U.S. patent application number 13/744958 was filed with the patent office on 2013-05-23 for articles for high temperature service and methods for their manufacture.
This patent application is currently assigned to GENERAL ELECTRIC COMPANY. The applicant listed for this patent is General Electric Company. Invention is credited to Curtis Alan Johnson, Krishan Lal Luthra, Peter Joel Meschter, Larry Steven Rosenzweig, Reza Sarrafi-Nour.
Application Number | 20130130042 13/744958 |
Document ID | / |
Family ID | 43625362 |
Filed Date | 2013-05-23 |
United States Patent
Application |
20130130042 |
Kind Code |
A1 |
Sarrafi-Nour; Reza ; et
al. |
May 23, 2013 |
ARTICLES FOR HIGH TEMPERATURE SERVICE AND METHODS FOR THEIR
MANUFACTURE
Abstract
An article for use in aggressive environments is presented. In
one embodiment, the article comprises a substrate and a
self-sealing and substantially hermetic sealing layer comprising an
alkaline-earth aluminosilicate disposed over the bondcoat. The
substrate may be any high-temperature material, including, for
instance, silicon-bearing ceramics and ceramic matrix
composites.
Inventors: |
Sarrafi-Nour; Reza; (Clifton
Park, NY) ; Meschter; Peter Joel; (Niskayuna, NY)
; Johnson; Curtis Alan; (Niskayuna, NY) ; Luthra;
Krishan Lal; (Niskayuna, NY) ; Rosenzweig; Larry
Steven; (Clifton Park, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
General Electric Company; |
Schenectady |
NY |
US |
|
|
Assignee: |
GENERAL ELECTRIC COMPANY
Schenectady
NY
|
Family ID: |
43625362 |
Appl. No.: |
13/744958 |
Filed: |
January 18, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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11941415 |
Nov 16, 2007 |
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13744958 |
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Current U.S.
Class: |
428/448 ;
106/286.6; 423/328.1; 428/446 |
Current CPC
Class: |
C23C 30/00 20130101;
C04B 41/89 20130101; C23C 26/00 20130101; C09D 1/02 20130101; C01B
32/956 20170801; C04B 41/52 20130101; C23C 28/042 20130101; B32B
9/04 20130101; C09D 5/00 20130101; C04B 41/52 20130101; C04B
41/4527 20130101; C04B 41/5096 20130101; C04B 41/52 20130101; C04B
41/4527 20130101; C04B 41/5024 20130101; C04B 41/52 20130101; C04B
41/0072 20130101; C04B 41/4527 20130101; C04B 41/5024 20130101 |
Class at
Publication: |
428/448 ;
423/328.1; 106/286.6; 428/446 |
International
Class: |
C09D 5/00 20060101
C09D005/00; B32B 9/04 20060101 B32B009/04 |
Goverment Interests
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH &
DEVELOPMENT
[0002] This invention was made with U.S. Government support under
contract number DE-FC26-05NT42643 awarded by the Department of
Energy. The Government has certain rights in the invention.
Claims
1. An article comprising: a substrate; and a self-sealing and
substantially hermetic sealing layer disposed over the substrate,
wherein the sealing layer comprises an alkaline-earth
aluminosilicate.
2. The article of claim 1, wherein the alkaline-earth
aluminosilicate comprises at least one alkaline-earth element
selected from the group consisting of strontium and barium.
3. The article of claim 2, wherein the sealing layer comprises
barium strontium aluminosilicate.
4. The article of claim 1, wherein the alkaline-earth
aluminosilicate comprises up to about 80 mole % silica.
5. The article of claim 1, wherein the alkaline-earth
aluminosilicate comprises up to about 60 mole % alumina.
6. The article of claim 1, wherein the alkaline-earth
aluminosilicate comprises up to about 50 mole % alkaline-earth
oxide.
7. The article of claim 1, wherein the alkaline-earth
aluminosilicate has a composition in the range bounded by a region
in alumina/silica/alkaline-earth oxide compositional space defined
by a first line connecting a first composition point at about (22.5
mole % alumina, 55 mole % silica, 22.5 mole % alkaline-earth oxide)
with a second composition point at about (43.8 mole % alumina, 44.6
mole % silica, 11.6 mole % alkaline-earth oxide); a second line
connecting the second composition point with a third composition
point at about (49.3 mole % alumina, 29.6 mole % silica, 21.1 mole
% alkaline-earth oxide); a third line connecting the third
composition point with a fourth composition point at about (38.4
mole % alumina, 23.6 mole % silica, 38.0 mole % alkaline-earth
oxide); a fourth line connecting the fourth composition point with
a fifth composition point at about (19.3 mole % alumina, 46.5 mole
% silica, 34.2 mole % alkaline-earth oxide); and a fifth line
connecting the fifth composition point with the first composition
point.
8. The article of claim 1, wherein the alkaline-earth
aluminosilicate has a composition in the range bounded by a region
in alumina/silica/alkaline-earth oxide compositional space defined
by a first line connecting a first composition point at about (25
mole % alumina, 50 mole % silica, 25 mole % alkaline-earth oxide)
with a second composition point at about (33.7 mole % alumina, 47.5
mole % silica, 18.8 mole % alkaline-earth oxide); a second line
connecting the second composition point with a third composition
point at about (45.5 mole % alumina, 36.4 mole % silica, 18.2 mole
% alkaline-earth oxide); a third line connecting the third
composition point with a fourth composition point at about (39.6
mole % alumina, 38.0 mole % silica, 22.4 mole % alkaline-earth
oxide); a fourth line connecting the fourth composition point with
a fifth composition point at about (31.5 mole % alumina, 37.0 mole
% silica, 31.5 mole % alkaline-earth oxide); a fifth line
connecting the fifth composition point with a sixth composition
point at about (19.3 mole % alumina, 46.5 mole % silica, 33.9 mole
% alkaline-earth oxide); and a sixth line connecting the sixth
composition point with the first composition point.
9. The article of claim 1, wherein the sealing layer is
substantially free of any additional material disposed within
internal surfaces of the sealing layer.
10. The article of claim 1, wherein the substrate comprises
silicon.
11. The article of claim 1, wherein the substrate comprises at
least one material selected from the group consisting of silicon
nitride, molybdenum disilicide, and silicon carbide.
12. The article of claim 11, wherein the substrate comprises a
ceramic matrix composite material.
13. The article of claim 12, wherein the composite comprises a
matrix phase and a reinforcement phase, and wherein the matrix
phase and the reinforcement phase comprise silicon carbide.
14. The article of claim 1, wherein the article comprises a
component of a gas turbine assembly.
15. The article of claim 1, further comprising a bondcoat disposed
between the substrate and the sealing layer.
16. The article of claim 15, wherein the bondcoat comprises
silicon.
17. The article of claim 15, wherein the bondcoat comprises at
least one material selected from the group consisting of elemental
silicon and a silicide.
18. The article of claim 1, further comprising a topcoat disposed
over the sealing layer.
19. The article of claim 18, wherein the topcoat comprises a
ceramic material.
20. The article of claim 19, wherein the ceramic material is
selected from the group consisting of silicates, aluminosilicates,
and yttria-stabilized zirconia.
21. The article of claim 19, wherein the topcoat comprises at least
one material selected from the group consisting of a rare earth
monosilicate and a rare earth disilicate.
22. The article of claim 21, wherein the topcoat comprises an outer
layer of rare earth monosilicate and an inner layer of rare earth
disilicate.
23. The article of claim 15, further comprising an intermediate
layer disposed between the sealing layer and the bondcoat, wherein
the intermediate layer comprises a barrier material that is
substantially inert with respect to silica.
24. The article of claim 23, wherein the barrier material comprises
a rare-earth disilicate.
25. The article of claim 24, wherein the barrier material comprises
yttrium disilicate.
26. An article comprising: a substrate comprising silicon; a
bondcoat disposed over the substrate, the bondcoat comprising
silicon; a self-sealing and substantially hermetic sealing layer
disposed over the bondcoat, the sealing layer comprising an
alkaline-earth aluminosilicate having a composition in the range
bounded by a region in alumina/silica/alkaline-earth oxide
compositional space defined by a first line connecting a first
composition point at about (11.8 mole % alumina, 76.1 mole %
silica, 12.1 mole % alkaline-earth oxide) with a 225497-2 second
composition point at about (58.6 mole % alumina, 29.8 mole %
silica, 11.6 mole % alkaline-earth oxide); a second line connecting
the second composition point with a third composition point at
about (44.3 mole % alumina, 8.2 mole % silica, 47.5 mole %
alkaline-earth oxide); a third line connecting the third
composition point with a fourth composition point at about (13.6
mole % alumina, 43.8 mole % silica, 42.6 mole % alkaline-earth
oxide); and a fourth line connecting the fourth composition point
with the first composition point; an intermediate layer disposed
between the sealing layer and the bondcoat, wherein the
intermediate layer comprises a barrier material that is
substantially inert with respect to silica; and a topcoat disposed
over the sealing layer.
Description
RELATED APPLICATIONS
[0001] This application is a divisional of U.S. patent application
Ser. No. 11/941,415, filed 16 Nov. 2007, which is herein
incorporated by reference.
BACKGROUND
[0003] This invention relates to high-temperature machine
components. More particularly, this invention relates to coating
systems for protecting machine components from exposure to
high-temperature environments. This invention also relates to
methods for protecting articles.
[0004] High-temperature materials, such as, for example, ceramics,
alloys, and intermetallics, offer attractive properties for use in
structures designed for service at high temperatures in such
applications as gas turbine engines, heat exchangers, and internal
combustion engines, for example. However, the environments
characteristic of these applications often contain reactive
species, such as water vapor, which at high temperatures may cause
significant degradation of the material structure. For example,
water vapor has been shown to cause significant surface recession
and mass loss in silicon-bearing materials. The water vapor reacts
with the structural material at high temperatures to form volatile
silicon-containing species, often resulting in unacceptably high
recession rates.
[0005] Environmental bather coatings (EBC's) are applied to
silicon-bearing materials and other material susceptible to attack
by reactive species, such as high temperature water vapor; EBC's
provide protection by prohibiting contact between the environment
and the surface of the material. EBC's applied to silicon-bearing
materials, for example, are designed to be relatively stable
chemically in high-temperature, water vapor-containing
environments. One exemplary conventional EBC system, as described
in U.S. Pat. No. 6,410,148, comprises a silicon or silica bond
layer applied to a silicon-bearing substrate; an intermediate layer
comprising mullite or a mullite-alkaline earth aluminosilicate
mixture deposited over the bond layer; and a top layer comprising
an alkaline earth aluminosilicate deposited over the intermediate
layer. In another example, U.S. Pat. No. 6,296,941, the top layer
is a yttrium silicate layer rather than an aluminosilicate.
[0006] The above coating systems can provide suitable protection
for articles in demanding environments, but opportunities for
improvement in coating performance exist. Current EBC technology
generally uses plasma spray processes to deposit the coatings,
primarily because of the flexibility of the process to deposit a
large variety of materials, its ability to provide a wide spectrum
of coating thicknesses without major process modifications, and the
relative ease of depositing a coating layer. However, ceramic
coatings processed by plasma spraying often contain undesirable
open porosity in the form of a network of fine cracks
("microcracks") intercepting otherwise closed pores and voids. The
microcrack network is formed primarily by quench and solidification
cracks and voids inherent in the coating deposition process; cracks
often form between layers of successively deposited material and
between the individual "splats" formed when melted or partially
melted particles are sprayed onto the coating surface. For EBC
applications, open porosity in the coating can be detrimental. It
provides a rapid path for penetration of water vapor and other
gaseous species and, hence, accelerated localized deterioration of
the underlying coating layers.
[0007] Various methods have been implemented to alleviate the
problem of open porosity in ceramic coatings. In some applications,
the coatings are applied onto a hot substrate (T>800 degrees
Celsius) using plasma spray processing. Deposition on a hot
substrate reduces the difference between the substrate temperature
and the melting temperature of the coating material, and thus
reduces the tendency for formation of quench cracks. However,
extension of the hot deposition process technique to large
components is challenging, owing to the high substrate temperatures
and the constraints associated with manipulation of the parts and
the coating hardware. In other applications, the plasma sprayed EBC
coating is submitted to a post-deposition process to impregnate the
non-hermetic coating structure with precursors of suitable
materials, for example, soluble organic and inorganic salts and
alcoxides that yield upon heat-treatment a final pore-filling
material compatible with the coating matrix. The filler material
blocks or restricts the pathway for water vapor penetration. Such a
process is described in U.S. patent application Ser. No.
11/298,735. Although this method is relatively easy to implement,
it may require multiple impregnation-burnout cycles to achieve
coating permeability improvements, and in certain cases may provide
an incompletely hermetic coating structure.
[0008] Therefore, there is a need for articles protected by robust
coating systems having improved capability to serve as a barrier to
water vapor and other detrimental environmental species. There is
also a further need for methods to produce these articles
economically and reproducibly.
BRIEF DESCRIPTION
[0009] Embodiments of the present invention are provided to meet
this and other needs. One embodiment is an article comprising a
substrate and a self-sealing and substantially hermetic sealing
layer disposed over the substrate. The sealing layer comprises an
alkaline-earth aluminosilicate. The substrate may be any
high-temperature material, including, for instance, silicon-bearing
ceramics and ceramic matrix composites.
[0010] Another embodiment is an article comprising a substrate
comprising silicon; a bondcoat disposed over the substrate, the
bondcoat comprising silicon; a self-sealing and substantially
hermetic sealing layer disposed over the bondcoat; an intermediate
layer disposed between the sealing layer and the bondcoat, wherein
the intermediate layer comprises a barrier material that is
substantially inert with respect to silica; and a topcoat disposed
over the sealing layer. The sealing layer comprises an
alkaline-earth aluminosilicate having a composition in the range
bounded by a region in alumina/silica/alkaline-earth oxide
compositional space defined by (1) a first line connecting a first
composition point at about (11.8 mole % alumina, 76.1 mole %
silica, 12.1 mole % alkaline-earth oxide) with a second composition
point at about (58.6 mole % alumina, 29.8 mole % silica, 11.6 mole
% alkaline-earth oxide); (2) a second line connecting the second
composition point with a third composition point at about (44.3
mole % alumina, 8.2 mole % silica, 47.5 mole % alkaline-earth
oxide); (3) a third line connecting the third composition point
with a fourth composition point at about (13.6 mole % alumina, 43.8
mole % silica, 42.6 mole % alkaline-earth oxide); and (4) a fourth
line connecting the fourth composition point with the first
composition point.
[0011] Another embodiment is a method for making an article. The
method comprises providing a substrate; disposing a self-sealing
layer over the substrate; and heating the sealing layer to a
sealing temperature at which at least a portion of the sealing
layer will flow. The sealing layer comprises an alkaline-earth
aluminosilicate.
[0012] Another embodiment is a method for making an article. The
method comprises providing a substrate comprising silicon;
disposing a bondcoat over the substrate, the bondcoat comprising
silicon; disposing an intermediate layer over the bondcoat, wherein
the intermediate layer comprises a barrier material that is
substantially inert with respect to silica; disposing a
self-sealing layer over the intermediate layer; heating the sealing
layer to a sealing temperature at which at least a portion of the
sealing layer will flow and maintaining the sealing layer at the
sealing temperature for an effective time to form a substantially
hermetic layer; and disposing a topcoat over the sealing layer. The
self-sealing layer comprises an alkaline-earth aluminosilicate
having a composition in the range bounded by a region in
alumina/silica/alkaline-earth oxide compositional space defined by
(1) a first line connecting a first composition point at about
(11.8 mole % alumina, 76.1 mole % silica, 12.1 mole %
alkaline-earth oxide) with a second composition point at about
(58.6 mole % alumina, 29.8 mole % silica, 11.6 mole %
alkaline-earth oxide); (2) a second line connecting the second
composition point with a third composition point at about (44.3
mole % alumina, 8.2 mole % silica, 47.5 mole % alkaline-earth
oxide); (3) a third line connecting the third composition point
with a fourth composition point at about (13.6 mole % alumina, 43.8
mole % silica, 42.6 mole % alkaline-earth oxide); and (4) a fourth
line connecting the fourth composition point with the first
composition point.
DRAWINGS
[0013] These and other features, aspects, and advantages of the
present invention will become better understood when the following
detailed description is read with reference to the accompanying
drawings in which like characters represent like parts throughout
the drawings, wherein:
[0014] FIG. 1 is a schematic illustration of
alumina/silica/alkaline-earth oxide compositional space, drawn for
convenience on a ternary-style composition diagram of a type
commonly used in the art, with certain compositions highlighted in
accordance with embodiments of the present invention; and
[0015] FIG. 2 is a schematic cross-section illustration of one
exemplary embodiment of the present invention.
DETAILED DESCRIPTION
[0016] According to one embodiment of the present invention, an
article comprises a substrate and a self-sealing and substantially
hermetic coating, referred to herein as a "sealing layer," disposed
over the substrate. The term "self-sealing" as used herein means
that at least a fraction of the coating is made of material
("sealing material") capable of forming a flowable phase, such as a
liquid or a glassy phase, at or above a known temperature ("sealing
temperature") that is below a melting temperature of the bulk of
the coating. This liquid or glassy phase has a viscosity at the
sealing temperature suitable to allow the flowable phase to flow
into and at least partially fill defects such as cracks and pores,
thereby enhancing the ability of the coating to block the movement
of detrimental species from the external environment into the
substrate. By this mechanism, the coating can seal itself; that is,
it can increase its resistance to transport of detrimental species
without the use of, for example, a separate sealing material
deposited within pores and cracks. Thus, in some embodiments, the
sealing layer is substantially free of any additional material
disposed within internal surfaces of the sealing layer; this
limitation, of course, does not preclude embodiments where an
additional layer is disposed over the sealing layer. The term
"substantially hermetic" as used herein means that the coating has
a gas permeability that is below about 2.times.10.sup.-14 cm.sup.2
(about 2.times.10.sup.-6 Darcy), the detection limit of commonly
used measurement techniques.
[0017] The fraction of the sealing layer made of the sealing
material may be selected depending on a number of factors,
including, for example, the expected density of defects that need
to be sealed and the expected viscosity of the flowable phase. In
some embodiments, this fraction is at least about 1% by volume of
total sealing layer; in particular embodiments, the fraction is at
least 10% by volume.
[0018] The sealing temperature typically is related to a phase
transition or transformation that occurs within the sealing
material. For instance, the sealing temperature may be chosen to be
above a glass transition temperature for a glassy phase that forms
in the sealing material. Alternatively, the sealing temperature may
be chosen to be at or above a melting temperature, such as a
eutectic temperature or a solidus temperature, for a particular
phase or composition present in the sealing material. In some
embodiments, the sealing temperature is at least about 950 degrees
Celsius, and in particular embodiments, the sealing temperature is
at least about 1220 degrees Celsius. In certain embodiments, the
operating temperature of the article is selected to be below the
sealing temperature, so that the coating will not re-form a
flowable phase during service. However, there may be certain
applications where having a flowable phase in the sealing layer
during service is acceptable or desirable, and so embodiments of
the present invention also include those where the sealing
temperature is below the service temperature.
[0019] In general terms, the composition of the sealing layer is
selected so that, at a given selected sealing temperature, at least
a fraction of the sealing layer is either a liquid or a flowable
glassy phase, as described above. The phase transformation behavior
as a function of composition and temperature is well known in the
art for many materials, and thus the procedure for selecting
suitable materials for use in embodiments of the present invention
will be apparent to practitioners based on the general descriptions
presented herein. In addition to the phase transformation
characteristics described above, other material characteristics
such as, for instance, environmental resistance, ease of
manufacture, chemical compatibility with adjacent materials, and
other properties, are generally taken into account when selecting a
particular material for use in a specific application.
[0020] The sealing layer comprises an alkaline-earth
aluminosilicate. These materials are selected because of their
utility as environmental barrier coatings for use in such high
temperature applications as turbomachinery components. As used
herein, the term "alkaline-earth aluminosilicate" is broadly
applicable to any material that is the product of mixing or
reacting (1) at least one alkaline-earth oxide, (2) silicon oxide,
and (3) aluminum oxide, and this term applies to any material
having a composition that falls within a ternary isothermal section
having alkaline-earth oxide, silicon oxide, and aluminum oxide at
respective apexes, as depicted in FIG. 1. It should be noted that,
although a ternary isothermal section is depicted, the
alkaline-earth oxide component may, in some embodiments, encompass
more than one alkaline-earth element, thereby making the overall
material a mixture or product of more than three oxides. For
example, a composition made by mixing and/or reacting (1) two or
more alkaline-earth oxides, (2) silicon oxide, and (3) aluminum
oxide, is considered to be within the scope of the term
"alkaline-earth aluminosilicate" as used herein. In some
embodiments, the alkaline-earth aluminosilicate comprises at least
one alkaline-earth element selected from the group consisting of
strontium and barium.
[0021] Throughout this description, the composition of the sealing
layer will be described in terms of equivalent mole percent of
aluminum oxide (Al.sub.2O.sub.3, or "alumina"), silicon oxide
(SiO.sub.2 or "silica"), and alkaline-earth oxide. This notation is
consistent with that commonly used in the art, where, for example,
a compound such as barium strontium aluminosilicate is often
written as (Ba,Sr)O.Al.sub.2O.sub.3.2SiO.sub.2 (50 mol. %
SiO.sub.2+25 mol. % Al.sub.2O.sub.3+25 mol. % (Ba,Sr)O) instead of
(Ba,Sr)Al.sub.2Si.sub.2O.sub.8.
[0022] Certain alkaline-earth aluminosilicate compositions provide
relative advantages due to their ability to form effective amounts
of desirable flowable phases (i.e., liquid or glass), to resist
high temperature environments, to be economically processed, or a
combination of these or other factors. Generally, the silica,
alumina, and alkaline-earth oxide are provided in relative
proportions that enable the formation of a glassy phase or a liquid
phase above a temperature of about 950 degrees Celsius. In one
embodiment, the alkaline-earth aluminosilicate comprises up to
about 80 mole % silica. In another embodiment, the alkaline-earth
aluminosilicate comprises up to about 60 mole % alumina. In yet
another embodiment, the alkaline-earth aluminosilicate comprises up
to about 50 mole % alkaline-earth oxide.
[0023] Depending on the particular application desired for the
coating, other alkaline-earth aluminosilicate compositions may be
selected for service. The details of composition selection for the
seal layer may be controlled by several factors, including, but not
limited to, the nature and the volume fraction of the flowable
phases, the overall thermal expansion coefficient of the seal
layer, the phase composition of the seal layer and the vapor
pressure and chemical activity of volatile species formed as a
consequence of interaction with the environment (should an open
pathway exist between the seal layer and the atmosphere). Referring
to FIG. 1, in some embodiments the alkaline-earth aluminosilicate
has a maximum silica content that is a function of the respective
contents of alumina and alkaline-earth oxide. In one embodiment,
the alkaline-earth aluminosilicate has a composition in the range
bounded by a region in alumina/silica/alkaline-earth oxide
compositional space defined by quadrilateral ABCD in FIG. 1, where
point A is (11.8 mole % alumina, 76.1 mole % silica, 12.1 mole %
alkaline-earth oxide), point B is (58.6 mole % alumina, 29.8 mole %
silica, 11.6 mole % alkaline-earth oxide), point C is (44.3 mole %
alumina, 8.2 mole % silica, 47.5 mole % alkaline-earth oxide), and
point D is (13.6 mole % alumina, 43.8 mole % silica, 42.6 mole %
alkaline-earth oxide). In certain embodiments, the composition is
in the range defined by polygon EFGHI in FIG. 1, wherein point E is
(22.5 mole % alumina, 55 mole % silica, 22.5 mole % alkaline-earth
oxide); point F is (43.8 mole % alumina, 44.6 mole % silica, 11.6
mole % alkaline-earth oxide); point G is (49.3 mole % alumina, 29.6
mole % silica, 21.1 mole alkaline-earth oxide); point H is (38.4
mole % alumina, 23.6 mole % silica, 38.0 mole % alkaline-earth
oxide); and point I is (19.3 mole % alumina, 46.5 mole % silica,
34.2 mole % alkaline-earth oxide). These compositions generally
provide a lower volume fraction of flowable phases for a given
temperature, and a smaller CTE mismatch with many Si-bearing
substrates, than those compositions from outside the EFGHI polygon.
Even further reductions in flowable phase volume fraction and in
CTE mismatch may be obtained in particular embodiments in which the
alkaline-earth aluminosilicate has a composition in the range
defined by polygon JKLMNI in FIG. 1, where point J is (25 mole %
alumina, 50 mole % silica, 25 mole % alkaline-earth oxide); point K
is (33.7 mole % alumina, 47.5 mole % silica, 18.8 mole %
alkaline-earth oxide); point L is (45.5 mole % alumina, 36.4 mole %
silica, 18.1 mole % alkaline-earth oxide); point M is (39.6 mole %
alumina, 38.0 mole % silica, 22.4 mole % alkaline-earth oxide);
point N is (31.5 mole % alumina, 37.0 mole % silica, 31.5 mole %
alkaline-earth oxide); and point I is as defined above.
[0024] FIG. 2 depicts an exemplary article 200 of the present
invention. In this particular embodiment, sealing layer 210 is
disposed over a substrate 202. Substrate 202 may be made from any
suitable material, such as a ceramic, a metal alloy, or an
intermetallic material. In some embodiments the substrate comprises
a ceramic, for example an oxide, nitride, or carbide. Substrate 202
may include a silicon-containing material, such as silicon nitride,
molybdenum disilicide, or silicon carbide. This material, in
certain embodiments, is a ceramic-matrix composite material, such
as a material made of a matrix phase and a reinforcement phase; in
particular embodiments, the matrix phase and the reinforcement
phase comprise silicon carbide. In certain embodiments, article 202
is a component of a gas turbine assembly, such as, for example, a
combustion liner, transition piece, shroud, vane, or blade. The
ability of the sealing layer to protect substrate 202 from exposure
to water vapor at high temperatures may be advantageous for its
application to silicon-bearing turbine components. It will be
understood that although the application of embodiments of the
present invention may be described with reference to applications
on silicon-bearing substrates for protection against attack by
water vapor, such references are exemplary and that embodiments of
the present invention include substrate materials other than
silicon-bearing materials.
[0025] In certain applications, a bondcoat 204 is disposed over
substrate 202, with sealing layer 210 disposed over bondcoat 204.
Bondcoat 204 may be used, for example, to mitigate thermal stresses
or to inhibit chemical reactions between substrate 202 and sealing
layer 210. In some embodiments, such as where substrate 202 is a
silicon-bearing material, the bondcoat 204 comprises silicon. For
example, bondcoat 204 in some embodiments is elemental silicon or a
silicide. In particular embodiments, such as where bondcoat 204
contains silicon or silicon oxide, an intermediate layer (not
shown) is disposed between sealing layer 210 and bondcoat 204. The
intermediate layer is made of a barrier material that is
substantially inert with respect to silicon oxide to promote
chemical stability in the coating system. "Substantially inert"
means that there is at most only incidental interaction (solubility
or reactivity) between silica and the barrier material. Rare-earth
disilicates, such as disilicates of yttrium, ytterbium, lutetium,
scandium, and other rare-earth elements, are non-limiting examples
of suitable barrier materials.
[0026] A topcoat 206, in some embodiments, is disposed over sealing
layer 210. Topcoat 206 may be used to provide thermal insulation (a
thermal barrier coating), environmental protection (an
environmental barrier coating), or a combination of these
functions. The selection of a suitable topcoat material will depend
on the type of environment the article is to be exposed to, the
composition of the underlying coatings and substrate, the cost of
processing, and other factors known in the art. In some
embodiments, topcoat 206 is a ceramic material. Many classes of
ceramic materials are known for their ability to serve as thermal
and/or environmental barrier coatings; these materials include, but
are not limited to, silicates, aluminosilicates, and
yttria-stabilized zirconia. In certain embodiments, topcoat 206
contains a rare earth monosilicate and/or rare earth disilicate; in
particular embodiments, topcoat 206 is a dual-layer coating, with
an outer layer of rare earth monosilicate and an inner layer of
rare earth disilicate. The rare earth elements associated with
these monosilicate and disilicate materials, in some embodiments,
may include one or more of yttrium, ytterbium, lutetium, and
scandium. A particular example is where the outer layer is yttrium
monosilicate and the inner layer is a rare earth disilicate (such
as yttrium disilicate, for instance).
[0027] The thickness of any of the various coating layers described
above is generally chosen to provide adequate protection for a
given service time while keeping thermal stresses to a sustainable
level. Moreover, coating thickness may also be determined by the
ability of a selected coating method to produce a continuous layer
over the deposition area. Non-limiting examples of approximate
thickness ranges for the various coatings include the following:
for the sealing layer, from about 25 micrometers to about 150
micrometers; for the bondcoat, from about 75 micrometers to about
125 micrometers; for the intermediate layer, from about 50
micrometers to about 100 micrometers; for the topcoat layer, from
about 50 micrometers to about 500 micrometers. For the dual-layer
topcoat embodiment described above, the yttrium monosilcate outer
layer can be from about 25 micrometers to about 50 micrometers in
certain embodiments.
[0028] The coatings described above can be deposited using coating
technology known to the art. Embodiments of the present invention
are of particular interest where methods for coating deposition are
used that typically result in a substantial amount of cracking and
internal open porosity. Plasma spray technology and slurry-based
coating processes are examples of commonly used coating methods
that generate coatings with such features. In such cases, the
presence of the sealing layer serves to considerably enhance the
hermeticity, and thus the efficacy of protection, of the coating.
Moreover, in some embodiments the sealing layer may be effective in
sealing cracks or other damage to the coating that may occur after
processing, including for instance damage created during
installation of components, or service of components.
[0029] In order to activate the self-sealing nature of the sealing
layer, the sealing layer is heated to the sealing temperature
(described above) at which at least a portion of the sealing layer
will flow; the flowable portion thus moves into cracks and pores
and, upon solidification, seals off these defects that would
otherwise serve as pathways for detrimental species, such as water
vapor, from the environment to the substrate. Depending upon the
nature of the coating, the economics of the processing, and other
factors, the heating step may be performed immediately after
depositing the sealing layer, after all coatings have been
deposited but prior to putting the finished article into service,
or even during service itself if the service temperature is allowed
to be sufficiently high.
[0030] The sealing temperature is maintained for an effective time
to allow time for the flowable material to reach and at least
partially fill or otherwise seal off the defects. The length of
time needed to achieve this is generally selected based on the
number and nature of the defects to be sealed and the quantity of
flowable material available in the sealing layer. In one
embodiment, the sealing layer is heated to a sealing temperature in
a range from about 950 degrees Celsius to about 1350 degrees
Celsius for a time in the range from about 30 minutes to about 10
hours; in particular embodiments the time is in the range from
about 30 minutes to about 4 hours. In some embodiments, the
temperature is in the range from about 950 degrees Celsius to about
1050 degrees Celsius for a time in the range from about 30 minutes
to about 4 hours, while in other embodiments the temperature is
from about 1250 degrees Celsius to about 1350 degrees Celsius for a
time in the range from about 30 minutes to about 4 hours. The
heating step to seal the coating may be performed in air, vacuum,
an inert atmosphere, or other environment, depending at least in
part on the requirements of the materials being heated (i.e., the
substrate and other coating layers, if present).
[0031] A method for forming an article 200 according to embodiments
of the present invention includes disposing sealing layer 210 over
a substrate 202 and heating the sealing layer 210 as described
above. In particular embodiments, bondcoat 204 is disposed over the
substrate and under the sealing layer 210. In certain embodiments,
topcoat 206 is disposed over sealing layer 210. An intermediate
layer (not shown) as described above may be disposed between
bondcoat 204 and sealing layer 210.
EXAMPLES
Example 1
[0032] A silicon carbide ceramic matrix composite substrate was
coated by plasma spraying the substrate with a silicon bondcoat and
then a layer of yttrium disilicate. Then an alkaline earth
aluminosilicate sealing layer having the following composition: 50
mole % SiO.sub.2-25 mole % Al.sub.2O.sub.3-25 mole % alkaline earth
oxide, where the alkaline earth oxide in this case was a mixture of
BaO and SrO, was deposited on the yttrium disilicate layer. The
substrate was sectioned and metallographically examined after
spraying, and a network of fine cracks was observed throughout the
alkaline-earth aluminosilicate layer. The coated substrate was then
heat treated in air for 30 minutes at 950 degrees Celsius followed
by 30 minutes at 1020 degrees Celsius. Another specimen having the
same set of coatings was heated to 1000 degrees Celsius at a slow
heating rate and was removed from the furnace immediately. Each of
the heat treated specimens described above was sectioned and
metallographically examined, and the network of fine cracks,
visible prior to heat treating, was not visible after heat
treating, indicating the cracks had been sealed during the heat
treatment step. Air permeability tests showed that the permeability
to air of the alkaline earth aluminosilicate layer after heat
treatment was at least a factor of ten lower than that measured in
the as-sprayed condition, demonstrating an improvement in coating
hermeticity.
Example 2
[0033] A multi-layered coating assembly comprising a first layer of
yttrium disilicate (about 100 micrometers nominal thickness), a
second layer of the alkaline earth aluminosilicate described in
Example 1 (about 75-100 micrometers nominal thickness), and a third
layer of yttrium disilicate (about 100 micrometers nominal
thickness) was fabricated using plasma spray deposition. Air
permeability tests showed that the permeability to air of the
multi-layered coating assembly after heat treatment for 10 hours at
1315 degrees Celsius was at least a factor of ten lower than that
measured in the as-sprayed condition, demonstrating an improvement
in coating hermeticity.
Example 3
[0034] A multi-layered coating assembly comprising a first layer of
yttrium disilicate, a second layer of the alkaline earth
aluminosilicate described in Example 1, a third layer of yttrium
disilicate, and a fourth layer of yttrium monosilicate was
fabricated using plasma spray deposition. The first through third
layers were nominally about 75-125 micrometers thick, and the
monosilicate layer was nominally about 50-75 micrometers thick. Air
permeability tests showed that the permeability to air of the
multi-layer assembly after heat treatment (same heat treatment as
in Example 1) was at least a factor of ten lower than that measured
in the as-sprayed condition, demonstrating an improvement in
coating hermeticity.
Example 4
[0035] The effectiveness of the sealing layer in slowing the
degradation of underlying silicon-bearing layers was demonstrated.
Three silicon carbide--silicon carbide ceramic matrix composite
specimens were plasma-spray coated with nominally about 100-125
micrometers of silicon as a bondcoat. The first specimen was
plasma-spray coated with a layer of yttrium disilicate having a
nominal thickness of about 175-200 micrometers. The second specimen
was plasma-spray coated with a first layer of yttrium disilicate
having a nominal thickness of about 75-100 micrometers, a middle
(sealing) layer of the alkaline-earth aluminosilicate of Example 1
having a nominal thickness of about 75-100 micrometers, and an
outer layer of yttrium disilicate having nominal thickness of about
175-200 micrometers. The third specimen was plasma spray coated
using a layer architecture similar to the second specimen but with
an additional outer layer of yttrium monosilicate that was
nominally 50-75 micrometers thick. The three specimens were exposed
to multiple 2-hour exposure cycles in a 90% water vapor/10% oxygen
environment at 1315 degrees Celsius. After 500 hours of exposure,
the specimens were sectioned and metallographically examined for
microstructural evaluations and to measure the thickness of the
oxide scale formed at the interface between the silicon bond layer
and the lower yttrium disilicate layer. The silicon bondcoat of the
first specimen had an oxide layer with a thickness of about a
factor of 5 higher than those measured for the second and the third
specimens, demonstrating that the improved hermeticity achieved by
the presence of the sealing layer in the second and third specimens
considerably inhibited bondcoat degradation due to the influx of
environmental species.
[0036] While only certain features of the invention have been
illustrated and described herein, many modifications and changes
will occur to those skilled in the art. It is, therefore, to be
understood that the appended claims are intended to cover all such
modifications and changes as fall within the true spirit of the
invention.
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