U.S. patent number 3,898,052 [Application Number 05/516,114] was granted by the patent office on 1975-08-05 for corrosion resistant coating system for ferrous metal articles having brazed joints.
This patent grant is currently assigned to Chromalloy American Corporation. Invention is credited to Hossein Borougerdi, Michael F. Dean, John A. Puchot.
United States Patent |
3,898,052 |
Dean , et al. |
August 5, 1975 |
Corrosion resistant coating system for ferrous metal articles
having brazed joints
Abstract
Ferrous metal articles, such as stainless steel articles,
characterized by at least one brazed joint, in which the braze is a
non-ferrous alloy are aluminized by first selectively coating the
braze alloy with an aluminide-forming metal, such as nickel, and
then thermally diffusing aluminum over the entire surface of the
article including the selectively coated braze, such that a
sacrificial corrosion resistant coating is produced wherein the
aluminum coating on the ferrous metal surface is characterized by
the presence of iron aluminide, and wherein the aluminum coating on
the metal-coated braze is characterized by the presence of metal
aluminide, such as nickel aluminide. The aluminide coatings are
further enhanced by the application of a non-metallic coating,
e.g., a conversion coating.
Inventors: |
Dean; Michael F. (San Antonio,
TX), Borougerdi; Hossein (San Antonio, TX), Puchot; John
A. (San Antonio, TX) |
Assignee: |
Chromalloy American Corporation
(New York, NY)
|
Family
ID: |
26998050 |
Appl.
No.: |
05/516,114 |
Filed: |
October 18, 1974 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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353677 |
Apr 23, 1973 |
|
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Current U.S.
Class: |
428/632; 428/672;
428/673; 428/684; 428/668; 428/674; 428/941 |
Current CPC
Class: |
C23C
10/50 (20130101); B23K 35/30 (20130101); C23F
13/02 (20130101); C23C 10/02 (20130101); C23C
18/36 (20130101); C23C 18/1841 (20130101); F01D
5/288 (20130101); C23C 10/60 (20130101); Y10T
428/12611 (20150115); Y10T 428/12896 (20150115); Y10T
428/12972 (20150115); F02B 2075/027 (20130101); Y02T
50/60 (20130101); Y10T 428/12903 (20150115); Y10T
428/12861 (20150115); Y10S 428/941 (20130101); Y10T
428/12889 (20150115) |
Current International
Class: |
C23C
10/50 (20060101); C23C 10/02 (20060101); C23C
10/00 (20060101); C23F 13/02 (20060101); C23C
10/60 (20060101); C23C 18/31 (20060101); C23C
18/36 (20060101); C23C 18/18 (20060101); F01D
5/28 (20060101); B23K 35/30 (20060101); C23F
13/00 (20060101); F02B 75/02 (20060101); B32b
015/18 () |
Field of
Search: |
;117/71M,135,127
;29/195M,195Y,195T,194,196.2,196.3,199 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3597172 |
August 1971 |
Bunghardt et al. |
3859061 |
January 1975 |
Speirs et al. |
|
Primary Examiner: Rutledge; L. Dewayne
Assistant Examiner: Steiner; Arthur J.
Attorney, Agent or Firm: Hopgood, Calimafde, Kalil
Parent Case Text
This application is a continuation-in-part of application Ser. No.
353,677, filed Apr. 23, 1973.
Claims
What is claimed is:
1. A stainless steel article having at least one brazed joint,
the braze of said joint being formed of a non-ferrous brazing alloy
of melting point ranging from about 1,125.degree. to
1,925.degree.F,
said braze being characterized by the presence of an
aluminide-forming metal selected from the group consisting of
nickel, cobalt, iron, titanium, chromium, manganese, molybdenum and
vanadium at the surface thereof,
the stainless steel article having a thermally diffused aluminum
coating on substantially the entire surface of said article,
the coating on the stainless steel surface outside the braze being
characterized by the presence of iron aluminide,
the aluminum coating on the braze being characterized by the
presence of an aluminide of said metal group,
the thermally diffused aluminum coating also having bonded thereto
a cured non-metallic barrier layer formed from a silicate selected
from the group consisting of sodium silicate, potassium silicate,
lithium silicate and ethyl silicate.
2. A stainless steel article having at least one brazed joint,
the braze of said joint being formed of a non-ferrous brazing alloy
of melting point ranging from about 1,125.degree. to
1,925.degree.F,
said braze being characterized by the presence of nickel at the
surface thereof,
the stainless steel article having a thermally diffused aluminum
coating on substantially the entire surface of said article.
the coating on the stainless steel surface outside the braze being
characterized by the presence of iron aluminide,
the aluminum coating on the braze being characterized by the
presence of nickel aluminide,
the thermally diffused aluminum coating also having bonded thereto
a cured non-metallic barrier layer formed from a silicate selected
from the group consisting of sodium silicate, potassium silicate,
lithium silicate and ethyl silicate.
3. The stainless steel article of claim 2, wherein the non-ferrous
brazing alloy has a melting point of about 1,175.degree. to
1,850.degree.F and wherein said brazing alloy is either a
copper-base, silver-base or gold-base alloy.
4. The staniless steel article of claim 2, wherein said
non-metallic barrier layer also includes a chromate and a phosphate
of at least one metal.
5. The stainless steel article of claim 4, wherein said chromates
and phosphates of said at least one metal are chromates and
phosphates of aluminum and magnesium.
6. The article of manufacture of claim 5, wherein the silicate of
the non-metallic barrier layer is derived from sodium silicate.
7. The article of manufacture of claim 5, wherein the silicate of
the non-metallic barrier layer is derived from potassium
silicate.
8. A stainless steel article having at least one brazed joint,
the braze of said joint being formed of a non-ferrous brazing alloy
of melting point ranging from about 1,125.degree. to
1,925.degree.F,
said braze being characterized by the presence of an
aluminide-forming metal selected from the group consisting of
nickel, cobalt, iron, titanium, chromium, manganese, molybdenum and
vanadium at the surface thereof,
the stainless steel article having a thermally diffused aluminum
coating on the whole surface of said article,
the coating on the stainless steel surface outside the braze area
being characterized by the presence of iron aluminide,
the aluminum coating on the braze being characterized by the
presence of an aluminide of said metal group.
9. A stainless steel article having at least one brazed joint,
the braze of said joint being formed of a non-ferrous brazing alloy
of melting point ranging from about 1,125.degree. to 1,925.degree.
F,
said braze being characterized by the presence of nickel at the
surface thereof,
the stainless steel article having a thermally diffused aluminum
coating on the whole surface of said article,
the coating on the stainless steel surface outside the braze area
being characterized by the presence of iron aluminide,
the aluminum coating on the braze being characterized by the
presence of nickel aluminide.
10. The stainless steel article of claim 7, wherein the non-ferrous
brazing alloy has a melting point of about 1,175.degree. to
1,850.degree.F and wherein said brazing alloy is either a
copper-base, silver-base or gold-base alloy.
Description
This invention relates to the protection of ferrous metal articles
corrosion in highly saline and/or marine or other corrosive
environments by employing thermally diffused aluminum as the main
sacrificial coating, the invention being particularly applicable to
ferrous metal articles, such as stainless steel articles,
characterized by at least one brazed joint, wherein the braze is a
non-ferrous alloy. The invention also relates to the production of
aluminized coatings on ferrous metal articles comprising brazed
joints and also having a barrier-type non-metallic overcoat.
FIELD OF THE INVENTION
Jet and gas turbine engine compressor components are subject to
corrosion in highly saline environments at the air intake end of
the engine and also to the direct impact of abrasive particulate
matter, such as coral dust. Additionally, the compressor blades are
subjected to tremendous mechanical stresses from centrifugal
forces, thermal shock, vibration and other sources of stresses.
Thus, corrosion can accelerate catastrophic failure, since pits and
other corrosion defects can act as stress raisers.
High strength ferrous alloys are employed in the construction of
compressor blades and other aircraft engine components such as
vane/shrouds (e.g., Society of Automotive Engineers alloy
designation AMS 5508, AMS 5616, AMS 6304 and others) but, because
of their low resistance to saline corrosion, they are generally
provided with a protective surface treatment. One in particular is
the provision of an aluminum-base diffusion coating on the ferrous
substrate by pack-aluminizing at coating temperatures ranging up to
1,000.degree.F and preferably not higher so as to avoid undesired
crystallographic or metallurgical changes in the substrate during
coating which might have an adverse or undesired effect on the
mechanical property of the parts. Such coatings have provided
advantageous oxidation and erosion resistance and have minimized
the production of pulverous corrosion by-products and have been
very useful in extending the operating life of jet engine
components.
However, where the jet and gas turbine engine components are
comprised of at least one brazed joint, such as vane/shroud
assemblies in which the braze is a non-ferrous alloy based on a
metal selected from the group consisting of copper, silver and
gold, e.g., copper-, silver- and/or gold-base brazing alloys,
certain problems arise in the production of a uniform aluminized
coating having requisite physical characteristics. The braze, being
markedly different than the ferrous metal surface, reacts
differently during the diffusion of aluminum therein. The extent of
diffusion of aluminum in different materials is governed mainly by
the aluminide phases that are formed which act as diffusion
barriers. Generally speaking, the lower the melting point of a
particular braze alloy, the deeper is the diffusion of aluminum
into it.
Thus, in the case of aluminum diffusion in a brazed component in
which stainless steel elements are brazed together to form the
joints, the aluminum case depth on the stainless steel element
might be 0.0005 inch, whereas the aluminum may penetrate as much as
0.007 inch deep into the brazed portions of the joints for a braze
alloy comprising by weight 50% Ag, 18% Cd, 16% Zn and 16% Cu; or as
much as 0.002 inch for a braze composition comprising by weight 54%
Ag, 40% Cu and 6% Zn.
Mechanical tests have indicated that the uncontrolled diffusion of
aluminum into the braze alloy tends to degrade the brazed joint as
evidence by fatigue test data.
Thus, it would be desirable to provide a method of controlling the
diffusion at the brazed joint commensurate with the diffusion at
the unbrazed portion of the component such as to insure uniform
properties over the whole surface of the component.
OBJECTS OF THE INVENTION
It is thus the object of the invention to provide a sacrificial
coating of aluminum on ferrous metal parts characterized by the
presence of at least one brazed joint comprising a non-ferrous
brazing alloy and wherein the properties of the coating are
substantially uniform at both the unbrazed areas and the brazed
joint.
Another object of the invention is to provide a method of
aluminizing a ferrous metal part having at least one brazed joint,
wherein the braze at the joint is selectively coated with a layer
of aluminide-forming metal, e.g., nickel, prior to aluminzing of
the whole part such that the fatigue properties at the joint are
maintained at acceptable levels or are enhanced.
A further object is to provide, as an article of manufacture, an
aluminized ferrous metal part, such as a stainless steel aircraft
part, characterized by at least one brazed joint of non-ferrous
metal or alloy, the braze having been first provided with a layer
of an aluminide-forming metal, such as nickel, such that the
aluminum coating in the unbrazed area at the steel substrate is
characterized by the presence of iron aluminide and in the brazed
areas by the presence of a metal aluminide.
A still further object is to provide a method of preparing a
ferrous metal part having at least one brazed joint for aluminizing
wherein the brazed joint is selectively plated with a coating of
nickel while inhibiting nickel from plating out in the unbrazed
areas.
These and other objects will more clearly appear from the following
disclosure and the accompanying drawings.
DRAWINGS
FIG. 1 represents a vane/shroud assembly of stainless steel in
which the vanes are brazed across the annular space between inner
and outer rings making up the shroud;
FIG. 2 is a close-up of a fragment of the shroud showing the
plurality of brazed joints making up the vane/shroud assembly;
and
FIG. 3 is a representation of a micrograph of a brazed joint at 100
times magnification.
STATEMENT OF THE INVENTION
One aspect of the invention resides in a method of aluminizing a
brazed ferrous metal article, such as an aircraft engine component
comprised of at least one brazed joint. The brazing material in the
joint is made of a non-ferrous brazing alloy having a melting point
ranging from about 1,125.degree.F (607.degree.C) to 1,925.degree.F
(1,052.degree.C), such as an alloy based on at least one metal
selected from the group consisting of copper, silver and gold.
Because the aluminum tends to diffuse more deeply into the
non-ferrous brazing alloy than in the steel substrate, the method
resides in selectively coating the brazed area with a barrier metal
selected from the group consisting of nickel, cobalt, iron,
titanium, chromium, manganese, molybdenum and vanadium and then
thermally diffusing the aluminum, preferably by pack cementation,
into the entire surface of the ferrous component, including the
selectively coated brazed area and thereby produce a substantially
uniform coating of aluminum, wherein the thermally diffused
aluminum coating on the ferrous metal surface outside the brazed
area is characterized by the presence of iron aluminide and wherein
the thermally diffused aluminum coating on the barrier metal coated
braze is characterized by the presence of metal aluminide, e.g.,
nickel aluminide. Fatigue tests on cantilevered specimens have
indicated that the fatigue properties of aluminized nickel-coated
brazed specimens are comparable to uncoated specimens and superior
to aluminized brazed specimens without the nickel protective
layer.
The foregoing method is also applicable to the coating of ferrous
metal articles which uses a protective duplex coating system, that
is, a system in which following the production of a thermally
aluminized coating on the ferrous metal substrate, a non-metallic
silicate overcoat is applied to the aluminum coating which is
highly adherent. With respect to the non-metallic overcoat,
reference is made to copending application Ser. No. 143,842, filed
May 17, 1971, now U.S. Pat. No. 3,729,295. The disclosure of said
patent relating to the production of such non-metallic overcoats on
aluminized ferrous metal surfaces is incorporated herein by
reference.
As stated hereinbefore, the non-ferrous brazing alloys which
present the problem of uncontrolled diffusion of aluminum therein
preferably include those which are based on one or more metals
selected from the group consisting of copper, silver and gold. When
the expression "based on one or more metals of the group copper,
silver and gold" is employed, what is meant is that the non-ferrous
brazing alloy contains at least one of the foregoing copper group
metals as a main ingredient, with one or more of other non-ferrous
metals making up substantially the balance, such as zinc, nickel,
palladium, cadmium, tin, manganese, and the like.
Apparently, the lower the melting point of the braze alloy, the
deeper is the aluminum diffusion into it. Thus, it may be stated
generally that the non-ferrous brazing alloys include those having
melting points ranging from about 1,125.degree.F (607.degree.C) to
1,925.degree.F (1,052.degree.C) and preferably 1,175.degree.F
(635.degree.C) to 1,850.degree.F (1,010.degree.C). As will be
understood by those skilled in the art, the non-ferrous brazing
alloy must have a lower melting point than the metal substrates
being joined and yet must be high enough to resist softening at
elevated temperatures to which the aircraft part (e.g., vane/shroud
assemblies) is subjected during use.
Examples of non-ferrous brazing alloy compositions commonly
employed for producing brazed joints in aircraft components made of
ferrous metals, e.g., stainless steel are by weight as follows: (1)
50% Ag, 18% Cd, 16% Zn and 16% Cu [designated as AMS 4770 C] ; (2)
54% Ag, 40% Cu, 6% Zn and up to 1% Ni [designated as AMS 4772 B] ;
(3) 82% Au, 18% Ni [designated as PWA 698 ]; (4) 54% Ag, 25% Pd and
21% Cu [designated as PWA 706 ] and (5) 55% Cu, 35% Mn and 10% Ni
among many others. The diffusion of aluminum in alloy (1) may
proceed up to a depth of 0.007 inch and in the others up to 0.002
inch. Such diffusion by aluminum into the braze has a weakening
effect on the joint and adversely affects its resistance to
fatigue.
Illustrative brazing alloy compositions range in weight percent
(for brazing stainless steel) including their solidus, liquidus and
brazing temperatures are as follows: Exam- ple Temperature
.degree.F Nos. % Ag % Cu % Zn % Cd % Ni Solidus Liquidus Brazing
__________________________________________________________________________
1145- 1A 44-46 14-16 14-18 23-25 -- 1125 1145 1400 1175- 2A 49-51
14.5-16.5 14.5-18.5 17-19 -- 1160 1175 1400 1270- 3A 49-51
14.5-16.5 13.5-17.5 15-17 2.5-3.5 1170 1270 1500 1435- 4A 39-41
29-31 26-30 -- 1.5-2.5 1240 1435 1650 1370- 5A 44-46 29-31 23-27 --
-- 1250 1370 1550 1575- 6A 54 bal. 5 -- 1 1325 1575 1785 1325- 7A
60 bal. -- -- 10% Sn 1115 1325 1550 1610- 8A 92.5 bal. -- -- 0.2 Li
1435 1635 1800
__________________________________________________________________________
Another brazing alloy based on gold comprises 81.5% Au and the
balance nickel. This alloy has a solidus-liquidus temperature of
1,740.degree.F and is employed over a brazing temperature of about
1,740.degree. to 1,840.degree.F.
Most stainless steels can be brazed by any one of several different
filler metals, including silver-base alloys, gold-base alloys,
copper-base alloys and the like. Stating it another way, the
non-ferrous brazing alloy may contain at least about 40% by weight
of the copper group metals and preferably at least about 50% and
the balance non-ferrous alloying ingredients so long as the melting
point of the alloy ranges from about 1,125.degree. to
1,925.degree.F and preferably from about 1,175.degree. to
1,850.degree.F. The melting point is generally taken as the
liquidus temperature of the alloy. The minimum of at least 40% of
the copper group metal is met where the alloy contains at least 40%
Ag, or 40% Cu or 40% Au, or at least 40% of a combination of two or
more of the foregoing copper group metals. As stated hereinbefore,
the other non-ferrous alloying elements may comprise one or more of
Zn, Cd, Ni, Sn, Mn, Pd and the like. Thus, the brazing alloy may
contain 40 to 95% of at least one of the copper group metals and
the balance at least one other non-ferrous metal.
When the foregoing brazing alloys are employed in the production of
certain aircraft components, it has been found essential to
selectively coat the brazed areas with said aluminide-forming
barrier metal before thermally aluminizing the whole component. In
the case of nickel, various methods may be employed in selectively
coating the brazed joint therewith. One method is to apply a resist
to the unbrazed areas (e.g., a thin wax coating) while leaving the
brazed portion of the joint exposed for nickel plating. Following
nickel plating of the braze, the resist is removed from the
component and the component then embedded in an aluminizing pack
containing alumina, some aluminum powder and a small but effective
amount of a halide, e.g., AlCl.sub.3. The use of the foregoing
halide is advantageous in that very good aluminum coating can be
produced at temperatures ranging up to about 1,000.degree.F
(538.degree.C) while avoiding the production of undesired
crystallographic or metallurgical changes in the substrate. The
aluminizing temperature should not exceed the melting point of the
braze, otherwise, the brazed joint will be deleteriously affected
during aluminizing.
The same method may be applied to such aluminide-forming metals as
cobalt, iron, palladium, chromium, manganese and the like. In the
case of titanium, molybdenium and vanadium, these metals can be
selectively applied as powder slurries dispersed in a fugitive
organic binder, the coating dried and sintered in place at a
temperature below the melting point of the braze alloy in the
joint.
The aluminized surface produced in the foregoing manner is
characterized metallographically by the presence of iron aluminide
in the unbrazed areas adjacent the ferrous substrate outside of the
brazed portions and by the presence of a metal aluminide at the
metal-plated braze portions, e.g., nickel aluminide.
Where the aircraft component is made of stainless steel, such as
those bearing the designations AMS 5508, AMS 5616, AMS 6304,
17-4PH, type 410 and others, we prefer to use nickel as a barrier
metal which is applied as a nickel mask on the brazed areas by
chemical plating. We find this method to be very advantageous in
that we can passivate the exposed stainless steel substrate while
activating the brazed areas, such that during the subsequent step
of chemical plating, the nickel selectively coats only the brazed
areas and not the stainless steel substrate. The method is also
applicable to cobalt and iron.
Of the foregoing steels, the composition of AMS 5616 comprises 13%
Cr, 2% Ni, 3% W and the balance essentially iron; type 410
comprises about 11.5 to 13.5% Cr, 1% Si max., 1% Mn max., 0.15% C
max., and the balance essentially iron; and 17-4 PH comprises about
17% Cr, 4% Ni, 3% Cu, small amounts of Co, Mn, Si, etc., and the
balance essentially iron. Broadly speaking, the steels may comprise
about 5 to 25% Cr, up to 5% W, up to 25% Ni, up to 4% Cu, up to 3%
Al, up to 2% Ti and the balance essentially iron.
The passivation of the steel substrate is achieved by employing a
chemical anodizing solution comprised of cupric chloride, mercuric
chloride, bismuth chloride, hydrochloric acid, alcohol and water.
Broadly, the aqueous solution may have the following composition
calculated in grams per liter (gpl) and milliliters per liter
(ml/l):
10 to 70 gpl cupric chloride
20 to 140 gpl mercuric bichloride
10 to 70 gpl bismuth chloride
100 to 400 ml/l of ethyl alcohol and
100 to 400 ml/l concentrated hydrochloric acid balance essentially
water to make 1 liter equivalent.
Examples of actual bath compositions are as follows:
I II III IV ______________________________________ Cupric chloride
(gpl) -- 60 30 20 12 Mercuric Bichloride (gpl) -- 120 60 40 28
Bismuth Chloride (gpl) -- 60 30 20 12 Ethyl Alcohol (ml/l) -- 300
150 100 60 Hydrochloric Acid (ml/l) -- 375 188 125 75 Water (ml/l)
-- bal. bal. bal. bal. ______________________________________
The foregoing solutions are used at room temperature, the steel
parts being immersed therein for generally about 1/4 to 10
minutes.
Following preparation of the solution, the cleaned stainless steel
component (e.g., in the grit-blasted honed condition) is immersed
in it. The steel surface tends to darken while mecury reduction
occurs cathodically (due to galvanic action) on the braze at
immersion times of 1/4 to 10 minutes. However, chemical or
electroless plating of nickel will not occur on the surfaces of the
component unless the steel substrate is further treated. This is
done by subsequent nitric or chromic acid dipping at room
temperature to remove any observable mercury, thereby activating
the braze surface.
Typical passivating solutions for this treatment are: (A) 50%
nitric acid solution, (B) saturated chromic acid solution, and (C)
or varying combinations of both. The chromic acid solution may
range in concentration from 100 grams/liter to saturation, the
steel substrate being immersed for 10 to 30 minutes followed by
immersion in 10 - 30 volume % nitric acid for 30 to 60 seconds.
Following nitric acid dipping, the stainless steel component is
then preferably nickel plated in a chemical or electroless plating
bath of nickel, such as nickel baths based on dimethylamine borane
or sodium hypophosphite. The aqueous sodium hypophosphite may
comprise the following:
Nickel sulfate 15 to 30 gpl Sodium Hypophosphite 15 to 30 gpl
Sodium Glycolate 20 to 40 gpl Sodium Succinate 10 to 20 gpl The pH
is adjusted to 4.5 to 6.
The temperature is preferably 180.degree.-195.degree.F.
A typical aqueous solution is one containing 25 gpl nickle sulfate,
25 gpl sodium hypophosphite, 30 gpl sodium glycolate and 17 gpl
sodium succinate.
Chromium-containing steel components have been immersed for one
hour to deposit approximately 0.0005 inch of nickel and for as long
as 2 hours to produce a nickel plate approaching 0.001 inch thick
on the braze, while inhibiting nickel plating out in the stainless
steel substrate. Nickel plates found adequate for the purpose
generally exceed about 0.0002 inch.
A stainless part that has been successfully treated in the
foregoing manner is the vane/shroud component shown in FIGS. 1 to
3. FIG. 1 shows a vane/shroud 10 of AMS 5616 steel comprising inner
and outer rings 11 and 12, respectively, with vanes 13 brazed
therebetween.
The brazed joints 14 are clearly shown in FIG. 2. Referring to FIG.
3, vane 13 is shown attached by braze 14 to inner ring 11. The
fillet of the AMS 4772B brazed joint has been selectively coated
with nickel such that following aluminizing of the part by pack
cementation, a layer 15 containing nickel aluminide is provided
following the contour of the fillet. As will be noted, an aluminide
layer 16 is shown adjacent the surface of the inner ring comprising
iron aluminide by reaction with the steel substrate during pack
cementation. As will be noted in FIG. 3, the specimen has an
overplate of copper and nickel 17 to provide the necessary support
for mounting and polishing said specimen without adversely
affecting the coating.
In thermally aluminizing the selectively nickel-plated vane/shroud
component shown in FIG. 1, a preferred pack cementation method is
employed as follows:
The method comprises preparing an aluminizing pack comprised for
example of 800 lbs. of -60+140 mesh aluminum powder blended with
200 lbs. of Al.sub.2 O.sub.3, also -6+140 mesh size. To the 1,000
lb. mixture is added 30 lbs. of dry AlCl.sub.3 under a humidity
preferably not exceeding 45%.
The pack is mixed in a vibrating blender under dry conditions for
about 5 to 10 minutes. If the charge is a fresh charge, it is
subjected to burn-out at 795.degree.825.degree.F (425.degree. to
440.degree.C) for 35 hours. However, where a charge has already
been used and is recycled for another pack, burn-out is not
required. The pack is placed in a dry condition in a retort with
the vane/shroud component of AMS 5616 steel to be treated, the
vane/shroud being completely embedded in the pack using vibration
to fill in the spaces between the vanes. The cover is sealed to the
retort body with multiple layers of aluminum foil in the form of a
gasket sufficient to prevent air from getting in but to allow
out-gassing of gaseous by-products.
The retort is placed in an oven at ambient temperature and the
temperature allowed to rise to the desired coating temperature by
the application of heat. As the temperature rises, it is preferred
that it go through an endothermic arrest at about 350.degree.F
(176.degree.C) due to vaporization of AlCl.sub.3 to effect further
cleansing of the surface of the component of any oxide film thereon
and then allowed to reach a temperature not exceeding about
1,000.degree.F (538.degree.C), for example, a range of about
795.degree. to 825.degree.F (425.degree. to 440.degree.C) and the
retort maintained at substantially that temperature range for about
36 hours. Upon completion of the heating cycle, the retort is
removed from the oven and allowed to cool approximately to
400.degree.F (205.degree.C), after which it is placed in a dry
environment for cooling to ambient temperature.
The cooled retort is then placed in a humidity control cabinet, the
cover removed and the aluminum-coated vane/shroud taken out of the
cementation pack. The part is cleaned of adhering coating compound
by blowing with dry air and immersed in water to remove fine dust
and other residues to provide a very clean aluminum deposit
containing an iron aluminide intermetallic compound, such as
FeAl.sub.3, on the braze-free portion of the component and a nickel
aluminide intermetallic compound on the nickel-plated brazed
portion of the component. The aluminized surface, like other
thermally diffused aluminum coatings, is characterized by
sacrificial properties in that it will corrode in preference to the
ferrous substrate in saline environments and, therefore,
substantially protect the ferrous substrate against corrosion.
Generally speaking, the pack composition may comprise by weight
about 60 to 100% aluminum, about 1 to 5% dry AlCl.sub.3 and the
balance essentially a stable inert refractory oxide.
As stated hereinbefore, unless the braze of the joint is plated
with an aluminide-forming metal, such as nickel, prior to
aluminizing the stainless steel component, the fatigue properties
at the joint are generally degraded. This has been confirmed by
tests in which specimens of the joint have been subjected to
cantilever loading to provide maximum bending stress at the joint
during fatigue testing. In a test series conducted, the fatigue
samples were shpaed in the form of a "tee" from type 410 stainless
steel by brazing a machined cantilevered arm to the surface of the
sample with alloy AMS 4772B. Prior to brazing, the specimens were
solution treated, quenched and tempered.
In one specimen, the brazed joint was aluminized in the manner
described hereinbefore without applying a nickel plate. That is to
say, the braze was bare prior to aluminizing. In other specimen,
the braze was first selectively nickel plated and subsequently
aluminized. The aluminized specimens are then subjected to an
oxodation/corrosion/fatigue screening test using the following
cycle:
1. 10,000 fatigue cycles at 50,000 psi root load
2. 5 hours oxidation at 700.degree.F
3. 16 hours salt spray
The salt spray test used is ASTM B117.
The foregoing cycle is repeated until the sample fails. The results
on the bare brazed joint and the aluminized nickel-plated brazed
joint are as follows:
Total Fatigue Cycles Salt Oxida- Number to Failure at Spray tion
Specimen of Cycles 50,000 psi Hours Hours
______________________________________ Bare Joint 5 58,000 80 25
Nickel- Plated Joint 19 200,000* 304 95
______________________________________ *This specimen did not
fail.
The failed joint showed general oxidation and corrosion attack to a
depth of 0.0035 inch. The nickel-plated joint showed no evidence of
braze corrosion after 19 test cycles. A bare joint without
corrosion ran 300,000 cycles to failure at a load of 50,000
psi.
One of the attributes of an aluminide coating on a metal substrate
is its ability to absorb readily a silicate liquid in the
production of a protective non-metallic overcoat.
As pointed out in the aforementioned U.S. Pat. No. 3,729,295, it is
believed that the high affinity of the thermally aluminized coating
or surface for the silicate is associated with the
physical-chemical character of the aluminized surface arising out
of the method of growth of the aluminide. The expression "thermally
aluminized coating or surface" is meant to cover the thermal
diffusion of aluminum in a metal surface in which iron and/or
nickel aluminide is formed at the surface.
In one embodiment, the non-metallic overcoat or barrier layer is
formed by applying to the thermally aluminized surface of the
article a solution of a soluble silicate salt at a temperature
ranging up to about 100.degree.C, for example, about 70.degree. to
95.degree.C (about 160.degree. to 200.degree.F), removing excess
liquid from the surface, such as by blowing it off with air, to
form a uniform layer of said silicate salt, and then drying the
layer on said surface.
While the aluminized surface in and of itself exhibits resistance
to saline corrosion, a typical salt spray test shows that
sacrificial products form on the aluminized surface after
approximately 15 hours of testing, whereas times in excess of 200
hours have been obtained when the aluminized surface is coated with
a uniform silicate layer.
A wide range of sodium silicate solutions can be employed in
producing the non-metallic overcoat. For example, the solutions can
be prepared from solutions of 50 to 100% concentrations of Na.sub.2
O.sup.. 3.22 SiO.sub.2. Various other sodium silicates can be
employed to prepare solutions such as Baume 40, 45, 47 and 50.
Potassium silicate may be similarly employed. Lithium silicate and
also organic silicates can be used, such as ethyl silicate.
A preferred solution for producing a uniform pre-coat or barrier
layer on the intermetallic iron aluminide substrate is one
containing by weight about 0.05 to 2% SiO.sub.2 equivalent, for
example, a soluble silicate in the form of Na.sub.2 O.sup.. 3.22
SiO.sub.2. The temperature of the substrate during application
should preferably range from about 70.degree. to 95.degree.C.
A preferred method for applying the silicate solution pre-coat at
the foregoing concentration comprises immersing the thermally
aluminized ferrous component in a tank maintained at a temperature
of abouot 70.degree. to 95.degree.C with sufficient time in the
bath to bring the component to temperature and assure absorption of
the solution into the aluminized surface. The excess liquid is then
blown off with air and the part allowed to dry. It is immersed
again for a brief period for a time sufficient to allow the article
to be covered with liquid, after which it is removed, blown off
with air and air dried. The steps may be repeated until the desired
thickness is obtained. It has been found that when using the
air-drying technique, only short dips in the tank need be employed
to ensure a continuous build-up of the silicate layer. Leaving the
part in the bath too long can result in the layer being redissolved
in the solution. To assure wettability of the coating on the
intermetallic substrate, an anionic surfactant or wetting agent may
be employed, for example, an anionic phosphate surfactant, such as
Triton QS-30 (manufactured by Rohm & Haas).
An alternate method which yields a more stable silicate coating
resides in applying a succession of layers as described hereinabove
followed by curing in an oven. Infra-red or forced air heated ovens
may be employed in the temperature ranges of about 150.degree. to
430.degree.C (about 300.degree. to 805.degree.F) with enhanced
corrosion protection. The silicate coating applied by any of the
methods described herein will produce a uniform layer with a
thickness of approximately 0.0001 inch (0.1 mil) while avoiding as
far as is possible areas of excess silicate on the surface. A
preferred method is to apply at least one pre-coat from a dilute
silicate bath containing 0.05 to 2% by weight of SiO.sub.2
equivalent by a series of dipping, drying and curing steps followed
by at least one spray coating of silicate from a more concentrated
solution containing about 2.5 to 17.5% (e.g., 6.8%) by weight of
SiO.sub.2 equivalent.
The advantage of curing the silicate coating which allows multiple
layers to be formed is that the cured coating can withstand ten
oxidation-corrosion cycles comprising heating the coated substrate
to 1,000.degree.F (about 538.degree.C) for 1 hour followed by 5
hours of salt spray testing, the foregoing test being repeated for
ten cycles. Applications of the silicate coating followed by curing
at about 400.degree.F (205.degree.C) have yielded high degrees of
protection and, in many cases, very little sacrificial products
have been observed after 10 cycles of heating to 1,000.degree.F
(538.degree.C) followed by the salt spray test. The foregoing tests
are helpful as controls in assuring the quality of the silicate
coating before the next coating treatment is applied.
The corrosion resistance of the intermetallic layer is further
enhanced by applying a conversion coating to the cured silicate
layer. The conversion coating in turn may be covered by a silicate
layer. The conversion coating may be applied by spraying, using
commercially available reciprocating guns. Following the
application of the conversion coating, the silicate solution
containing 6.8% by weight equivalent of SiO.sub.2 and containing
about 0.002% by weight of an anionic phosphate surfactant may
optionally be sprayed over the conversion coating having a surface
temperature not exceeding about 150.degree.F (65.degree.C) followed
by curing at temperatures from about 300.degree.F (150.degree.C) to
about 805.degree.F (430.degree.C) for 10 minutes in an infra-red
furance. Another method of covering the conversion coating is to
dip the article in a hot solution of about 180.degree. to
200.degree.F (82.degree. to 93.degree.C), using a sodium silicate
concentration of about 0.9 to 2.4% by weight of SiO.sub.2
equivalent with a 0.002% addition of an anionic phosphate
surfactant.
The article or component is immersed in the bath and allowed to
come to temperature and excess liquid removed rapidly by means of
an air gun. It is then immersed again and immediately pulled out of
the solution and air dried. A third application is made in the same
manner. It is important that excess liquid be removed from the part
to avoid foaming during curing. The purpose of repeated immersion
and drying is to assure uniform coating of the surface. As stated
above, the curing is preferably carried out at about 800.degree.F
in an infra-red furnace.
A simple production procedure which has been found successful for
applying uniform layers of silicate is as follows:
A component of AMS 5616 steel is subjected to 4 cycles of treatment
in the solution by supporting the component, e.g., a vane/shroud
component, on a rack which is immersed in the solution and
immediately withdrawn. The liquid is allowed to drain for
approximately 15 seconds, after which it is immersed again and
withdrawn. Following the second dip, air pressure means is disposed
about the rack to blow off the excess liquid. This group of steps
constitutes one cycle. Four cycles are employed to produce the
desired silicate layer. If necessary, an air gun can be used to
remove excess liquid from the root of the blades. After the fourth
cycle, the blades are dried free of mositure by, for example,
blowing with air. The temperature at which the silicate layers are
applied may range from about 160.degree.F (70.degree.C) to
200.degree.F (90.degree.C). Following completion of the four
cycles, the coating on the dried blade is then cured at about
800.degree.F (425.degree.C) in an infra-red oven.
Apparently the combination of the silicate coating and the
aluminide compound in the aluminized surface markedly improves the
resistance of the aluminized surface to corrode sacrificially,
wherein the life of the sacrificial coating is unexpectedly
extended for longer periods of time in saline environments than
obtained with the aluminized surface alone.
However, as stated in U.S. Pat. No. 3,729,295, the life of the
silicated sacrificial aluminized coating is further enhanced by the
application of a conversion coating from a solution in
substantially the same manner in which the silicate coating is
applied. An aqueous conversion coating solution which is preferred
may range by weight from about 5 to 30% phosphoric acid (preferably
10 to 30%), about 0.0235 to 3% aluminum, about 3 to 8% chromic acid
(CrO.sub.3), about 0.75 to 6% magnesium and the blance essentially
water. A formulation found particularly preferred in producing the
solution is as follows:
Wt. % ______________________________________ Phosphoric acid 15.0
Aluminum powder 0.225 Chromic acid (CrO.sub.3) 5.0 Magnesium
turnings 1.5 A non-anionic surfactant comprising a condensation
product of ethylene oxide with an alkylphenol (Triton X-100 by Rohm
& Haas) 0.1 Water 78.175 100.00
______________________________________
The aluminum and magnesium are dissolved in the solution by virtue
of the free acid present.
In conversion coating a silicated steel substrate, the substrate is
sprayed and then dried and cured in the oven which heats the
substrate to a temperature of about 800.degree.F (427.degree.C).
The substrate is then cooled prior to the next application of the
coating. The steps of spraying, baking and cooling constitute one
spray cycle. Three spray cycles are normally used in applying the
conversion coating.
The application of the conversion coating as described above
results in a smooth uniform surface layer which provides
oxidation-corrosion protection without the need for supplementary
surface finishing. A build-up of approximately 0.1 mil can be
obtained by employing a plurality of silicate and conversion
coating applications.
It is believed that the baking of the duplex silicate-conversion
coating results in a reaction product which provides new and
improved resistance to corrosion in saline environments. While the
silicate is preferably first applied to the thermally aluminized
surface, it is appreciated that it can be applied as a solution
together with the conversion coating materials. Thus, the
conversion coating solution prior to spraying may contain about
0.05 to 2% by weight SiO.sub.2 equivalent as sodium silicate,
potassium silicate, ethyl silicate, and the like.
it will be noted from copending U.S. Pat. No. 3,729,295 that, in
addition to the conversion coating formulation described herein,
various conversion coatings of the phosphatechromate types may be
employed in conjunction with the soluble silicate salt. Stating it
broadly, the conversion coating comprises phosphates and chromates
of at least one metal, for example, Al, Mg, Zn, Be, Ba, Sr, Ce,
group metals and other metals. As a preferred embodiment, a
conversion coat containing phosphates and chromates of aluminum and
magnesium is particularly desirable.
Broadly speaking, the conversion solutions may range in composition
by weight of at least about 0.5% of at least one phosphate and
chromate-forming metal, e.g. about 0.5 to 10%, about 5 to 30%
phosphoric acid, about 3 to 8% chromic acid (CrO.sub.3) and the
balance essentially water. A preferred conversion solution is one
containing by weight about 0.02 to 3% dissolved aluminum, about
0.75 to 6% dissolved magnesium, about 5 to 30% phosphoric acid
(preferably 15 to 30%), about 3 to 8% chromic acid and the balance
essentially water. A more specific composition is one containing by
weight about 1/4% aluminum, about 1.5% magnesium, about 15%
phosphoric acid, about 5% chromic acid and the balance essentially
water.
While specific examples are directed to nickel as the
aluminide-forming metal, the invention is applicable to the other
stated aluminide-forming metals. Thus, in applying chromium to the
braze area, the steel substrate is selectively coated with a
resist, e.g., wax, while leaving the braze exposed and chromium
then plated on the brazed areas making the steel substrate the
cathode in an electrolyte containing 250 to 400 grams/liter chromic
acid (CrO.sub.3) and 2.5 to 4 grams/liter of sulfate ions. The
current density may range from 10 to 45 amps/dm.sup.2. Following
formation of the chromium layer on the braze, the steel substrate
is de-waxed, cleaned and then aluminized as described hereinbefore,
the aluminide at the braze being chromium aluminide. The same
method may be employed for cobalt and iron. As for molybdenum,
titanium and vanadium, these may be applied to the braze as a
powder slurry and dried prior to aluminizing.
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.
* * * * *