U.S. patent number 3,754,903 [Application Number 05/072,512] was granted by the patent office on 1973-08-28 for high-temperature oxidation-resistant coating alloy.
This patent grant is currently assigned to United Aircraft Corporation. Invention is credited to Donald H. Boone, George W. Goward, Frederick S. Pettit.
United States Patent |
3,754,903 |
Goward , et al. |
August 28, 1973 |
HIGH-TEMPERATURE OXIDATION-RESISTANT COATING ALLOY
Abstract
A coating alloy for the gas turbine engine super-alloys is
described which consists primarily of nickel, aluminum and a
reactive metal such as yttrium, particularly at the composition, by
weight, 14-30 percent aluminum, 0.01-0.5 percent reactive metal
balance nickel. A preferred embodiment also includes 15-45 weight
percent chromium.
Inventors: |
Goward; George W. (North Haven,
CT), Boone; Donald H. (North Haven, CT), Pettit;
Frederick S. (North Haven, CT) |
Assignee: |
United Aircraft Corporation
(East Hartford, CT)
|
Family
ID: |
22108077 |
Appl.
No.: |
05/072,512 |
Filed: |
September 15, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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734740 |
Jun 5, 1968 |
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Current U.S.
Class: |
420/443; 428/667;
428/938; 420/452; 428/680 |
Current CPC
Class: |
C23C
4/073 (20160101); C23C 14/16 (20130101); C22C
19/007 (20130101); C22C 19/052 (20130101); Y10T
428/12854 (20150115); Y10T 428/12944 (20150115); Y10S
428/938 (20130101) |
Current International
Class: |
C23C
4/08 (20060101); C22C 19/00 (20060101); C22C
19/05 (20060101); C23C 14/16 (20060101); C22c
019/08 () |
Field of
Search: |
;75/138,171 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Bizot; Hyland
Parent Case Text
This is a division of Application Ser. No. 734,740, filed June 5,
1968.
Claims
We claim:
1. An oxidation-erosion resistant coating alloy which consists
essentially of, by weight, 14-25 percent aluminum, 15-45 percent
chromium, 0.01-0.5 percent yttrium, up to 10 percent of an alloying
ingredient selected from the group consisting of cobalt, iron and
the refractory metals, balance essentially nickel.
2. An oxidation-erosion resistant coating alloy which consists
essentially of, by weight, 15-20 percent aluminum, 20-35 percent
chromium, 0.05-0.3 percent yttrium, balance essentially nickel.
Description
BACKGROUND OF THE INVENTION
the present invention is directed to oxidation-resistant alloys,
particularly alloy compositions having application as coatings on
the superalloys utilized in the gas turbine engine industry.
A nickel-base superalloy is typically a nickel-chromium solid
solution, hardened by the additions of aluminum and titanium to
precipitate the intermetallic compound or gamma prime phase
Ni.sub.3 (Al,Ti). The contemporary superalloys also usually contain
cobalt to raise the solvus temperature of the gamma prime phase,
refractory metals such as tungsten or tantalum for solution
strengthening, and carbon, boron and zirconium to promote ductility
and fabricability.
A limiting factor in the application of the current superalloys to
jet engine hardware is their susceptibility to oxidation at very
high temperatures with a consequent progressive loss of substrate
material. For this reason, the nickel-base superalloys are
generally coated with a composition different from and more
oxidation-resistant than the structural alloy. In most instances
the requisite layer of icnreased oxidation resistance is provided
by reacting aluminum with the surface of the alloy to form an
aluminide which in turn oxidizes to provide a surface oxide layer
through which the transport rates of the reacting species are low.
Typical of the processes of this type is that described in the U.S.
Pat. to Joseph No. 3,102,044.
Although the aluminide coatings as currently provided significantly
enhance the lifetimes of superalloy hardware, the theoretically
expected behavior of the nickel aluminide intermetallic compound is
not in fact realized in dynamic oxidizing environments. This is the
result of thermal shock spalling. In the dynamic environment of a
gas turbine engine, for example, temperature fluctuations caused by
the mixing of the hot combustion gases with cooler secondary air or
those associated with varying power levels give rise to
thermally-induced strains at the metal-oxide interface which are
sufficiently large to eventually spall the oxide layer. This layer
then reforms by the consumption of more aluminum from the
intermetallic coating phase. In general, this is a rapidly
recurring process and the aluminum is more rapidly depleted from
the coating phase than would be the case in a truly isothermal
environment wherein no thermal shock spalling would occur.
In a copending application of the same assignee, Ser. No. 734,706,
filed June 5, 1968, entitled NICKEL BASE SUPERALLOY RESISTANT TO
OXIDATION-EROSION, by D. H. Boone et al., there is described a
nickel-base superalloy system having an oxidation-erosion
resistance significantly superior to the conventional super-alloys.
While the utilization of this alloy obviates the need for coatings
for satisfactory oxidation resistance, such coatings may be
advantageous in some circumstances, perhaps for economic reasons.
In such instances the coating herein described will be seen to have
particularly advantageous properties.
SUMMARY OF THE INVENTION
This invention relates to coating alloys of the type generaly
identified as the nickel-aluminum intermetallics. It contemplates a
basic nickel-aluminum alloy of relatively specific chemistry
containing as an essential ingredient one or more of the reactive
metals.
It has been found that two factors contribute to the improved
oxidation-erosion resistance of the alloys of the present
invention. First, the chemistry of the alloy is formulated such
that, upon oxidation, essentially a single oxide, specifically
alumina, is formed rather than other oxides or mixtures of oxides.
This is done through maintenance of a particular aluminum level in
the alloy. Secondly, the alloy is provided with at least a minor
amount of retained reactive metal such as yttrium, scandium,
thorium, or lanthanum and the other rare earth elements.
In terms of their composition, the alloys of the present invention
consist of, by weight, 14-30 percent aluminum, 0.01-1 percent
reactive metal, balance nickel together with, on an optional basis,
one or more of alloying ingredients compatible with the basic alloy
chemistry. Specifically, the compatability of the optional
ingredients must be such that they do not interfere with the basic
oxidation mechanism of the alloy.
A preferred embodiment of the invention comprises an alloy
consisting essentially of, by weight, about 14-25 percent aluminum,
0.01-0.5 percent reactive metal, 15-45 percent chromium, balance
nickel. This alloy possesses both oxidation-erosion and sulfidation
resistance.
The most preferred coating alloy consists essentially of, by
weight, 15-20 percent aluminum, 20-35 percent chromium, 0.05-0.3
percent reactive metal, balance nickel.
BRIEF DESCRIPTION OF THE DRAWING
The drawing is a graph depicting the oxidation-erosion behavior of
an alloy of the present invention as compared to certain
representative contemporary materials.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Although not so confined, the alloys of the present invnetion find
particular utility in imparting long-term, oxidation-erosion
resistance to the gas turbine superalloys, when utilized as
coatings thereon, in the dynamic oxidizing environments of gas
turbine engines. Representative of the centemporary superalloys
requiring such oxidation protection is the alloy identified in the
industry as B-1900, the nominal composition of which, by weight, is
as follows: 8 percent Cr, 10 percent Co, 1 percent Ti, 6 percent
Al, 6 percent Mo, 4.3 percent Ta, 0.11 percent C, 0.015 percent B,
0.07 percent Zr, balance Ni.
As previously mentioned, the prior art coatings are, in general,
most commonly provided by reacting aluminum with the deoxidized
surface of the article to be protected and an aluminide layer is
formed with consumption of the substrate components. This aluminide
layer in turn oxidizes to form the desired inert barrier oxide.
However, because of the complex nature of most of the contemporary
alloys, and because the coating composition thereon is derived in
part from the components of the substrate alloys, it is difficult
to control the coating composition so as to cause the formation of
a suitable barrier oxide resistant to thermal shock spalling. This
is particularly true in the case of the contemporary coatings after
exposure to an oxidizing environment for an extended period of
time, because in the reformation of the oxide barrier at this point
the oxides reform as mixtures of many oxides due to the
preferential depletion of certain species with time. Such mixtures
are more prone to thermal shock spalling than the single oxide.
The alloys of the present invention are in themselves oxidation
resistant and do not depend for their protective effect upon a
reaction with the substrate material. Their particular formulation
is such that the most desirable barrier oxide is preferentially
formed in a high temperature oxidizing environment and this oxice
is significantly more resistant to thermal shock spalling than that
formed on competitive coatings.
The desired results in this case are achieved with a basic alloy
containing, by weight, 14-30 percent aluminum, 0.01-1 percent
reactive metal, balance nickel. Of course, whatever
oxidation-erosion does occur with this coating, or with other
coatings for that matter, results in the loss of aluminum from the
system. A relatively high aluminum content is, accordingly,
preferred from a durability standpoint. In addition, below about 14
percent, or possibly in some instances as low as about 12 weight
percent aluminum, complete surface coverage by the desired
protective oxide is not formed. The upper limit of the aluminum
content, on the other hand, is established primarily by mechanical
considerations. Aluminum contents in excess of about 31.5 weight
percent result in the development of a brittle hyperstoichiometric
beta phase of the aluminide which, while satisfactory in terms of
its oxidation resistance, is in terms of its suitability to the
dynamic conditions associated with jet engine operation generally
unsatisfactory because of its poor mechanical properties.
Those materials which promote adherence of the oxide to the
underlying substrate will include those having an affinity for
oxygen approximating or exceeding that of aluminum. As used herein,
however, the term "reactive metal" has reference to the elements
yttrium, scandium, thorium, and lanthanum and the other rare
earths, including mixtures of the same.
In those environments where not only oxidation but sulfidation may
also be a problem, as is the case with many if not most gas turbine
engine systems, 15-45 weight percent chromium is advantageously
included in the coating composition. With the chromium addition,
the aluminum content of the alloy is preferably reduced and limited
to a maximum of about 25 weight percent to forestall the formation
of a brittle phase or phases as previously mentioned.
Experimentation has also revealed that, as a general rule, the
higher chromium contents are to be preferred, about 30 percent
chromium representing about the optimum amount from a sulfidation
standpoint.
As the best balance between chemical and physical properties, the
most preferred alloy composition corresponds to, by weight, 15-20
percent aluminum, 20-35 percent chromium, 0.05-0.3 percent reactive
metal, balance nickel.
Those skilled in the art will recognize that certain other elements
are known to be compatible with the basic chemistry of the present
alloys. Accordingly, other elements such as cobalt, iron or
tantalum may be advantageously added to the alloy as required in
certain applications for modification of the mechanical,
diffusional or hot corrosion characteristics of the coatings.
The alloys are relatively easily prepared by the conventional arc
melt-drop cast technique. Among the compositions so prepared and
tested were the following, by weight:
Ni -- 16% Al -- .5%Y
Ni -- 25% Al -- .5% Y
Ni -- 30% Al -- .5% Y
Ni -- 16% Al -- .1% Sc
Ni -- 30% Al -- .25% Sc
Ni -- 12% Al --.85% Y
Ni -- 12% Al -- .6% Nd
Ni -- 20% Cr -- 14.5% Al -- .5% Y
Ni -- 30% Cr -- 15% Al -- .1% Sc
Ni -- 15% Cr -- 15% Al -- .1% Sc
Ni -- 15% Cr -- 12% Al -- 4% Ta -- .25% Sc
With respect to the processes whereby the alloy is applied as a
coating to the surface to be protected, the necessary presence in
the alloy of the reactive metals precludes synthesis of these
alloys in coating form by the widely used slurry or simple pack
cementation techniques. It appears, however, that various of the
other methods discussed in the literature including vapor
deposition, plasma spraying, mechanical bonding, electrolysis,
electrophoresis, gaseous ion plating and sputtering may be adapted
to applying the specific compositions herein discussed. Several of
these techniques have been utilized in connection with this
invention as discussed in the following examples:
Example 1
A sputtering target of, by weight, Ni-26 percent Al-0.12 percent Y
was prepared by a standard arc melting process. A 2.5 mil coating
of this composition was deposited on a specimen of B-1900 alloy by
a sputtering process. Basically this method consists of bombarding
the target of correct coating composition with high energy argon
ions which causes sublimation of the target material. The sublimed
atoms are then condensed on the substrate alloy to form a coating
of essentially the same composition as the original target
material. The whole process is carried out in a vacuum of a few
microns of argon.
The coated specimen of this example was tested in a hot, high
velocity gas stream generated by the combustion of propane in air.
The coating protected the specimen from oxidation damage for 115
hours at 2,000.degree. F and for a subsequent period of 37 hours at
2,100.degree. F at which time the test was terminated to permit
metallographic examination of the specimen.
Example 2
A sputtering target of, by weight; Ni-30 percent Cr -- 12 percent
Al -- 0.5 percent Sc was prepared as above. A one mil coating of
this composition was deposited on a B-1900 specimen by the
sputtering technique described above.
Testing of this specimen was conducted in a hot high velocity
propane exhaust stream contaminated with 0.4 percent sulfur
(sulfur/fuel ratio) and 3.5 ppm sea salt (salt/air ratio) to
simulated gas turbine hot corrosion (sulfidation) conditions. At a
specimen temperature of 1,650.degree. F, the test article survived
for a total of 330 hours. Uncoated B-1900 is catastrophically
attacked under these test conditions.
Example 3
An ingot of the composition, by weight, Ni -- 28 percent Cr -- 14
percent Al -- 0.4 percent Y was prepared by a standard melting
method. A B-1900 erosion bar was coated to a thickness of 4.5 mils
of this composition by electron beam evaporation. Subjected to
dynamic oxidation-erosion in JP5R fuel exhaust at 2,000.degree. F,
the erosion bar was protected from oxidation for 208 hours.
It has thus been clearly established that the alloys of the present
invention are effective in imparting long-term oxidation-erosion
protection to the superalloys. While the invention has been
described in connection with certain preferred embodiments and
examples, these will be understood to be illsutrative only.
Numerous improvements to and variations of the present invention,
some of which are discussed herein, will be evident to those
skilled in the art from the teachings herein and will, in the true
spirit of the invention, be embraced within the scope of the
appended claims.
* * * * *