U.S. patent application number 10/256602 was filed with the patent office on 2003-02-06 for method for applying a high-temperature bond coat on a metal substrate, and related compositions and articles.
Invention is credited to Hasz, Wayne Charles, Sangeeta, D..
Application Number | 20030024430 10/256602 |
Document ID | / |
Family ID | 24460446 |
Filed Date | 2003-02-06 |
United States Patent
Application |
20030024430 |
Kind Code |
A1 |
Hasz, Wayne Charles ; et
al. |
February 6, 2003 |
Method for applying a high-temperature bond coat on a metal
substrate, and related compositions and articles
Abstract
A method for applying a bond coat on a metal-based substrate is
described. A slurry which contains braze material and a volatile
component is deposited on the substrate. The slurry can also
include bond coat material. Alternatively, the bond coat material
can be applied afterward, in solid form or in the form of a second
slurry. The slurry and bond coat are then dried and fused to the
substrate. A repair technique using this slurry is also described,
along with related compositions and articles.
Inventors: |
Hasz, Wayne Charles;
(Pownal, VT) ; Sangeeta, D.; (Cincinnati,
OH) |
Correspondence
Address: |
General Electric Company
CRD Patent Docket Rm 4A59
M.N. Salamone
P.O. Box 8, Bldg. K1
Schenectady
NY
12301
US
|
Family ID: |
24460446 |
Appl. No.: |
10/256602 |
Filed: |
September 30, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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10256602 |
Sep 30, 2002 |
|
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09614248 |
Jul 12, 2000 |
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Current U.S.
Class: |
106/1.05 ;
428/545 |
Current CPC
Class: |
C23C 28/325 20130101;
Y10T 428/12063 20150115; C23C 24/10 20130101; C23C 28/347 20130101;
Y10T 428/12611 20150115; C23C 4/02 20130101; Y02T 50/60 20130101;
C23C 26/02 20130101; C23C 28/345 20130101; Y10T 428/12472 20150115;
C23C 28/3455 20130101; Y10T 428/12007 20150115; C23C 28/321
20130101; C23C 28/3215 20130101; Y10T 428/12931 20150115; Y10T
428/12993 20150115 |
Class at
Publication: |
106/1.05 ;
428/545 |
International
Class: |
B05B 001/00 |
Claims
What is claimed:
1. A method for applying a bond coat on a metal-based substrate,
comprising the following steps: a) applying a slurry which
comprises braze material to the substrate, wherein the slurry also
contains a volatile component; b) applying bond coat material to
the substrate; c) drying the slurry and bond coat material to
remove at least a portion of the volatile component; and d) fusing
the braze material and bond coat material to the substrate.
2. The method of claim 1, wherein the braze material comprises at
least one metal selected from the group consisting of nickel,
cobalt, iron, a precious metal, and a mixture which includes at
least one of the foregoing.
3. The method of claim 2, wherein the braze material comprises at
least about 40% by weight nickel.
4. The method of claim 2, wherein the braze material further
comprises a constituent which lowers the melting point of the braze
alloy.
5. The method of claim 4, wherein the constituent is silicon,
boron, or mixtures thereof.
6. The method of claim 1, wherein the braze material has an average
particle size in the range of about 20 microns to about 150
microns.
7. The method of claim 1, wherein the slurry further comprises at
least one additive selected from the group consisting of binders,
stabilizers, thickening agents, dispersants, deflocculants,
anti-settling agents, plasticizers, emollients, lubricants,
surfactants, anti-foam agents, and curing modifiers.
8. The method of claim 1, wherein the slurry is applied to the
substrate by a technique selected from the group consisting of
slip-casting, brushing, painting, dipping, flow-coating,
roll-coating, spin coating, and spraying.
9. The method of claim 1, wherein the bond coat material comprises
an alloy of the formula MCrAlX, where M is selected from the group
consisting of Fe, Ni, Co, and mixtures of any of the foregoing; and
where X is selected from the group consisting of Y, Ta, Si, Hf, Ti,
Zr, B, C, and combinations thereof.
10. The method of claim 1, wherein the bond coat comprises a
material selected from the group consisting of aluminide,
platinum-aluminide; nickel-aluminide; platinum-nickel-aluminide;
and mixtures thereof.
11. The method of claim 1, wherein the bond coat material has an
average particle size of at least about 45 microns.
12. The method of claim 11, wherein the bond coat material has an
average particle size in the range of about 150 microns to about
300 microns.
13. The method of claim 1, wherein the volatile component comprises
at least one aqueous solvent or at least one organic solvent, or
mixtures thereof.
14. The method of claim 1, wherein step (c) is carried out by
air-drying.
15. The method of claim 1, wherein step (d) is carried out at a
temperature in the range of about 525.degree. C. to about
1650.degree. C.
16. The method of claim 1, wherein the metal-based substrate is a
superalloy.
17. The method of claim 16, wherein the superalloy is a nickel-base
or cobalt-base material.
18. The method of claim 1, wherein the bond coat has a root mean
square roughness (R.sub.a) value of greater than about 200
micro-inches, after step (d).
19. The method of claim 1, wherein the slurry also contains the
bond coat material, so that the braze material and the bond coat
material are applied to the substrate simultaneously.
20. The method of claim 19, wherein the slurry is prepared by
combining the bond coat material and the braze material with a
solvent and at least one additive selected from the group
consisting of binders, stabilizers, thickening agents, dispersants,
deflocculants, anti-settling agents, plasticizers, emollients,
lubricants, surfactants, anti-foam agents, and curing
modifiers.
21. The method of claim 19, wherein the braze material has an
average particle size in the range of about 20 microns to about 150
microns, and the bond coat material has an average particle size of
at least about 45 microns.
22. The method of claim 1, wherein the slurry of step (a) is
substantially dried after being applied, thereby forming a green
layer, prior to the application of the bond coat material.
23. The method of claim 22, wherein an adhesive material is applied
to the green layer, prior to the application of the bond coat
material.
24. The method of claim 23, wherein the bond coat material is in
the form of dry particles, and is applied to the adhesive
material.
25. The method of claim 24, wherein the bond coat material is
poured or sprinkled onto the adhesive.
26. The method of claim 1, wherein the bond coat material is in the
form of a second slurry, applied in step (b) on top of the slurry
applied in step (a).
27. The method of claim 26, wherein each slurry comprises at least
one additive selected from the group consisting of binders,
stabilizers, thickening agents, dispersants, deflocculants,
anti-settling agents, plasticizers, emollients, lubricants,
surfactants, anti-foam agents, and curing modifiers.
28. The method of claim 26, wherein each slurry is applied to the
substrate by a technique selected from the group consisting of
slip-casting, brushing, painting, dipping, flow-coating,
roll-coating, spin coating, and spraying.
29. The method of claim 1, wherein the bond coat is in the form of
a second slurry, and the second slurry is pre-mixed with the first
slurry to form a pre-mixture, said pre-mixture being applied to the
substrate prior to step (c).
30. The method of claim 29, wherein the pre-mixture is applied to
the substrate by a technique selected from the group consisting of
slip-casting, brushing, painting, dipping, flow-coating,
roll-coating, spin coating, and spraying.
31. The method of claim 1, wherein an overcoat is applied over the
bond coat after step (d).
32. The method of claim 31, wherein the overcoat is a thermal
barrier coating.
33. The method of claim 32, wherein the thermal barrier coating is
zirconia-based.
34. The method of claim 32, wherein the thermal barrier coating is
applied by a thermal spray technique.
35. The method of claim 34, wherein the thermal spray technique is
a plasma spray process.
36. The method of claim 31, wherein the overcoat is a
wear-resistant coating.
37. The method of claim 31, wherein the overcoat comprises a
material selected from the group consisting of metal carbides;
alumina, mullite, zircon, cobalt-molybdenum-chromium-silicon;
strontium-calcium-zirconate glass; and mixtures thereof.
38. A method for applying a metal aluminide- or MCrAlY-based bond
coat on a superalloy substrate, where M is nickel, cobalt, or a
mixture thereof, comprising the following steps: (I) applying a
slurry which comprises a volatile component and a mixture of braze
material and bond coat material to the substrate, wherein the braze
material contains at least about 40% by weight nickel; (II) drying
the slurry under conditions sufficient to remove at least a portion
of the volatile component, forming a green coating; and (III)
brazing the green coating to the substrate.
39. The method of claim 38, wherein the braze material has an
average particle size in the range of about 40 microns to about 80
microns, and the bond coat material has an average particle size in
the range of about 150 microns to about 300 microns.
40. The method of claim 38, wherein a zirconia-based thermal
barrier coating is applied over the bond coat.
41. A method for replacing a bond coat applied over a metal-based
substrate, comprising the following steps: (i) removing the
existing bond coat from a selected area on the substrate; (ii)
applying a slurry which comprises braze material to the selected
area, wherein the slurry also contains a volatile component; (iii)
applying additional bond coat material to the selected area; and
(iv) fusing the braze material and bond coat material to the
selected area.
42. The method of claim 41, wherein the slurry also contains the
bond coat material, so that the braze material and the bond coat
material are applied to the substrate simultaneously.
43. The method of claim 41, wherein the bond coat material
comprises an alloy of the formula MCrAlX, where M is selected from
the group consisting of Fe, Ni, Co, and mixtures of any of the
foregoing; and where X is selected from the group consisting of Y,
Ta, Si, Hf, Ti, Zr, B, C, and combinations thereof.
44. The method of claim 41, wherein the metal-based substrate is a
portion of a turbine engine.
45. A slurry composition, comprising a braze material and a bond
coat material.
46. The composition of claim 45, wherein the braze material
comprises at least one metal selected from the group consisting of
nickel, cobalt, iron, a precious metal, and a mixture which
includes at least one of the foregoing.
47. The composition of claim 46, wherein the braze material
comprises at least about 40% by weight nickel.
48. The composition of claim 46, wherein the bond coat material
comprises an alloy of the formula MCrAlX, where M is selected from
the group consisting of Fe, Ni, Co, and mixtures of any of the
foregoing; and where X is selected from the group consisting of Y,
Ta, Si, Hf, Ti, Zr, B, C, and combinations thereof.
49. The composition of claim 46, wherein the bond coat comprises a
material selected from the group consisting of aluminide,
platinum-aluminide, nickel-aluminide; platinum-nickel-aluminide;
and mixtures thereof.
50. The composition of claim 46, wherein the bond coat material is
in the form of particles, and the particles have an average size of
at least about 45 microns.
51. An article, comprising: (a) a metal-based substrate; and (b) a
volatile-containing slurry on the substrate, comprising braze
material and bond coat material.
52. The article of claim 51, wherein the substrate is a
superalloy.
53. The article of claim 51, wherein the substrate is a component
of a turbine engine.
54. The article of claim 51, wherein the braze material comprises
at least about 40% by weight nickel, and the bond coat material
comprises an alloy of the formula MCrAlX, where M is selected from
the group consisting of Fe, Ni, Co, and mixtures of any of the
foregoing; and where "X" is selected from the group consisting of
Y, Ta, Si, Hf, Ti, Zr, B, C, and combinations thereof.
55. The article of claim 51, wherein the volatile component in the
slurry has been substantially removed, so as to form a green
coating.
56. The article of claim 55, wherein the green coating is fused to
the substrate, forming a bond coat.
57. The article of claim 56, wherein the braze material forms a
continuous matrix phase in which the bond coat particles are
embedded.
58. The article of claim 57, wherein an overcoat is disposed over
the bond coat.
59. The article of claim 58, wherein the overcoat is a
zirconia-based TBC.
60. The article of 58, wherein the overcoat is a wear-resistant
coating.
61. An article, comprising: (i) a metal-based substrate, and (ii) a
brazed bond coat comprising bond coat particles, disposed over the
substrate, wherein the braze material forms a continuous matrix
phase in which the bond coat particles are embedded.
62. The article of claim 61, wherein the brazed bond coat has a
root mean square roughness (R.sub.a) value of greater than about
200 micro-inches.
63. The article of claim 61, wherein the brazed bond coat is
characterized by micro-roughness.
64. The article of claim 61, wherein the brazed material is
nickel-based or cobalt-based.
65. The article of claim 61, wherein the bond coat is a
higher-temperature material.
66. The article of claim 61, wherein the bond coat particles are
roughness-producing.
Description
BACKGROUND OF THE INVENTION
[0001] This invention was made with government support under
Contract No. DEFC21-95-MC31176 awarded by the Department of Energy.
The government may have certain rights to the invention.
[0002] The invention disclosed herein generally relates to bond
coatings and thermal barrier coatings applied to metals. The metals
are frequently portions of components used in turbine engines. The
invention also relates to processes for depositing such
coatings.
[0003] Components formed of specialty materials like superalloys
are used in various industrial applications, under a diverse set of
operating conditions. In many cases, the components are provided
with coatings which impart several characteristics, such as
corrosion resistance, heat resistance, oxidation resistance, and
wear resistance. As an example, the various components of turbine
engines, which typically can withstand in-service temperatures in
the range of about 1100.degree. C.-1150.degree. C., are often
coated with thermal barrier coatings (TBC's), to effectively
increase the temperature at which they can operate.
[0004] Most TBC's are ceramic-based, e.g., based on a material like
zirconia (zirconium oxide), which is usually chemically stabilized
with another material such as yttria. For a jet engine, the
coatings are applied to various superalloy surfaces, such as
turbine blades and vanes, combustor liners, and combustor nozzles.
Usually, the TBC ceramics are applied to an intervening bond
coating (sometimes referred to as a "bond layer" or "bond coat")
which has been applied directly to the surface of the metal part.
The bond coat is often critical for improving the adhesion between
the metal substrate and the TBC.
[0005] The effectiveness of a TBC is often measured by the number
of thermal cycles it can withstand before it delaminates from the
substrate which it is protecting. In general, coating effectiveness
decreases as the exposure temperature is increased. The failure of
a TBC is often attributed to weaknesses or defects related in some
way to the bond coating, e.g., the microstructure of the bond
coating. TBC failure can also result from deficiencies at the bond
coating-substrate interface or the bond coating-TBC interface.
[0006] The microstructure of the bond coating is often determined
by its method of deposition. The deposition technique is in turn
determined in part by the requirements for the overlying protective
coating. For example, many TBC's usually require a very rough bond
coat surface (e.g., a root mean square roughness (R.sub.a) value of
greater than about 200 micro-inches), for effective adhesion to the
substrate. An air plasma spray (APS) technique is often used to
provide such a surface.
[0007] There continues to be a need in the art for bond coatings
which provide very good adhesion between the substrate and a
subsequently-applied TBC, e.g., bond coatings with a relatively
rough surface. Furthermore, new processes for applying and curing
such coatings in regions of a substrate which are somewhat
inaccessible are also of great interest. (Conventional thermal
spray equipment is sometimes too large and cumbersome for such
regions). Moreover, the entire TBC system--bond coating with the
TBC itself--should exhibit good integrity during exposure to high
temperatures and frequent thermal cycles. Such a system should be
effective in protecting components used in high performance
applications, e.g., superalloy parts exposed to high temperatures
and frequent thermal cycles.
SUMMARY OF THE INVENTION
[0008] One embodiment of the present invention is directed to a
method for applying a bond coat on a metal-based substrate,
comprising the following steps:
[0009] a) applying a slurry which comprises braze material to the
substrate, wherein the slurry also contains a volatile
component;
[0010] b) applying bond coat material to the substrate;
[0011] c) drying the slurry and bond coat material under conditions
sufficient to remove at least a portion of the volatile component;
and
[0012] d) fusing the braze material and bond coat material to the
substrate.
[0013] The braze material is usually based on nickel, cobalt, or
iron. The bond coat material is often an "MCrA1X" material or a
metal carbide, as discussed below.
[0014] There are a variety of methods for applying the bond coat
according to this invention. One method calls for combining the
bond coat material and the braze material with a solvent and one or
more additives, as described below. The combined slurry mixture can
then be deposited on the substrate by various techniques, such as
flow-coating, brushing, or spraying. As an alternative, the slurry
applied in step (a) includes the braze material but not the bond
coat material, and is substantially dried to form a green layer. An
adhesive can be applied to the green layer, and the bond coat
particles can then be applied to the adhesive, prior to the fusing
step. As another alternative, two separate slurries can be
employed--one containing the braze material, and the other
containing the bond coat material. Each slurry can contain the
additives described below. In this embodiment, the braze slurry is
usually applied first, followed by the application of the bond coat
slurry. The slurries can then be dried and fused to the substrate.
An overcoat can optionally be applied over the bond coat. The
overcoat is usually a conventional thermal barrier coating, e.g.,
one based on zirconium. Alternatively, the overcoat can be of
another type, such as a metal carbide-based wear coating.
[0015] A method for replacing a bond coat applied over a
metal-based substrate is also described below. The following steps
are usually included in this method:
[0016] (i) removing the existing bond coat from a selected area on
the substrate;
[0017] (ii) applying a slurry which comprises braze material to the
selected area, wherein the slurry also contains a volatile
component;
[0018] (iii) applying additional bond coat material to the selected
area; and
[0019] (iv) fusing the braze material and bond coat material to the
selected area.
[0020] This technique can be part of the overall process for
repairing a worn or damaged TBC system.
[0021] Another embodiment of this invention is directed to a unique
slurry composition, containing a braze material and a bond coat
material, along with other conventional slurry ingredients, such as
a solvent. As discussed elsewhere, the braze material is usually
nickel, cobalt, iron, a precious metal, or some mixture containing
one of those components. The bond coat material is usually of the
MCrAlX-type (discussed below), or can be a metal carbide or other
type of material. The slurry composition is very useful in the
formation of a TBC system.
[0022] An article constitutes another embodiment of this invention.
It comprises:
[0023] (a) a metal-based substrate, and
[0024] (b) a volatile-containing slurry on the substrate,
comprising braze material and bond coat material (e.g.
roughness-producing bond coat particles).
[0025] The substrate is often a superalloy, and the braze material
and bond coat materials are as described below. When the volatile
component in the slurry has been substantially removed, a green
coating remains, which is fused to the substrate, e.g., by brazing.
As fused, the braze material forms a continuous matrix phase in
which the bond coat particles are embedded.
[0026] Other features and advantages of the present invention will
be more apparent from the following detailed description of the
invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] FIG. 1 is a cross-sectional photomicrograph of a comparative
coating system which includes a bond coat and a TBC, both applied
by conventional methods.
[0028] FIG. 2 is a cross-sectional photomicrograph of a bond
coat/TBC coating system, in which the bond coat was applied by a
slurry technique according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0029] The braze material used in this invention can be formed of
an alloy composition which is known in the art and commercially
available. Two classes of braze compositions are frequently used:
standard liquid brazes and activated diffusion brazes. Very often
(but not always), the braze alloy has a composition similar to that
of the substrate. For example, if the substrate is a nickel-base
superalloy, the braze alloy usually contains at least about 40% by
weight nickel, along with various other elements, like chromium,
aluminum, and yttrium. (Nickel-containing braze or
cobalt-containing braze alloys are usually used with cobalt-base
superalloys). The braze alloy composition also typically contains
one or more components for lowering its melting point. Examples of
melting point suppressants for nickel-base and cobalt-base braze
alloy compositions are silicon, boron, and phosphorous. Silicon or
boron, or combinations thereof, are often preferred. The braze
alloy composition may also contain other additives known in the
art, e.g., fluxing agents. The average particle size of the braze
alloy is usually in the range of about 20 microns to about 150
microns, and more preferably, in the range of about 40 microns to
about 80 microns.
[0030] Illustrative nickel-base and cobalt-base braze alloy
compositions are described in the commonly-assigned U.S. patent
application Ser. No. 09/444,737 (W. Hasz), filed on Nov. 23, 1999,
and incorporated herein by reference. Some preferred nickel-base
braze alloy compositions for the present invention comprise about 5
wt % to about 15 wt % silicon or boron; and about 15 wt % to about
25 wt % chromium, with the balance being nickel. Silicon is
sometimes preferred over boron. Mixtures of silicon and boron are
also possible.
[0031] Other types of braze alloys may be used, e.g., precious
metal compositions containing silver, gold, platinum, and/or
palladium, in combination with other metals, such as copper,
manganese, nickel, chromium, silicon, and boron. Mixtures which
include at least one of the braze alloy elements are also possible.
Many of the metal braze compositions are available from Praxair
Surface Technologies, Inc.
[0032] As mentioned above, the braze material is utilized in the
form of a slurry. The slurry usually contains at least one binder
and a solvent. Selection of the solvent depends on various factors,
such as its capacity for solubilizing the binder and dispersing the
braze powder; as well as the manner in which the slurry will be
applied to the substrate. The braze material can usually be
dispersed in either an aqueous or organic solvent. Examples include
water, ethanol or other alcohols; ketones, nitrile solvents (e.g.,
acetonitrile); ketone-type solvents like acetone; aromatic solvents
like toluene, xylene, or xylenol; and compatible mixtures thereof.
Sometimes, a two-solvent system is preferred, in which one solvent
flash-evaporates, while the other evaporates more slowly and
provides leveling properties. (As used in this disclosure, the term
"volatile component" generally refers to the solvent (or multiple
solvents) used in the slurry. It should also be understood that the
binders and other ingredients in the slurry will also volatilize,
or will decompose, as the temperature is raised, e.g., as fusing
temperatures are approached).
[0033] A variety of binder materials may be used in the slurry,
e.g., water-based organic materials such as polyethylene oxide and
various acrylics, or solvent-based binders. The slurry may also
contain various other additives, such as dispersants, wetting
agents, deflocculants, stabilizers, anti-settling agents,
thickening agents, plasticizers, emollients, lubricants,
surfactants, anti-foam agents, and curing modifiers. In general,
the additives are each used at a level in the range of about 0.01%
by weight to about 10% by weight, based on the weight of the entire
slurry composition. Those skilled in the art can determine the most
effective level for any of the additives, without undue effort.
[0034] Conventional details related to the mixing of the slurry are
described in various references, such as U.S. Pat. No. 4,325,754,
which is incorporated herein by reference. (Slurry compositions are
also commercially available). A variety of techniques can be used
to apply the slurry to the substrate. Examples include
slip-casting, brushing, painting, dipping, flow-coating,
roll-coating, spin coating, and spraying. Various texts are
instructive in this regard, e.g., the Kirk-Othmer Encyclopedia of
Chemical Technology, 4th Edition, Vol. 5, pp. 606-619; as well as
the Technology of Paints, Varnishes and Lacquers, Edited by C.
Martens, Reinhold Book Corporation, 1968. U.S. patent application
Ser. No. 09/378,956 (D. Sangeeta et al, filed Aug. 23, 1999 and
commonly-assigned) also describes some aspects of slurry
technology, and is incorporated herein by reference.
[0035] Various types of bond coat materials can be used in the
present invention. Most are well-known in the art.
"High-temperature" bond coats are often (but not always) preferred.
These are bond coats used in applications where the substrate is
exposed to service temperatures of at least about 500.degree. C.,
and more often, at least about 900.degree. C. Very often, the bond
coat material is of the MCrAlX type, where "M" can be various
metals or combinations of metals, such as Fe, Ni, or Co; and where
"X" is selected from the group consisting of Y, Ta, Si, Hf, Ti, Zr,
B, C, and combinations thereof. ("X" is usually yttrium). Some of
the preferred alloys of this type have a broad composition (in
weight percent) of about 17% to about 23% chromium; about 4% to
about 13% aluminum; and about 0.1% to about 2% yttrium; with M
constituting the balance. In some embodiments, M is a mixture of
nickel and cobalt, wherein the ratio of nickel to cobalt is in the
range of about 10: 90 to about 90 :10, by weight.
[0036] As alluded to earlier, other types of bond coat materials
can be used. Non-limiting examples include aluminide,
platinum-aluminide; nickel-aluminide; platinum-nickel-aluminide,
and mixtures thereof. Moreover, mixtures of MCrAl-type materials
with metals such as zirconium or hafnium may also be used. Those
skilled in the art will be able to select the most appropriate bond
coat material, based on end use, cost, processing method, and other
considerations.
[0037] The size of the bond coat particles may vary somewhat, and
is related in part to the desired roughness for the bond coat.
Usually, the bond coat particles have an average particle size of
at least about 45 microns. In those instances in which a subsequent
TBC is to be applied by air plasma spray (which often requires a
rough, underlying surface), the bond coat particles usually have an
average particle size of at least about 150 microns. In some
preferred embodiments, the bond coat particles have a size in the
range of about 150 microns to about 300 microns. Larger particle
sizes may be used in some cases, e.g., when greater roughness is
desired. Sometimes, these particles are referred to herein as the
"primary bond coat particles", which provide the conventional type
of roughness (R.sub.a) discussed below.
[0038] In preferred embodiments, especially in situations where an
air plasma-sprayed TBC is to be applied, the bond coat particles
have a particular shape. The shape is sufficient to produce
micro-roughness in the bond coat after the material has been fused
to the substrate with the braze. The micro-roughness is distinct
from, and in addition to, the roughness (R.sub.a) provided by the
primary bond coat particles. (The conventional roughness is usually
measured by surface profilometry.) Micro-roughness is a fine-scale
roughness and back-folding on the primary particle. All embodiments
of the present invention provide very good adhesion for a
subsequently-applied TBC. However, the presence of the
micro-roughness greatly increases that adhesion in many instances,
during the service life of the TBC.
[0039] There are several ways of obtaining micro-roughness, and
they usually involve the use of bond coat powder which is
commercially available and known to provide such an effect. The
micro-roughness may be in the form of smaller spheres of the bond
coat material (e.g., having a size in the range of about 5% to
about 50% of the primary particle diameter) which are bonded to the
larger, primary particles.
[0040] Alternatively, the micro-roughness may be in the form of an
irregular or rough surface on the primary particles. In this
instance, the surface of the primary particles is convoluted and
somewhat jagged, with undercut sections which appear to back-fold
in some areas. Such a particle surface has an appearance similar to
that resulting when one would tear an English muffin in half.
Powder particles having these characteristics (e.g., with an
MCrAlX-type composition) are commercially available.
[0041] In one embodiment of this invention, the slurry also
contains the bond coat material, so that the braze material and the
bond coat material are applied to the substrate simultaneously. Any
convenient technique for combining the braze and bond coat
materials in a single slurry may be employed, e.g., mechanical
mixers. In addition to following general safety procedures, care
should be taken to keep each of the metal components well-dispersed
in the slurry. At least one aqueous or organic solvent is used for
the slurry. Choice of a particular solvent or solvent mixture for
this embodiment will depend in part on the solvent's compatibility
with both the braze and bond coat materials, as well as with any
melting point suppressant which may be present. The solvents should
also be capable of maintaining the solid components substantially
dispersed. Moreover, the additives (mentioned above) which are used
in the slurry should be compatible with each other, and with the
other components in the slurry.
[0042] The slurry is usually deposited on the substrate as a single
layer. However, in some instances, it may be desirable to deposit
the slurry in the form of at least two "sub-layers", i.e., in at
least two applications. For example, each sub-layer may include the
same composition, but the size of the bond layer particles may be
varied. Smaller particles may be used in the sub-layer closest to
the substrate, for increased coating density. Larger particles may
be used in one or more upper sub-layers, to provide a desired
amount of roughness. (A heat treatment could be applied after the
application of each sub-layer).
[0043] As another alternative, the composition of two or more
sub-layers can be varied, to provide different properties at
different depths of the bond coat. As an example, a first sub-layer
could contain a standard NiCrAlY-type bond coat material, along
with the braze alloy. A second sub-layer applied over the first
sub-layer could contain braze alloy, along with a different bond
coat material, e.g., an MCrAlX-type bond coat material in which M
is a mixture of nickel and cobalt. The second sub-layer, which is
closer to the atmosphere during service, should provide greater
corrosion resistance than the standard NiCrAlY material in some
environments.
[0044] In a similar fashion, the composition of two or more
sub-layers could be varied to adjust the degree to which oxidation
occurs, e.g., oxidation at the bond coat-substrate interface, as
discussed in the examples. Moreover, the composition of the bond
coat could be graded or layered, (e.g., by a metering system), so
that the change in particular constituents is gradually made as the
slurry component is applied over the substrate.
[0045] After the slurry mixture has been deposited, at least a
portion of the volatile material contained therein is removed. This
step is sometimes referred to as an "evaporation step" or
"evaporation stage", and results in a substantially-devolatilized
(solvent-free) coating, i.e., a "green" coating. Any convenient
drying technique can be used to remove the volatile component.
Drying may include air-or vacuum-drying at room temperature. In
some instances, it may be desirable to heat the slurry mixture to
accelerate drying.
[0046] The green coating, which contains the braze material and the
bond coat material, is then fused to the substrate. The fusing step
can be carried out by various techniques. Very often, it is a
brazing step, and is similar to any conventional brazing operation.
(As used herein, "brazing" is generally meant to include any method
of joining metals that involves the use of a filler metal or
alloy.) One exemplary reference for details regarding brazing is
the text Modem Metalworking, by J. R. Walker, The Goodheart-Willcox
Co., Inc., 1965, pp. 29-1 to 30-24. Those of ordinary skill in the
art are familiar with other details regarding brazing. Brazing
temperatures depend in part on the type of braze alloy used, and
are typically in the range of about 525.degree. C. to about
1650.degree. C. In the case of nickel-based braze alloys, braze
temperatures are usually in the range of about 800.degree. C. to
about 1260.degree. C. When possible, brazing is often carried out
in a vacuum furnace. The amount of vacuum will depend in part on
the composition of the braze alloy. Usually, the vacuum will be in
the range of about 10.sup.-1 torr to about
[0047] 10.sup.31 8 torr. Furnace brazing also removes any volatile
materials (e.g., the binder) remaining in the green coating.
Volatile content can be determined by a variety of techniques, such
as differential thermal analysis (DTA) and thermal gravimetric
analysis (TGA).
[0048] In some cases, the slurry may have to be applied to an area
which does not lend itself to the use of a furnace. As an example,
the component itself may be too large for insertion into a furnace.
In such a case, alternatives are possible. For example, a torch or
other localized heating means can be used. These techniques are
known in the art and briefly described in the commonly-assigned
patent application of W. Hasz, Ser. No. 09/444,737, mentioned above
and incorporated herein by reference.
[0049] In an alternative embodiment, the slurry contains the braze
material and any necessary additives, but does not contain the bond
coat material. In this instance, the slurry is substantially dried
after being applied, to form a green layer. Any convenient drying
technique can be used, like those described above, e.g., air
drying, prior to or following an optional heat treatment to
increase the evaporation of the volatile component.
[0050] The bond coat material--usually in the form of dry powder
particles--is then applied over the green layer. Usually, an
adhesive is applied to a surface of the green layer, prior to the
application of the bond coat powder. A variety of adhesives can be
used, as long as they are capable of completely volatilizing during
the subsequent fusing step. Some of the suitable adhesives are
described, for example, in The Condensed Chemical Dictionary, 10th
Edition, B. Hawley, Van Nostrand Reinhold Company Inc., 1981, pp.
20-21, which is incorporated herein by reference. Illustrative
examples of adhesives include polyethylene oxide and acrylic
materials. Commercial examples of braze adhesives include "4B Braze
Binder.TM.", available from Cotronics Corporation. The adhesive can
be applied by various techniques. For example, liquid-like
adhesives can be sprayed or coated onto the surface. A thin mat or
film with double-sided adhesion could alternatively be used, e.g.,
3M Company's 467 .TM. Adhesive Tape.
[0051] The bond coat powder can then be randomly applied over the
adhesive by a variety of techniques, e.g., sprinkling, pouring,
blowing, roll-depositing, and the like. After the deposition, the
excess powder is removed from the substrate (e.g., by shaking or by
being blown off), leaving substantially a single layer of bond coat
particles. As described previously, the size of the particles
depends in large part on the degree of roughness required for the
bond coat. The green coating (to which the braze material is
attached) is then fused to the substrate, as described above. The
resulting coating system is substantially identical to that formed
in the first embodiment.
[0052] In another alternative embodiment, the bond coat material
can be used in the form of a second slurry, i.e., separate from the
slurry which contains the braze material. The second slurry would
be formed with at least one solvent, i.e., a solvent compatible
with the particular bond coat composition. The slurry would also
contain one or more of the other additives described previously,
e.g., binders, dispersants, and the like. Moreover, the slurry can
be applied over the first slurry by any of the techniques described
above, such as spraying. In preferred embodiments, some or all of
the volatile component in the first slurry is removed before the
application of the second slurry, to avoid bubbling. Removal of the
volatiles is usually carried out by heating, as described above.
Volatiles are then removed from the second slurry in a same or
similar manner, prior to the fusing step. The resulting coating
system is substantially identical to that formed in the other
embodiments.
[0053] As another alternative, the bond coat can be in the form of
a second slurry which is then pre-mixed with the first slurry. The
resulting pre-mixture can be applied to the substrate, prior to
removal of the volatile component. Fusing is then carried out in
the manner described previously.
[0054] In some embodiments of the present invention, an overcoat is
applied over the bond coat, after the bond coat material has been
fused to the substrate with the braze material. The overcoat is
usually a thermal barrier coating, but it could be any type of
coating which provides environmental protection, i.e., protection
of the substrate from the adverse effects of oxidation, corrosion,
or chemical attack. The overcoat could also be a wear-resistance
coating. Moreover, the overcoat is usually ceramic, but could
alternatively be metallic.
[0055] Ceramic thermal barrier coatings are often (but not always)
zirconia-based. As used herein, "zirconia-based" embraces ceramic
materials which contain at least about 50% zirconia, by weight.
Zirconia is a well-known compound for barrier coatings. Its use is
described, for example, in Kirk-Othmer's Encyclopedia of Chemical
Technology, 3rd Edition, V. 24, pp. 882-883 (1984). In preferred
embodiments, the zirconia is chemically stabilized by being blended
with a material such as yttrium oxide, calcium oxide, magnesium
oxide, cerium oxide, scandium oxide, or mixtures of any of those
materials. In one specific example, zirconia can be blended with
about 1% by weight to about 20% by weight yttrium oxide (based on
their combined weight), and preferably, from about 3%-10% yttrium
oxide.
[0056] Various techniques can be used to apply the ceramic coating.
Non-limiting examples include a thermal spray technique such as
APS; physical vapor deposition (PVD); or electron beam physical
vapor deposition (EB-PVD). Those of ordinary skill in the art are
familiar with the details regarding each of these deposition
techniques. Related references include Kirk-Othmer's Encyclopedia
of Chemical Technology, 3rd Edition, Vol. 15, (1981) and Vol. 20
(1982); Ullmann's Encyclopedia of Industrial Chemistry, Fifth
Edition; Volume A6, VCH Publisher (1986); Scientific American, H.
Herman, September 1988; and U.S. Pat. No. 5,384,200. Ceramic slurry
techniques or sol gel techniques can also be used to apply the
ceramic coating.
[0057] Examples of other types of materials for the overcoat
include wear-resistant coatings, e.g., carbide coatings such as
chromium carbide and tungsten carbide, and those formed from
cobalt-molybdenum-chromium-si- licon. Other types of material could
be used as well, e.g., alumina, mullite, zircon, and glassy-type
materials such as strontium-calcium-zirconate glass. Those of
ordinary skill in the art will be able to select the most
appropriate material for a given end use application. Methods for
preparing and applying such materials are those described above for
the zirconia TBC's, or consist of other techniques well-known in
the art. Moreover, some of the overcoats can be prepared and
applied in the form of a slurry over the bond coat, as mentioned
above. Slurry-based overcoats are also described in the
commonly-assigned U.S. patent application of D. Sangeeta, Ser. No.
09/557,393, filed on Apr. 24, 2000 and incorporated herein by
reference. For example, the Summary of the Invention and other
sections of that patent application are instructive.
[0058] Another embodiment of this invention is directed to a method
for replacing a bond coat previously applied to a metal-based
substrate. The replacement of the bond coat is often a part of the
overall process of repairing a worn or damaged TBC. Careful repair
of a TBC "system" (bond coat and TBC) is critical in preventing
degradation of the substrate. In the case of a turbine engine
component, for example, it may be necessary to repair the coating
while the turbine is in service, i.e., after its delivery from the
manufacturing site. The process disclosed herein provides a means
for rapidly repairing or replacing selected areas of an existing
TBC system, without having to completely remove the coatings from
the entire part. The process is especially useful for repairing
coatings which are situated in areas not easily accessible to other
repair techniques.
[0059] The steps for replacing the bond coat usually comprise:
[0060] (i) removing the existing bond coat (and a worn or damaged
overcoat, if present) from a selected area on the substrate;
[0061] (ii) applying a slurry which comprises braze material to the
selected area, wherein the slurry also contains a volatile
component;
[0062] (iii) applying additional bond coat material to the selected
area; and
[0063] (iv) fusing the braze material and bond coat material to the
selected area.
[0064] As described previously, a single slurry can be used,
containing both the braze material and the bond coat material.
Alternatively, two separate slurries can be used. As another
alternative, a braze slurry can be applied and then dried, followed
by the application of an adhesive layer. Bond coat material can
then be applied to the adhesive layer.
[0065] The slurry and bond coat material can be air-dried between
steps (iii) and (iv). Heating means, such as an IR lamp, may be
used to accelerate removal of the volatile component. The fusing
step is often carried out by using a torch or other portable
heating apparatus.
[0066] In the case of a turbine engine component which includes the
coating being repaired, the heat evolved during engine operation
may be sufficient to remove the volatile component and carry out
fusing step (iv). This means of heating and curing could in fact be
postponed until a slurry-based overcoat has been applied, as
described below.
[0067] An overcoat can then be applied over the bond coat, in those
instances in which an overcoat is being replaced. Usually, the
overcoat (e.g., a TBC) will be applied by a thermal spray process
in a repair setting. Plasma spraying is one convenient technique.
However, the overcoat can alternatively be applied over the bond
coat in the form of a slurry, as discussed above (application Ser.
No. 09/557,393 of Sangeeta). As mentioned earlier, turbine engine
operation temperatures may be sufficient to remove all volatile
material, fuse the braze material and bond coat to the substrate;
and cure the overcoat, all in a single step.
[0068] Another embodiment of this invention is a slurry composition
which comprises braze material and bond coat material. Such a
slurry is useful for applying a bond coat, as described above.
Standard liquid brazes or activated diffusion brazes can be used in
the slurry. When the slurry is being applied to a nickel-base
superalloy, the braze alloy usually contains at least about 40% by
weight nickel, along with various other elements, like chromium,
aluminum, and yttrium. The average particle size of the braze alloy
is usually in the range of about 20 microns to about 150 microns,
as mentioned above.
[0069] The bond coat material in the slurry is usually of the
MCrAlX type, as described previously. The size of the bond coat
particles may vary somewhat. They often have an average particle
size of at least about 45 microns.
[0070] The choice of solvent for the slurry will depend in part on
the solid components contained therein, and on the manner in which
it will be applied to the substrate. Exemplary solvents are
described above, along with binder materials and a variety of other
additives, e.g., dispersants, wetting agents, and stabilizers. The
level of braze material and bond coat in the slurry will depend on
various factors, such as the desired thickness of the bond coat;
the solubility and dispersibility of the bond coat and braze
materials in the solvent or solvent mixture; and the manner in
which the slurry will be applied. Usually, the slurry comprises
about 20% by weight to about 50% by weight braze material, and
about 50% by weight to about 80% by weight bond coat material,
based on total slurry weight. The slurry typically contains about
10% or less by weight solvent, and about 10% or less by weight
binder.
[0071] Still another embodiment of this invention is directed to an
article, comprising:
[0072] (a) a metal-based substrate, e.g., one formed of a
superalloy; and
[0073] (b) a volatile-containing slurry on the substrate,
comprising braze material and bond coat material. The particular
components which may be found in such a slurry have been described
previously. When the volatile component in the slurry has been
substantially removed, a green layer remains. The green layer is
then fused to the substrate, e.g., by a brazing technique. In
preferred embodiments, the braze material forms a continuous matrix
phase in which the bond coat particles are embedded. The size of
the bond coat particles can be selected to cause them to protrude
beyond the matrix phase. In that instance, they serve as a
relatively rough surface, e.g., one having an R.sub.a of greater
than about 200 micro-inches, and preferably, greater than about 300
micro-inches. Such a surface provides excellent adhesion to a
subsequently-applied ceramic layer. An article containing such a
layer (e.g., a zirconia-based TBC) is also within the scope of this
invention.
[0074] In order that those skilled in the art may better understand
the invention, the following examples are provided by way of
illustration, and not by way of limitation.
EXAMPLE 1
[0075] Sample A was provided for the purpose of comparison, and
represents a typical TBC system. The substrate was a coupon made
from a nickel-base superalloy. The coupon was grit-blasted and
ultrasonically cleaned. A NiCrAlY-type bond coat was then air
plasma-sprayed (APS) onto the substrate surface. The nominal bond
coat composition was as follows: 68 wt % Ni, 22 wt % Cr, 9 wt % Al,
and 1 wt % Y. The thickness of the bond coat was in the range of
about 5-8 mils (about 127-203 microns). It had an average roughness
R.sub.a of about 500 to about 900 micro-inches. A TBC (thermal
barrier coating: yttria-stabilized zirconia, with 8 wt % by weight
yttria) was then air plasma-sprayed over the bond coat. The
thickness of the TBC was in the range of about 10-12 mils (about
254-305 microns).
[0076] Sample B represented an embodiment of the present invention.
A slurry was first prepared by adding the following components to
acetone, under agitation:
[0077] (a) coarse NiCrAlY-type bond coat powder, having an
approximate composition as follows: 68 wt % Ni, 22 wt % Cr. 9 wt %
Al, and 1 wt % Y. The powder had an average particle size of -30
+100 mesh, i.e., 150-600 microns.
[0078] (b) High-temperature braze powder, commercially available as
Amdry.RTM. 100, having the following approximate composition: 10%
by weight silicon; 19% by weight chromium, base nickel. The powder
had an average particle size of about-100 mesh, i.e., less than
about 150 microns.
[0079] (c) Nicrobraz.RTM. 300 binder (ethyl methacrylate in
trichloroethane; available from Wall Colmonoy, Inc., Madison
Heights, Mich.)
[0080] The metal powders were dry-mixed (50 wt % of component (a)
and 50 wt % of component (b)). Components (c) and (d) were then
added and mixed (10 wt % of each to the total slurry weight).
[0081] The slurry was applied (by brushing) to the same type of
superalloy coupon used for sample A. The wet thickness of the
slurry was about 5 mils (127 microns). The slurry was then allowed
to air-dry for about 12 hours, during which at least about 15 wt %
of the volatile material was removed. The resulting green coating
was then heated in a vacuum furnace at a brazing temperature of
about 1093-1204.degree. C. (2000-2200.degree. F.), for about 1
hour. A dense, rough bond coat was produced, having an R.sub.a of
about 25 microns (about 984 micro-inches). The same type of thermal
barrier coating (zirconia-based) used in sample A was then air
plasma-sprayed over the bond coat.
[0082] FIG. 1 is a cross-sectional photomicrograph of the coating
system for sample A. Region I is the substrate. Region II is an
oxide region which has begun to form between the substrate and the
bond coat, as a result of thermal testing. Region III is the bond
coat itself, exhibiting the typical overlapping of bond coat
material "splats" which result from APS deposition. Region IV is
the TBC.
[0083] The overall coating system of sample A exhibits good
integrity for some end uses, and for a projected service life.
However, Region II results from accelerated oxidation at the bond
coat-substrate interface, toward the end of a simulated service
life. The oxidation will eventually result in coating failure, by
causing most or all of the TBC and bond coat to become detached
from the substrate.
[0084] FIG. 2 is a cross-sectional photomicrograph of the coating
system for sample B, prepared according to an embodiment of the
present invention. The coating system was subjected to the same
amount of thermal testing as sample A. Region V is the substrate.
Region VI is the slurry layer applied and brazed over the
substrate. Region VII is the TBC. The absence of the oxidation
region seen in FIG. 1 indicates that accelerated oxidation at the
bond coat-substrate interface has not taken place.
[0085] The type of thermal testing carried out for each sample was
Furnace Cycle Testing (FCT). One cycle represented 45 minutes at
2000.degree. F. (1093.degree. C.). The process continued for 300
cycles for each sample. The results demonstrated that the present
invention (sample B) had a furnace cycle life which was about 3
times greater than that of the comparative base line sample (sample
A).
EXAMPLE 2
[0086] In this example, the same type of substrate was used, to
prepare sample C. A slurry was prepared, containing 80 wt % of the
Amdry.RTM. 100 high-temperature braze powder, along with 10 wt %
water and 10 wt % polyethylene oxide binder. The slurry was applied
to the substrate, to a wet thickness of about 5 mils (127 microns).
The slurry was then allowed to dry for about 14-16 hours. About 15
wt % of the volatile material was removed in this drying step,
leaving a green layer. A layer of braze contact adhesive
(Nicrobraz.RTM.300) was then applied over the green layer.
[0087] The coarse NiCrAlY-type bond coat powder used in Example 1
(sample B) was then sprinkled onto the contact adhesive, to produce
a mono-layer of coarse powder. The excess bond coat powder was
blown off. The coupon was then heated in a vacuum furnace at a
brazing temperature of about 1093-1204.degree. C.
(2000-2200.degree. F.), for about 0.25 --2 hours, to produce a
dense, rough bond coat (R.sub.a of about 25 microns/984
micro-inches). The same type of thermal barrier coating
(zirconia-based) used in sample A was then air plasma-sprayed over
the bond coat.
[0088] FCT tests were carried out, as in Example 1. Sample C
displayed approximately the same properties (resistance-to-cracking
and delamination) as those of sample B. Moreover, sample C showed
no indication of the accelerated oxidation at the bond
coat-substrate interface, i.e., as evidenced for sample A.
[0089] Preferred embodiments have been set forth for the purpose of
illustration. However, the foregoing description should not be
deemed to be a limitation on the boundaries of the invention.
Accordingly, various modifications, adaptations, and alternatives
may occur to one skilled in the art without departing from the
spirit and scope of the present invention.
[0090] All of the patents, articles, and texts mentioned above are
incorporated herein by reference.
* * * * *