the group consisting of Cb
and Ta, up to about 0.5% C, up to about 6.5% of a metal from the
group consisting of Ti and Al, the total amount of these metals not
exceeding about 10%, up to about 20% Co, up to about 2% Mn, up to
about 2% Si, up to about 0.1% B, up to about 1% Zr and the balance
at least about 45% nickel.
9. In a method of producing a highly impact and spall resistant
coating by pack cementation on a substrate of a cobalt-base
superalloy article containing about 10 to 30% Cr, up to about 15%
Ni, up to about 15% Fe, up to about 5% Cb, up to about 15% W, up to
about 5% Ti and/or A1, up to about 1% Zr, up to about 1.5% percent
C, up to about 2% Si, up to about 2% Mn, and the balance
essentially at least about 45% cobalt in which a layer of
diffusion-bonded nickel is produced as a first step in the ultimate
formation of said impact resistant coating, the improvement which
comprises,
embedding the article in a particulate cementation pack consisting
essentially of said nickel mixed with an inert refractory material,
the bed also containing a small but effective amount of sulfur for
effecting transfer of nickel from the pack to the substrate of the
article, and
then heating said pack and the embedded article to an elevated
diffusion coating temperature whereby to effect diffusion coating
of said article with nickel,
said coating being carried out while maintaining the oxygen in said
pack at a partial pressure below which the oxidation of sulfur to
sulfur oxide compounds is substantially inhibited.
10. The method of claim 9, wherein the oxygen is maintained at the
desired partial pressure by mixing with said pack a small but
effective amount of an oxygen-scavenging metal whose free energy of
formation of the oxide is at least about 115,000 calories per gram
atom of oxygen at about 25.degree. C.
11. The method of claim 10, wherein the oxygen-scavenging metal is
titanium.
12. The method of claim 11, wherein the pack cementation bed has a
composition ranging from about 5 to 60% Ni, about 1/8 to 1% Ti,
about 0.002 to 0.1% and the balance essentially the inert
refractory material.
13. The method of claim 11, wherein the bed comprises approximately
40% nickel, approximately 0.2% Ti, approximately 0.02% S and the
balance essentially aluminum oxide.
14. The method of claim 11, wherein following the production of the
diffusion-bonded nickel coating, the substrate of the article is
cleaned, and the coated surface then aluminized, whereby a highly
impact resistant coating containing nickel aluminide is
produced.
15. The method of claim 14, wherein the nickel-coated article is
aluminized by embedding it in a cementation pack containing by
weight about 10 to 30% Cr, about 1 to 5% A1, a small but effective
amount of a halide energizer and the balance a particulate inert
refractory material, the article being then aluminized at a
temperature of about 1,750.degree. to 2,050.degree. F. for 1 to 30
hours.
16. An article of manufacture produced in accordance with the
method of claim 1.
Description
This invention relates to the pack-nickelizing of heat-resistant
metal substrates and, in particular, to a method of producing a hot
corrosion resistant metal coating in which the metal substrate is
first nickelized to form a diffusion-bonded nickel coating thereon
and thereafter aluminized in a separate coating step to provide an
improved protective coating containing substantial amounts of
nickel aluminide which coating exhibits markedly improved impact
ductility.
Metallurgical developments in recent years have indicated the
necessity of high-cobalt and/or high-nickel heat-resistant alloys
(sometimes now referred to as "super alloys") having desirable
physical properties for various high temperature uses, such as, for
example, the manufacture of rotor blades and stator vanes for
high-temperature gas turbines where operation without failure is
desired of the part, such as during prolonged exposure to
temperatures well above 1,500.degree. F., and even substantially
above the temperature range at which failure or diminution of the
strength characteristics may be expected of even high temperature
austenitic or nickel chromium steel.
The use of superalloys by themselves with nothing more have not
always provided the necessary resistance to hot corrosion damage at
such elevated temperatures. Thus, corrosion resistant coatings have
been resorted to as one means of further augmenting the resistance
of the substrate to high-temperature corrosion, particularly on
complex-shaped components used in contemporary jet engines where
handling and gauging damage have been known to cause premature
failure of protective coatings which tend to be brittle in nature.
With regard to cobalt-base superalloys, the most current coatings
used in such applications are cobalt aluminides containing
dispersions of MC, M.sub.6 C and M.sub.23 C.sub.6 carbides.
Coatings of this nature afford good oxidation resistance, but are
too brittle for production assembly lines.
An attempt was made to evolve a two-step process for the
independent deposition of nickel and aluminum on cobalt-base
superalloys by using a nickel-alumina pack (40percent by weight
nickel powder and 60percent by weight alumina) containing a halide
energizer, e.g., one-quarter percent by weight of ammonium
bifluoride. However, such packs were not successful to effect the
transfer of nickel in that the energizer vapors tended to attack
the component surface in preference to depositing nickel from the
pack.
A method has now been found for effecting the transfer of nickel by
pack cementation onto superalloy substrates, such as cobalt-base
and nickel-base alloys, while avoiding the formation of
chromium-containing embrittling phases at the interface. While the
invention is particularly applicable to cobalt-base superalloys, it
is also applicable to the coating of nickel-base alloys containing,
for example, 10percent to 30 percent by weight of chromium where
the deposit nickel dilutes the chromium at the interface to inhibit
the formation of the aforementioned chromium-containing embrittling
phases, such as the chromium carbides, nitrides and the like.
It is thus the object of the invention to provide a method whereby
a high-impact and hot corrosion resistant coating may be produced
on superalloys, such as cobalt-base and high-chromium-bearing
nickel-base alloys.
Another object is to provide a method of nickelizing the substrate
of cobalt-base and nickel-base superalloys preliminary to
aluminizing said alloys for the production of hot corrosion
resistant coatings based on nickel aluminide which exhibit markedly
improved impact ductility.
Still another object is to provide a method of nickelizing
chromium-containing superalloys whereby to avoid the formation of
chromium-containing embrittling phases in the subsequent production
of nickel aluminide coating by aluminizing the nickelized
superalloys.
A further object is to provide a superalloy substrate, e.g., a
cobalt-base superalloy, having a ductile impact and hot corrosion
resistant coating diffusion bonded thereto.
These and other objects will more clearly appear from the following
description and the appended claims.
Broadly stated, the invention resides in a method of producing an
impact resistant coating on a superalloy substrate by pack
cementation wherein a layer of diffusion-bonded sulfur-activatable
transfer metal e.g., nickel, is produced as a first step in the
ultimate formation of the impact resistant coating. The improvement
resides in providing an article of said superalloy having a solute
metal, e.g., chromium, whose free energy of formation of the
sulfide is higher than that of the transfer metal (e.g., higher
then nickel), embedding the article in a particulate cementation
pack consisting essentially of said sulfur-activatable transfer
metal mixed with an inert refractory material (e.g., alumina), the
bed containing a small but effective amount of sulfur for effecting
the transfer of said sulfur-activatable metal to the substrate of
said article at an elevated diffusion coating temperature, and then
heating said pack and the embedded article to an elevated diffusion
coating temperature, whereby to effect diffusion coating of that
article with the transfer metal, the coating being carried out
while maintaining the oxygen in the pack below the partial pressure
at which oxidation of sulfur to sulfur dioxide is inhibited.
In carrying out the pack cementation process, the oxygen is
maintained at the desired partial pressure by mixing with the pack
a small but effective amount of an oxygen-scavenging metal (e.g.,
titanium) whose free energy of formation of the oxide is at least
about 115,000 calories per gram atom of oxygen at about 25.degree.
C.
Where nickel is employed as the transfer metal, the particulate
nickelizing pack has a composition ranging by weight from about 5
to 60% nickel, about one-eighth to 1% titanium, about 0.002 to 0.1%
of sulfur, and the balance essentially an inert refractory material
e.g., such refractory oxides as alumina, magnesia, silica and the
like. A particular pack composition is one containing approximately
40 % nickel, approximately 0.2% titanium, approximately 0.02%
sulfur and the balance essentially aluminum oxide. Following the
production of the diffusion bonded nickel coating, the substrate of
the article is cleaned and the coated surface then aluminized,
whereby an impact resistant coating containing nickel aluminide of
improved ductility is produced.
As stated above, the method is applicable to both nickel-base and
cobalt-base superalloys. In the case of nickel-base alloys, a
typical alloy composition range is one containing by weight about
10 to 30% Cr, up to about 20% of a metal from the group consisting
of Mo and W. up to about 10% of a metal from the group consisting
of Cb and Ta, up to about 0.5% C, up to about 6.5 percent by weight
of a metal from the group consisting of Ti and A1, the total amount
of these metals not exceeding about 10%, up to about 20% Co, up to
about 2% Mn, up to about 2% Si, up to about 0.1% B, up to about 1%
Zr, and the balance at least about 45% nickel.
With regard to the cobalt-base alloys, a typical composition range
is one containing by weight about 10 to 30% Cr, up to about 15% Ni,
up to about 15% Fe, up to about 5% Cb, up to about 15% W. up to
about 5% Ti and/or Al, up to about 1% Zr, up to about 1.5% C, up to
about 1 or 2% of Si, up to about 2% Mn and the balance essentially
at least about 45% Co.
A well-known commercial composition is a cobalt-base alloy referred
to by the designation WI-52 containing by weight about 0.45% C,
about 0.25% Mn. about 0.25% Si, about 21% Cr, about 11% W. about 2%
Cb, about 2% Fe and the balance essentially cobalt.
The optimum processing cycle for nickelizing the aforementioned
WI-52 alloy involves the deposition of nickel at about
9,925.degree. F..+-.25.degree. F., (about 1,050.degree.
C..+-.14.degree. C.) by embedding an article of the alloy, e.g., an
airfoil section, in a particulate pack containing by weight about
40 percent - 200 mesh electrolytic nickel and 60 percent - 325 mesh
alumina, the mixture containing by weight about three-sixteenth
percent of titanium, with the sulfur level ranging from about 0.015
to 0.05 percent. The primary source of the sulfur is the nickel
powder. With the foregoing pack, the thickness of nickel coating
ranges up to about 0.002 inch.
In determining the positive effect of sulfur, or sulfur-containing
compounds, as a metal transfer agent, the addition of small but
effective amount of flowers of sulfur and such sulfur compounds as
NiS, Cr.sub.2 S.sub.3 and (NH.sub.4 ).sub.x S was noted to increase
the quantity and depth of nickel of transfer. However, the presence
of too much sulfur may result in extensive attack of the grain
boundary carbide phases and the deposition of sulfur-compounds in
situ. Thus, the term "small but effective amount" is meant to cover
that amount of sulfur conducive to forming the desired coating of
nickel while avoiding the deposition of sulfur-rich compounds,
except for the formation of chromium sulfide at the surface of the
substrate which is easily removed by glass head honing. For
advantageous results, the amount of sulfur in the pack, whether
deliberately added, or whether present in the pack materials
employed, e.g., nickel powder and/or the alumina, may range from
about 0.002 to 0.1 percent by weight.
The sulfur is consumed in the formation of scale and reaction with
titanium (scavenger) and oxygen. Thus, the reaction of sulfur with
chromium in the alloy substrate may result in several kinds of
chromium sulfide which form on the surface of the article following
deposition of the nickel. The reaction with titanium in the pack
may result in the formation of some titanium sulfide. Residual
oxygen in the pack can react with the sulfur dioxide and with the
titanium to form titanium dioxide. The preference and degree to
which these reactions occur is dependent upon the relative
concentration of the elements in the pack.
In nickelizing the cobalt alloy identified hereinbefore by the
designation WI-52, the sulfur content of the pack at the low-range
results in a nickel zone in the substrate of about 0.5 mils thick
(0.0005 of an inch), with about 2 to 10% nickel diffused into the
surface. Generally, the lower the sulfur level in the pack over the
small but effective range, the less is the nickel transfer and the
smaller the depth of diffusion. Usually, a nickel zone is obtained
on the substrate of the alloy containing up to about 20 percent by
weight of nickel as determined by microprobe analysis.
In the normal process cycle, the parts as removed from the
nickelizing pack are covered with light scale which is removed by
low-pressure glass bead honing. The scale is composed of distinct
phases of chromium sulfide with entrapped powder from the pack, the
chromium sulfide ranging in composition from Cr.sub.2 S.sub.3 to
Cr.sub.5 S.sub.6. The scale thickness usually averages 0.3 mils,
the thickness increasing with sulfur additions and increased nickel
transfer.
It is important that the oxygen partial pressure in the pack be
maintained below a level at which oxidation of sulfur is
substantially inhibited. A titanium level of about three-sixteenth
percent has been determined to be particularly advantageous in
providing improved nickel transfer while minimizing oxidation
damage during the nickelizing process cycle. Alternatively, other
oxygen scavengers may be employed so long as the free energy of
formation of the oxide is at least about 115,000 calories per gram
atom of oxygen. As stated above, unless precautions are taken to
maintain the oxygen partial pressure in the pack to desirably low
levels, the transfer of nickel from the pack and onto the alloy
substrate is adversely affected. This can occur if too little
titanium is in the pack to avoid the formation of sulfur dioxide
and even chromium oxide on the alloy substrate. For example, no
titanium in the pack results in no nickel transfer and severe
oxidation of the substrate being coated. Another method of
maintaining the oxygen partial pressure to the desirable low level
is to sweep out the oxygen occluded in the pack by means of a
substantially oxygen-free inert gas, such as argon. Generally
speaking, where titanium is employed as the oxygen scavenger, the
amount in the pack may range from about 1/8 to about 1 percent. A
typical pack for processing the alloy WI-52 is one comprising about
40% nickel powder, the pack mixture containing about
three-sixteenth percent of titanium and about 0.015 to 0.05% of
sulfur with the balance essentially inert refractory oxide, e.g.,
alumina. A particularly advantageous range of titanium is about
three-sixteenth to about one-half percent.
As illustrative of the various superalloys that can be coated in
accordance with the invention, the following are given in Table 1
by way of example: ##SPC1##
The SM-302 and AIResist 215 alloys nickelized in a pack composition
containing by weight about 40% electrolytic nickel powder (-200
mesh), about three-sixteenth percent titanium about 0.03 sulfur and
the balance essentially alumina (-325 mesh) at a temperature of
about 1,925.degree. F..+-.25.degree. F. for 30 hours resulting in a
deposited nickel zone ranging in nickel content from about 20 to 22
percent by weight according to microprobe analysis.
Following the nickelizing of the alloys in Table 1, nickelized
alloys are then aluminized in a prereacted pack containing by
weight 20% Cr, 3% Al, 1/4% NH.sub.4 FHF and the balance essentially
alumina (-325 mesh) to yield a corrosion resistant coating of
substantially improved impact ductility. In the case of the
cobalt-base alloys, the 0.002 to 0.0025 inch coating produced
comprises nickel-cobalt aluminides containing chromium in solid
solution.
In the case of Hastelloy X (comprising 0.1% C, 22% Cr, 1.5% Co, 9%
Mo, 0.6% W. 18.5% Fe, 0.5% Mn, 0.5% Si and the balance essentially
nickel), the substrate is similarly nickelized in a pack containing
by weight 20% electrolytic nickel powder (-200 mesh), about 0.3%
titanium, about 0.02% of sulfur and the balance essentially -325
mesh alumina at a temperature of 1,925.degree. F..+-.25.degree. F.,
for about 10 hours, following which the surface of the alloy
substrate is cleaned by glass bean honing and then aluminized in
the aforementioned prereacted pack at 1,900.degree.F.+-.25.degree.
F. for 20 to 30 hours to yield a corrosion resistant nickel
amuminide coating (0.0025 to 0.003 inch thick) which is very highly
impact and spall resistant.
The treatment in the nickel pack causes chromium depletion in the
substrate which allows for the formation of a ductile aluminide
coating during the second diffusion bonding. Apparently, the
improved ductility of the coating compared to the more brittle
coatings currently used on such alloys is attributed to less
chromium-rich phases within the coating and the absence of porosity
at the coating substrate interface.
In the case of the alloy designated WI-52, the improved impact
resistant coating provides a resistance to at least about 17 inch
lbs. impact as compared to one-fourth inch lb. impact for the
conventionally produced single step aluminide coating.
A simple test devised to simulate the stress and temperature
environment of actual turbine hardware during engine service
comprises a simple bending load test in which the load is applied
to a coated test bar which is subjected to an end to end
temperature gradient developed by a concentrated oxyacetylene flame
which is applied to the center of the test bar and the heat allowed
to dissipate to the opposite ends of the bar. Each testpiece is
cycled from maximum temperature (e.g., 2,000.degree. F.) to black
heat during a 10 minute period. As the specimen is being cooled,
the simple beam load is lifted and dropped three times to reproduce
foreign object impact damage during service. Results have shown
that the coating produced in accordance with the invention exhibits
at least a 3 to 1 improvement over the conventional aluminized
coating mentioned hereinabove. With regard to the conventional
single step aluminide coating, chipping and spalling of the coating
occurred after 45 cycles, while in the improved coating produced in
accordance with the invention, the coating was still intact after
135 cycles.
As stated hereinbefore, the nickelizing pack may range by weight
from about 5 to 60 % nickel powder, about 1/8 to 1% titanium, about
0.002 to 0.1 % sulfur and the balance an inert refractory material,
such as particulate refractory oxides, e.g., Al.sub.2 O.sub.3, MgO,
SiO.sub.2 and the like. Examples of other oxygen scavengers are
thorium, cerium, yttrium and other rare earth metals. The
nickelizing temperature may range from about 1,500.degree. to
2,000.degree. F. for about 5 to 40 hours.
A cementation pack which may be employed in the aluminizing step
comprises about 10 to 30 percent of a buffering metal (e.g.,
chromium), about 1 to 5% of aluminum, a small but effective amount
of a halide energizer, e.g., one-quarter percent of NH.sub.4 FHF
(such as 1/8 to 1 percent energizer) and the balance a particulate
inert refractory material as mentioned hereinabove. The buffering
metal aids in controlling the transfer and deposition of the
aluminum. Examples of other buffering metals are nickel, iron and
cobalt. Generally speaking, the pack is mixed and prereacted at an
elevated temperatures of, for example, 1,750.degree. to
2,050.degree. F. for about 1 to 20 hours prior to use for coating
and the nickelized article then aluminized at a temperature of
about 1,750.degree. to 2,050.degree. F. for about 1 to 30
hours.
As illustrative of a preferred embodiment of the invention, the
following example is given:
EXAMPLE
An airfoil section made of an alloy (WI-52) comprising about 0.45%
C, about 0.25% Mn, 0.25% Si, about 21% Cr, about 11% W. about 2%
Cb, about 2% Fe and the balance essentially cobalt is embedded in a
nickelizing pack containing by weight about 40% electrolytic nickel
powder (-200 mesh), about 0.2% titanium powder, about 0.02% sulfur
and the balance essentially alumina (-325 mesh) in a retort. The
retort is sealed with low-melting silicate glass composition and
the retort then heated in a muffle furnace to a temperature of
about 1,925.degree. F..+-.25.degree. F. and held at temperature for
about 30 hours. The retort is thereafter cooled to room temperature
and the airfoil section cleaned by glass bead honing at low
pressure to remove chromium sulfide scale at the surface. A
diffused layer of nickel is obtained having an enriched zone of
about 0.002 inch thick containing about 20% nickel.
Following the cleaning of the airfoil element, the element is
similarly embedded in an aluminizing pack containing by weight 20
percent chromium (-100 mesh powder) as a buffering agent 3 percent
aluminum powder (-325 mesh), about one-quarter NH.sub.4 FHF and the
balance essentially -325 mesh alumina. The aluminizing was carried
out for 20 hours in a sealed retort to produce an extremely ductile
mixed nickel-cobalt aluminide coating containing chromium in solid
solution.
Although the present invention has been described in conjunction
with preferred embodiments, it is to be understood that
modifications and variations may be resorted to without departing
from the spirit and scope of the invention as those skilled in the
art will readily understand. Such modifications and variations are
considered to be within the purview and scope of the invention and
the appended claims.
* * * * *