U.S. patent number 3,655,425 [Application Number 04/838,319] was granted by the patent office on 1972-04-11 for ceramic clad flame spray powder.
This patent grant is currently assigned to Metco Inc.. Invention is credited to Frank N. Longo, Mahesh S. Patel.
United States Patent |
3,655,425 |
Longo , et al. |
April 11, 1972 |
CERAMIC CLAD FLAME SPRAY POWDER
Abstract
A flame spray powder comprises finely-divided core particles of
a metal or a metal alloy coated with discrete particles of a
ceramic or cermet that remains in solid phase at least 100.degree.F
above the fusing or melting temperature of the metal. The average
particle size of the ceramic is less than 25 percent of the average
particle size of the metal and the amount used is insufficient to
totally cover the surface of the metal particles so that on the
average in the range of 5 to 75 percent of the surface area of the
metal particles is exposed to ambient conditions. When used in
flame spraying, this new ceramic clad metal powderin one embodiment
forms a flame spray coating where the ceramic is in the continuous
phase and the coating is relatively soft and abradable, and in
another embodiment the metal of the coating is in the continuous
phase and the coating is relatively hard and erosion resistant.
Inventors: |
Longo; Frank N. (Ellwood,
Huntington, NY), Patel; Mahesh S. (Elmhurst, NY) |
Assignee: |
Metco Inc. (N/A)
|
Family
ID: |
25276804 |
Appl.
No.: |
04/838,319 |
Filed: |
July 1, 1969 |
Current U.S.
Class: |
75/230; 75/231;
75/234; 75/244; 428/403; 428/404; 428/539.5; 428/564; 428/570;
428/937; 501/119 |
Current CPC
Class: |
C23C
4/06 (20130101); Y10T 428/2991 (20150115); Y10T
428/12181 (20150115); Y10S 428/937 (20130101); Y10T
428/2993 (20150115); Y10T 428/12139 (20150115) |
Current International
Class: |
C23C
4/06 (20060101); B44d 001/094 (); B44d
001/02 () |
Field of
Search: |
;29/191.2
;117/1M,105.2,16R,169 ;106/1 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Whitby; Edward G.
Claims
What is claimed is:
1. A flame spray powder comprising finely-divided core particles of
a metal bonded to and coated with discrete particles of a ceramic
that remains in solid phase at least 100.degree. above the fusing
temperature of said metal, said ceramic having an average particle
size less than 25 percent of the average particle size of said
metal core and leaving exposed on the average in the range of 5 to
75 percent of the surface area of the metal core as determined by
the PLMG method.
2. The powder of claim 1 having a particle size in the range of
-100 mesh to 3 microns and wherein in the range of 10 to 50 percent
of the surface of said core particles is exposed by said discrete
particles which amount to in the range of 1 to 30 volume percent of
the volume of the core particles.
3. The powder of claim 1 wherein said discrete particles are bonded
to said core particles with a resinuous binder, said binder
amounting to in the range of 0.05 to 5 volume percent of the volume
of said core particles.
4. The powder of claim 1 wherein said metal is a nickel-chromium
and said ceramic is boron nitride.
5. The powder of claim 1 wherein said discrete particles
additionally include a material selected from the group comprising
metals and ceramics and having an average particle size of less
than 25 percent of the size of said metal core particles, the
additional material being present in an amount in the range of 0.5
to 15 percent of the volume of the amount of said metal.
6. The powder of claim 5 wherein said metal is a
cobalt-nickel-chromium alloy, said ceramic is a diatomaceous earth
and said additional material is aluminum.
7. The powder of claim 1 wherein said metal and ceramic particles
have a globular to generally spherical shape.
8. A flame sprayed composition obtained by passing a metal-ceramic
powder through a flame spray gun and melting at least the metal
component thereof; and thereafter impinging the heated powder
against a receptor surface, said powder comprising finely-divided
core particles of a metal bonded to and coated with discrete
particles of a ceramic that remains in solid phase at least
100.degree. F. above the fusing temperature of said metal, said
ceramic having an average particle size less than 25 percent of the
average particle size of said metal and leaving exposed on the
average in the range of 5 to 75 percent of the surface are thereof
as determined by the PLMG method.
9. The composition of claim 8 wherein said ceramic is in the
continuous phase and said composition is relatively soft and
abradable.
10. The composition of claim 8 wherein said metal is in the
continuous phase and said composition is relatively hard and
erosion resistant and not too abradable.
Description
PRIOR ART
U.S. Pat. No. 3,084,064 issued to Cowden et al., Apr. 2, 1963,
discloses that in the manufacture of turbines it is desirable to
reduce the clearance between the turbine blade and turbine housing
by flame spraying an abradable metal composition onto the housing
and then to allow the blades to seat themselves within the housing
by abrading the coating. This invention is particularly concerned
with a flame spray powder for producing abradable coatings.
U.S. Pat. No. 3,322,515 issued to Dittrich et al., May 30, 1967 and
assigned to the assignee of the present invention, discloses that
rather than using the wire rod flame spray method and separately
introducing a second material in powder form as disclosed in U.S.
Pat. No. 3,084,064 powders formed of two or more materials can be
used and in one embodiment proposes that aggregates be formed by
cladding a core powder with a second powder. The aggregate powders
basically comprise two metal components one of which will
exothermically react with the other when subjected to the flame
spray.
BACKGROUND OF THIS INVENTION
Flame spraying involves the heat softening of a heat fusible
material such as a metal or ceramic and the propelling of the
softened material in particulate form against the surface to be
coated to which the heat fusible material bonds. A flame spray gun
is usually used for the purpose and with one type, heat fusible
material is supplied in powder form to the gun. Such powders are of
quite small particle size, e.g., below 100 mesh U.S. standard
screen size to about one micron.
A flame spray gun normally utilizes a combustion or plasma flame to
effect melting of a powder but other heating means such as electric
arcs, resistant heaters or induction heaters can also be used,
alone or in combination. In a powder-type combustion flame spray
gun, the carrier gas for the powder can be one of the combustion
gases or it can be compressed air. In a plasma flame spray gun the
primary plasma gas is generally nitrogen or argon. Hydrogen or
helium is usually added to the primary gas. The carrier gas is
generally the same as the primary plasma gas although other gases
such as hydrocarbons are used in special cases.
The nature of the coating obtained by flame spraying a metal powder
can be quite specifically controlled by proper selection of the
composition of the powder, control of the physical nature of the
powder and the use of select flame spraying conditions. It is well
known and common practice to flame spray a simple mixture of a
ceramic powder and a metal powder. Hard coatings that are useful
may be produced with mixtures. Many ceramic powders such as boron
nitride or silicon carbide do not have normal melting points and
cannot be satisfactorily sprayed in mixtures. Others such as
tungsten carbide or zirconium diboride tend to oxidize and
decompose when heated to melting point in the flame. When softer
coatings are desired the ceramic is usually not melted to any
extent during the spraying and accidental entrapment of the
unmelted ceramic powder particles is relied on. If greater heat is
used to melt the ceramic, if the ceramic has a melting point, this
may be too much heat for the metal and may cause oxidation of the
metal and produce too hard a coating. In the case of the metal-clad
ceramic particles, as is taught in the U.S. Pat. No. 3,254,970, in
practice the powder usually comprises a major portion of ceramic
because it is difficult to obtain very thick cladding layers of the
metal onto the ceramic and the sprayed coating produced therefrom
often does not have suitable properties for the application, for
example the proper degree of abradability.
THIS INVENTION
In the present invention it has been found that by partially
cladding metal particles with a finer ceramic or cermet powder,
abradable coatings can be produced from the clad metal powder by
flame spraying that have properties not previously obtainable. The
reason for this is not known with any certainty. It is speculated
that by leaving a certain portion of the metal core particles
exposed, the melting of the core particles, i.e., their ability to
pick up heat from the flame, is greatly facilitated, which in the
end results in a more adherent uniform coating.
If the metal core particles were completely surrounded by the
ceramic, as has been the case in the past for some compositions,
the ceramic which has a low thermal conductivity may effectively
insulate the metal core particles from the flame. In one case,
wherein a nickel alloy was clad with boron nitride with 100%
coverage, coatings produced by flame spraying with this powder were
totally unsatisfactory.
DESCRIPTION AND EXAMPLES
There is no standard method for determining the percent of coverage
of one powder clad with another more finely divided powder. For
this reason an empirical test was devised wherein the clad powder
is observed under polarized light microscopically and a microscopic
grid is used to estimate the percent of the areas of the metal core
particles that is covered with the ceramic powder. This might be
termed the polarized light-microscopic grid method, or the PLMG
method for short.
More particularly, the PLMG method is carried out by placing about
one-half gram of powder on a 1-inch by 3-inch glass slide. The
powder is evenly distributed and then a mirror is gently placed on
top of the powder to make a cover glass. It is fastened with tape
with the reflector side of the mirror facing the powder. This slide
is then placed in a metallurgical microscope. Light is passed
through the glass slide across the powder and reflected back off
the mirror. When viewed under normal reflected light, a dull
outline of the powder is visible. When polarized light is used the
mirror appears grey, the exposed metal shows dark and the ceramic
is very bright. Examination of the specimen in a plain polarized
light requires a polarizing prism and analyzer. When the polarizer
and analyzer are rotated 90.degree. out of phase, or other angle as
determined by trial, the ceramic appears bright and the mirror and
exposed metal are darkened. If the ceramic is not sensitive to
polarized light, experimentation with incident light may be
required to contrast the ceramic with the metal.
The core and coating particles will usually appear to have a
generally globular to spherical shape. By measuring the relative
percentage of dark areas to bright areas on the particles the
amount of exposed metal can be determined. To do this, a square
grid is superimposed on the image magnified 150 times. This may be
done by using an appropriate eye piece reticle or by placing a grid
on a photograph, with the grid 1 inch by 1 inch comprising 100
squares each 0.1 inch square. The grid must be positioned so that
the particles are within the outer lines of the grid. By counting
the number of squares which are not covered by the particles, the
area of the particle is estimated. With the grid in the same
position, the metal surface area is also estimated by counting the
squares filled by dark areas. Dividing the estimated dark area by
the particle area gives the percent of the exposed metal surface.
This procedure is usually carried out on 25 to 30 particles
selected at random.
The ceramic powder should remain in solid phase, that is, it should
not melt, soften, vaporize or decompose significantly at a
temperature at least 100.degree. F above the melting or fusing
temperature of the core metal.
It often is desirable to additionally include particles of a third
material which, together with the ceramic particles, are coated on
to the metal core particles. The third material will usually be
less than 25 percent of the size of the core particles. It may be
either a metal or ceramic in an amount in the range of 0.5 to 15%
of the volume of the amount of metal core. As an example, when the
core is nickel, cobalt or iron, or an alloy thereof, it is
preferable to mix fine aluminum powder with the ceramic powder
before bonding the mix to the core particles. The aluminum addition
results in improved deposit efficiency and coating quality. The
reason for this is not clear by it is speculated that it involves
the exothermic reaction disclosed in U.S. Pat. No. 3,322,515.
The ceramic cladding powder is preferably bonded to the metal core
particles with a resinous binder although other types of bonding
methods can be used. The metal core particles will usually have a
size in the range of minus 100 mesh (U.S. standard screen size) to
3 microns, preferably of -140 to +325 mesh. The ceramic coating
particles will usually have the size of less than 25% of the size
of the core particles. The amount of the ceramic powder will
usually be in the range of 1 to 30 volume percent of the volume of
the core particles so that incomplete cladding of the core
particles is assured.
The cladding is accomplished by mixing the core particles, the
ceramic cladding particle and the resinuous binder, carried in a
suitable solvent, together followed by removing of the solvent and
the breaking up of any agglomerates that may have been formed. Upon
drying the binder is present in an amount between 0.05 and 5 volume
percent of the volume of the core particles. Any one of many types
of binders can be used such as starches, sugars, celluloses,
polyamides, rubbers, urethanes, phenols, polyesters, epoxies,
acetates and the like. The water soluble polyvinyl alcohols, the
inorganic and organic silicates and organic resins such as the
phenolics and vinyls are perhaps preferred. The incomplete ceramic
cladding can be achieved without a binder by other known methods
such as vapor deposition.
The term "ceramic" is used broadly, such as is described by W. D.
Kingery, Introduction to Ceramics, John Wiley & Sons, Inc., New
York (1960). Ceramics are usually compounds although carbon,
especially the higher temperature form of graphite, is now
considered a ceramic. Usually ceramics are resistant to high
temperatures. Preferably the ceramics used have a melting point, if
any, or are stable, at least 100.degree. F. above the melting point
of the metal of the core particles. Typical ceramics are carbides
such as tungsten carbide, chromium carbide and titanium carbide;
simple oxides such as aluminum oxide, zirconium oxide, titanium
oxide and chromium oxide; complex oxides such as magnesium
zirconate, borosilicate glasses, diatomaceous earth and talcum
powder; nitrides such as boron nitride, borides such as zirconium
diboride, halides such as calcium fluoride, silicides such as
chromium silicides, etc.
The core metal or alloy can include such metals as tungsten,
titanium, tantalum, columbium, zirconium, nickel, cobalt, iron,
aluminum, copper, tin, and alloys thereof. Typical core metals are:
essentially pure molybdenum; titanium with six parts aluminum and
four parts vanadium; nickel with 16 parts chromium and eight parts
iron; monel (67 percent nickel -- 33 percent chromium); a cobalt
alloy having 25.5 parts chromium, 10.5 parts nickel, 7.5 parts
tungsten, 0.5 parts carbon with the balance cobalt; Type 316 or
Type 431 stainless steel; aluminum with 12 parts silicon, and
aluminum-bronze such as one with 9.5 parts aluminum, 1 part iron
and the balance copper; and a Babbit of 7.5 parts antimony, 3.5
parts copper, 0.25 parts lead with the balance being tin.
EXAMPLES
Example I
Eighty-nine parts of a nickel-chromium alloy powder of -140 to +325
mesh was coated with 4 parts by weight of a 3 to 4 micron aluminum
powder and 7 parts of a -325 mesh boron nitride powder (HTP
grade-Carborundium Co., Latrobe, Pa.) using 5 parts of a phenolic
varnish (Metcoseal AP -- Metco, Inc., Westbury, N.Y.) as a binder.
The aluminum and boron nitride powders were first preblended, and
the varnish was mixed with the alloy powder. The materials were
then blended together using additional solvent as necessary. The
solvent was removed by stirring, agglomerates were broken up and
the clad powder was screened to -100 to +325 mesh. The yield was 94
percent based on original ingredients.
When examined by the PLMG method, the metal cores were 75 percent
covered by the boron nitride and aluminum. When flame sprayed at a
flame temperature of about 5,500.degree. F. (Thermospray 5 P gun,
Metco, Inc., acetylene gas and oxygen) onto a mild steel surface, a
soft and easily abradable coating resulted. The coating hardness
was measured on a superficial Rockwell Hardness Tester using a 15
kg load and a 1/8-inch-diameter ball. The hardness read as R
15w=-100 +55 = -45. The spray distance in this case was 8 inches.
An increase in the spray distance will increase the hardness.
A microscopic examination of the coating showed there was a
continuous interconnected boron nitride phase. The composition of
the coating was 49 volume percent boron nitride, 49 volume percent
nickel-chromium alloy and 2 volume percent free aluminum. The
balance of aluminum presumably combined exothermically with the
nickel.
Aircraft turbine engine tests of this coating gave excellent
results.
Example II
The nature of the coating, i.e., its abradability, erosion
resistance and hardness, will vary with the spray parameters. The
same clad powder as in Example I was sprayed with the same gun with
the essential conditions changed being air and spray distance to
give additional coating specimens: B, C and D. The coating of
Example I is designated as specimen A. The conditions and results
are given in Table I. ##SPC1##
In order to obtain the density, the coatings were sprayed on
1-inch- by 1-inch- time 1/8-inch-thick flat pieces of mild steel.
These coatings were ground flat and weighted. Then almost 0.03 inch
of the coating thickness were ground off and the specimen weighted
again. The difference in weight over the volume gave, fairly
accurately, the density of the coating.
The erosion resistance tests were carried out by spraying the
coatings on 1-inch by 2-inch by 1/8-inch mild steel plates prepared
by blasting with alumina grit (Metcolite "F"), upon which the
erosion tests were carried out for one minute. The test coatings
were blasted at a 45.degree. angle with Al.sub.2 O.sub.3 type
particles propelled by compressed air. The distance between the
nozzle and the coating was about 4 inches. The weight loss was
converted into volume using density. For the abradability test the
specimen were 1-inch by 3-inch plates coated to 0.05 inch and
ground flat. The tests were conducted on a scribe test machine
which moves a stylus back and forth on the coating to cut a scratch
using a 0.35-inch-wide pointed probe and a 1,650-gram load on the
probe. The tests were run for one minute each and the thickness
loss measured.
With Coating B the metal matrix was continuous whereas with Coating
A the boron nitride was in the continuous phase. The B-type coating
had a metallurgical structure that gave a high erosion resistance
with less abradability. Similarly, Coating C and D had a more
continuous metal phase than Coating B and this tended to make a
hard matrix and erosion resistant coating.
Example III
Eight weight percent of a diatomaceous earth is clad on a cobalt
alloy (25.5 Cr, 10.5 Ni, 7.5 W, 0.5C, balance cobalt) using the
same cladding method as above described. The size of the alloy
powder is -200 + 325 mesh. The diatomaceous earth has a size of
less than one micron. Three percent aluminum flake powder having a
size of 0.2 microns thick and 1 micron long is also added to the
mixture. The binder used is as in Example I.
The coating produced from this powder is capable of withstanding
temperatures up to 1,800.degree. F.
Example IV
A 3 percent weight carbon, having a size of less than 1 - 3 microns
is clad onto an aluminum powder of -170 + 325 mesh using organic
silicate as the binder. This is combustion flame sprayed to produce
a self lubricating and abradable coating.
Example V
Talc Mg.sub.3 Si.sub.4 O.sub.10 (OH).sub.2 is clad onto an aluminum
bronze powder of -270 + 15 microns using a resinuous binder. This
powder will produce a self lubricating bronze coating suitable for
bearing applications.
Example VI
Fifteen weight percent titanium oxide 0.1 micron to 1 micron is
clad on a titanium alloy (6 Al. 4 V) 100 to 325 mesh using
polyvinyl alcohol as a binder and water for solvent. If this is
plasma flame sprayed on titanium alloy shafts used in jet engines
it provides a wear resistance bearing surface which is lightweight
and capable of high temperature operation.
Example VII
An aluminum oxide powder (10 weight percent) 2 microns to 5 microns
is clad onto an aluminum powder 270 to 400 mesh and combustion
flame sprayed on steel to give an abrasion and corrosion resistance
protective coating.
Example VIII
Similarly, tungsten carbide particles (10 weight percent) 2 to 7
microns are clad onto Metco 15E self-fluxing alloy (1 C, 4 Si, 17
Cr, 3.5 B, 4 Fe, balance Ni). This will provide a very dense, hard,
wear-resistance coating.
Example IX
Silicon carbide particles (5 weight percent) 5 to 10 microns are
clad onto copper powder -170 + 325 mesh and combustion flame
sprayed on brake disks. This provides a wear and fade resistant,
thermally conductive coating for automobile brakes.
* * * * *