U.S. patent number 3,762,884 [Application Number 05/190,316] was granted by the patent office on 1973-10-02 for nickel aluminide coated low alloy stainless steel.
This patent grant is currently assigned to The United States of America as represented by the National Aeronautics. Invention is credited to Salvatore J. Grisaffe, Ernest W. Klechke.
United States Patent |
3,762,884 |
Grisaffe , et al. |
October 2, 1973 |
NICKEL ALUMINIDE COATED LOW ALLOY STAINLESS STEEL
Abstract
Low alloy austenitic stainless steel is protected from oxidative
corrosion and erosion at high temperatures in the presence of
exhaust gases from internal combustion engines by flame-spraying a
layer between about 0.003 inches and about 0.007 inches thick of an
alloy of 80 percent nickel and 20 percent chromium on the steel
base, and thereafter converting the layer to an intermetallic
chromium containing nickel aluminide coating by a low temperature
aluminum cementation process. A cementation pack comprising 96
percent aluminum oxide, 2 percent aluminum, 1 percent sodium
chloride, and 1 percent ammonium bifluoride is placed on the
nickel-chromium layer in an inert atmosphere for a period between
four hours and 24 hours at 1400.degree.F to 1600.degree.F to form
an intermetallic chromium containing nickel aluminide coating
containing 40 to 60 atomic percent aluminum. The coated steel is
highly resistant to oxidation corrosion and erosion by high
temperature exhaust gases from internal combustion engines. It is
particularly useful in the construction of thermal reactors for
exhaust systems in automobiles for the control of pollution from
exhausts.
Inventors: |
Grisaffe; Salvatore J. (Rocky
River, OH), Klechke; Ernest W. (Fairview Park, OH) |
Assignee: |
The United States of America as
represented by the National Aeronautics (Washington,
DC)
|
Family
ID: |
22700840 |
Appl.
No.: |
05/190,316 |
Filed: |
October 18, 1971 |
Current U.S.
Class: |
428/610; 428/926;
428/938; 428/679; 428/937 |
Current CPC
Class: |
C23C
4/18 (20130101); C23C 10/02 (20130101); F01N
13/16 (20130101); C23C 10/50 (20130101); Y10S
428/926 (20130101); Y10S 428/938 (20130101); Y10S
428/937 (20130101); Y10T 428/12458 (20150115); Y10T
428/12937 (20150115) |
Current International
Class: |
C23C
10/50 (20060101); C23C 10/02 (20060101); C23C
10/00 (20060101); C23C 4/18 (20060101); F01N
7/00 (20060101); F01N 7/16 (20060101); B32b
015/00 () |
Field of
Search: |
;29/196.2.196.6 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Bizot; Hyland
Claims
What is claimed is:
1. An article of manufacture resistant to oxidative corrosion and
erosion at high temperatures comprising an austenitic stainless
steel base having a nickel-chromium alloy coating with a thickness
of about 0.005 inch forming a diffused modified bonded junction
with the stainless steel base, said alloy coating having aluminum
diffused thereinto to form nickel aluminide which increases from
the base surface to the outer surface so that said outer surface
comprises substantially all nickel aluminide and chromium.
2. An article of manufacture as claimed in claim 1 wherein said
coating is produced by applying aluminum by means of low
temperature pack cementation to a flame-sprayed layer between about
0.003 inch and about 0.007 inch thick of 80 percent nickel-20
percent chromium alloy on said base, said aluminum reacting with
said layer to form said nickel aluminide.
3. An article of manufacture as claimed in claim 2 wherein said
austenitic stainless steel is a low nickel alloy stainless steel,
and said aluminum is applied from a cementation pack comprising 96
percent aluminum oxide, 2 percent aluminum, 1 percent sodium
chloride, and 1 percent ammonium bifluoride.
4. An article of manufacture as claimed in claim 2 wherein said
aluminum is applied in an inert atmosphere at about 1400.degree. to
1600.degree.F.
5. An austenitic stainless steel substrate having a flame sprayed
alloy coating of 80 percent nickel and 20 percent chromium with a
minimum thickness of 0.003 inch, said alloy coating having aluminum
diffused thereinto to form nickel aluminide which increases from
the stainless steel surface to the outer surface thereof so that
said outer surface comprises substantially all nickel aluminide and
chromium, said coating forming a diffused modified bonded junction
with the stainless steel substrate.
6. An article as claimed in claim 5 wherein said flame-sprayed
layer is about 0.005 inch thick.
Description
ORIGIN OF THE INVENTION
The invention described herein was made by employees of the United
States Government and may be manufactured and used by or for the
Government for governmental purposes without the payment of any
royalties thereon or therefor.
BACKGROUND OF THE INVENTION
Field of the Invention
This invention relates to a coating for low alloy austenitic
stainless steel to render the steel highly resistant to oxidation
corrosion and erosion from exhaust gases in internal combustion
engines.
The engine exhaust of automotive internal combustion engines
contains carbon monoxide, carbon dioxide, nitrogen dioxide,
unburned hydrocarbons, sulfur compounds, and other corrosive
products which are exhausted into the atmosphere in the absence of
means for controlling such emissions. Recently federal regulations
have been imposed which set progressively lower allowable engine
exhaust levels for such combustion products. Minor adjustments in
carburetion and spark control and the like are no longer
satisfactory in meeting such requirements. One way such engine
emissions can be reduced further in the future in order to meet the
requirements of controlling agencies is by the utilization of
thermal exhaust converters or reactors. Such thermal reactors
replace the exhaust manifold.
In some reactors, secondary air is introduced into the reactor in
order to promote the complete combustion of unburned hydrocarbons
and carbon monoxide. In order to achieve the desired ends, many
components of the thermal reactor must operate at temperatures on
the order of 1900.degree.F with the possibility that if the
ignition means fails, the temperature may increase up to
2300.degree.F.
It is a practical requirement of the automobile industry that such
reactors have useful lives of 2000 hours or more, which translates
to 50,000 miles of driving at an average speed of 25 miles per
hour. Under such stringent conditions of severe temperatures,
exhaust atmosphere, and term of life requirements, the oxidation
corrosion and erosion as well as the chemical attack by lead and
sulfur compounds on unprotected steel components are very
significant.
Since such thermal exhaust reactors are required in large
quantities, for example, up to fifteen million units a year at the
present automotive industry production rate, it is essential that
such thermal reactors be capable of being produced at the minimum
possible cost. One approach to avoid utilization of expensive
components is to use protective coatings on the metal materials
used in such thermal reactors.
DESCRIPTION OF THE PRIOR ART
It is known, of course, that materials such as extremely high alloy
steels are resistant to oxidation corrosion and erosion and thus
fulfill the technical requirements for materials in such thermal
exhaust reactors. The use of high alloy steels would be extremely
expensive for such applications, however, because of the vast
amounts of metal such as nickel that are required. It is known that
low alloy steels possess moderately high temperature strengths but
that they are not resistant to degradation by the environmental
conditions in the thermal exhaust reactors.
In U.S. Pat. No. 3,481,715, Whalen et al., there is disclosed a
sealing member which is moderately resistant to oxidation at high
temperatures in which the steel base is coated with an intermediate
layer of an alloy of nickel with aluminum or chromium applied by a
plasma gun, to which a surface layer of material comprising nickel
oxide and calcium fluoride is applied using a plasma gun. The
nickel with aluminum or chromium layer serves to improve the
adhesion of the oxide surface layer.
U.S. Pat. No. 3,338,733, Rowady, discloses metallic surface
coatings resistant to corrosion and wear such as that to which
internal combustion valves are exposed. In this case a steel base
is first preheated to 1300.degree. to 1800.degree.F and a
nickel-chromium alloy is applied by flame-spraying. The coated
object is then subjected to a first diffusion step at temperatures
of 1800.degree. to 2250.degree.F to promote alloying between the
coated alloy and the base metal. The coating subsequently may be
coated with an aluminum layer by first preheating the coated base
to 1200.degree. to 1400.degree.F and then thereafter dipping the
article in a molten bath of aluminum or applying the aluminum by a
flame-spraying technique. After the aluminum coating has been
applied, the object is then heated to 1500.degree.F to
2100.degree.F to diffuse and alloy the aluminum into the
nickel-chromium alloy.
SUMMARY OF THE INVENTION
The present invention provides a low alloy austenitic stainless
steel article highly resistant to oxidation corrosion and erosion
by a coating which comprises a chromium containing nickel aluminide
applied by the process of this invention. Low alloy stainless steel
material coated according to this invention exhibits oxidation
resistance equal to or better than the oxidation resistance
obtained on many highly alloyed steels either uncoated, or coated
with expensive alloys and other compounds, many applied by complex
processes.
A relatively low cost stock article suitable for use in
constructing thermal exhaust reactors is provided by this invention
by using low alloy austenitic stainless steel. It provides
resistance to corrosion using steels having only a relatively small
amount of nickel.
According to this invention, an oxidation corrosion and erosion
resistant article is provided by depositing on a low nickel alloy
austenitic stainless steel base a layer between about 0.003 to
0.007 inch, preferably 0.005 inch, thick of a nickel-chromium alloy
such as 80 percent nickel-20 percent chromium, by means of
flame-spraying or plasma spraying, then converting the
nickel-chromium alloy layer to one comprising an intermetallic
compound, as opposed to an alloy, of chromium-containing nickel
aluminide by a low temperature aluminum pack cementation process at
1400.degree. - 1600.degree.F for four to 24 hours which in a single
process step also serves to diffusion bond the coating to the steel
substrate. The chromium-containing nickel aluminide coating
contains from about 40 to about 60 atomic percent of aluminum.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Test specimens of austenitic 304 stainless steel
(Fe-18Cr-8Ni-0.008C) were cut from 1/16 inch thick sheet stock. One
set were 3/4 inch .times. 11/2 inches, and another were 1 inch
.times. 2 inches. Prior to coating according to this invention the
specimens were ball milled in a ceramic mill with no. 36 alumina
grit and water and thereafter vapor blasted with 100 mesh alumina,
degreased, and then ultrasonically cleaned in
trichloroethylene.
The samples are then coated with a 0.005 inch layer of 80 percent
nickel-20 percent chromium by flame-spraying, using a conventional
spray gun adapted for spraying nickel-chromium alloy fed in wire
form. The thickness of the layer can be between 0.003 and 0.007
inches. Layers having thicknesses at the lower end of the range
have less stresses while the thicker layers have longer lives.
The nickel-chromium layer is then converted to a chromium
containing nickel aluminide intermetallic compound by a pack
cementation step by treating the layer with a high activity
aluminum pack. The pack employed comprises 96 percent aluminum
oxide, 2 percent aluminum, 1 percent sodium chloride, and 1 percent
ammonium bifluoride. The coating is treated in a furnace under an
inert atmosphere such as argon for from four to 24 hours,
preferably for 16 hours, at 1600.degree.F. The process deposits
approximately 15 mg. of aluminum per square centimeter which reacts
to form a chromium enriched nickel aluminide intermetallic
protective layer on the low alloy austenitic stainless steel and at
the same time forms a diffusion bond between the coating and the
substrate.
Essentially no diffusion bonding takes place during the
flame-spraying application of the nickel-chromium layer. The bond
between the alloy layer and the steel base at this stage is itself
primarily a mechanical bond. Following the aluminum cementation,
the chromium-nickel alloy layer has been converted to a
chromium-containing nickel aluminide intermetallic compound coating
which is diffusion bonded to the steel substrate.
The 3/4 inch .times. 11/2 inches samples are then placed in a
horizontal multitube furnace on high purity recrystallized alumina
boats. Air is passed over the specimens at the rate of two cubic
feet per hour. One set of specimens is heated for 100 hours at
2000.degree.F, with cycling to room temperature. The cycles consist
of 20 hours at test temperature followed by cooling to room
temperature. At room temperature the specimens are lightly brushed
to remove any oxide scale and weighed to 0.05 mg. per square
centimeter accuracy. A second set of specimens is similarly cycled
for 600 hours at 1800.degree.F. Excellent resistance to oxidation
corrosion and erosion was evident from visual examination, x-ray
diffraction, microscopic and metallographic analysis. Furthermore,
there was no loss of weight of the samples, but a slight weight
gain, for example, the specimens gain about 3 mg. per square
centimeter after 600 hours exposure to the 1800.degree.F cycling
tests. During all of the tests, the metal temperature is measured
by thermocouples which are mounted on adjacent uncoated
specimens.
The 1 inch .times. 2 inches coated specimens are tested in an
experimental automotive thermal reactor connected to a high
performance 472 cubic inch V-8 automobile engine with air injection
and carburetion. Leaded gasoline is used as a fuel and the engine
is operated to provide test specimen cycles of 10 minutes at
1900.degree.F, 5 minutes at 1200.degree.F, and repeat. After 170
cycles, the specimens exhibit no significant deterioration and gain
approximately 0.1 gram. All coatings after testing exhibit
excellent weight stability, coating preservation and metallographic
stability. The specimens when examined visually appear almost
unchanged from the as coated condition.
The coatings obtained according to the process of the present
invention impart excellent high temperature corrosion and erosion
resistance to low alloy austenitic stainless steel. The protection
of the low alloy austenitic stainless steel is achieved by a
process which involves primarily only two steps as opposed to other
methods of applying different oxidation resistant coatings which
are often quite complex. The invention is particularly advantageous
in providing an article suitable for utilization in automotive
thermal reactors which are necessary to reduce exhaust pollution in
automobiles. Significantly the present invention provides an
excellent material for such reactors at relatively low cost and a
low consumption of expensive nickel metal. By way of illustration,
in order to provide 15 million thermal exhaust reactors annually
utilizing a high alloy stainless steel such as aluminum coated Inco
800 containing 32 percent nickel, about 15 percent of the total
nickel consumed annually in the United States would be required,
whereas utilizing material according to the present invention about
7 percent of the nickel consumed annually would be required. This
is based upon the use of 41/2 square feet of material 1.5 mm. thick
for a typical thermal core reactor.
While the invention has been explained by a detailed description of
a specific embodiment, it is understood that various modifications
and substitutions can be made within the scope of the appended
claims which are intended to include equivalents of such
embodiments.
* * * * *