US008216687B2

(12) United States Patent (10) Patent N0.: US 8,216,687 B2

Burd et a]. (45) Date of Patent: *Jul. 10, 2012

(54) THERMAL BARRIER COATING (52) US. Cl. .................... .. 428/469; 428/472; 427/419.2
_ (58) Field of Classi?cation Search ...................... .. None
(75) Inventors: lsgegent‘gl‘
0 er
Bsurd’tcheiilnre’hcTt
. onn ag, anc es er,
See application ?le for complete search history.
(US); Kevin W. Schlichting, Storrs, CT
(Us) (56) References Cited
(73) Assignee: United Technologies Corporation, U-S~ PATENT DOCUMENTS
Hartford, CT (US) 4,405,659 A 9/1983 Strangman
4,898,368 A 2/1990 Schaffer et a1.
( * ) Notice: Subject to any disclaimer, the term of this
' ' , ,
i glgglntsi iln et a1~
asz e a.
patent 1s extended or adjusted under 35 5,683,761 A 11/1997 Bruce et a1‘
U-S-C- 154(1)) by 452 days- 5,773,141 A 6/1998 HasZ 61711.
- - - - - 6,060,177 A 5/2000 B t ' t 1.
This patent 1s 511131601 to a termmal d1s- 6,382,920 B1 5/2002 Dgggefme a
Clalmer- 6,413,578 B1 7/2002 Stowell et a1.
6,572,981 B2 6/2003 Spitsberg
(21) Appl. N0.: 12/054,801 6,620,525 B1 9/2003 Rigney et a1.
6,821,641 B2 11/2004 Bruce et a1.
(22) Filed: Mar- 25, 2008 7,226,672 B2 6/2007 Litton et a1.

(65) Prior Publication Data Primary Examiner * Timothy Speer

Us Zoos/0171222 A1 Jul 17 2008 (74) Attorney, Agent, or Firm * Bachman & LaPointe, P.C.

Related US. Application Data (57) ABSTRACT

(62) Division of application NO- 10/968’322’ ?led on 001- An article has a metallic substrate having a ?rst emissivity. A
18’ 2004’ HOW Pat' NO' 7,413,808 thermal barrier coating atop the substrate may have an emis
(51) I t Cl sivity that is a substantial fraction of the ?rst emissivity.
n . .

B32B 9/00 (2006.01)

B05D 1/36 (2006.01) 22 Claims, 5 Drawing Sheets
US. Patent Jul. 10, 2012 Sheet 1 of5 US 8,216,687 B2

FIG.1
US. Patent Jul. 10, 2012 Sheet 2 of5 US 8,216,687 B2
US. Patent Jul. 10, 2012 Sheet 3 of5 US 8,216,687 B2

#w mm

an

Nw
US. Patent Jul. 10, 2012 Sheet 4 of5 US 8,216,687 B2

ww No

mmmm
US. Patent Jul. 10, 2012 Sheet 5 of5 US 8,216,687 B2

mm III:I!0

I .‘
 US 8,216,687 B2
1 2
THERMAL BARRIER COATING heat shield, noZZle ?aps or seals, and the like. The TBC may
have a uniform composition over a thickness span starting at
CROSS-REFERENCE TO RELATED most 10% beloW an outer surface and extending to at least
APPLICATION 50%.
Another aspect of the disclosure involves a method for
This is a divisional application ofSer. No. 10/968,322, ?led manufacturing an article. A metallic substrate is provided. A
Oct. 18, 2004, and entitled THERMAL BARRIER COAT bondcoat layer is applied over a surface of the substrate. A
ING, issued Aug. 19, 2008 as US. Pat. No. 7,413,808, the TBC layer is applied over the bondcoat layer. The TBC con
disclosure of Which is incorporated by reference herein in its sists in major part of a combination of alumina and chromia.
entirety as if set forth at length. The TBC layer has a thickness in excess of 250 pm.
In various implementations, the bondcoat layer may have a
BACKGROUND thickness less than the thickness of the TBC layer. The sub
strate may be formed by at least one of casting, forging, and
The disclosure relates to thermal barrier coatings (TBCs). machining of a nickel- or cobalt-based superalloy, refractory
More particularly, the disclosure relates to TBCs applied to material, or composite system.
superalloy gas turbine engine components. Another aspect of the disclosure involves a method of
The application of TBCs, such as yttria-stabiliZed Zirconia remanufacturing an apparatus or reengineering a con?gura
(YSZ) to external surfaces of air-cooled components, such as tion of the apparatus from a ?rst condition to a second con
air-cooled turbine and combustor components is a Well devel dition. The method involves replacing a ?rst component With
oped ?eld. US. Pat. No. 4,405,659 to Strangman describes 20 a second component. The ?rst component has a ?rst substrate
one such application. In Strangman, a thin, uniform metallic in a ?rst coating system. The second component has a second
bonding layer, e. g., betWeen about 1-10 mils, is provided onto substrate and a second coating system. A ?rst emissivity
the exterior surface of a metal component, such as a turbine difference betWeen the ?rst substrate and the ?rst coating
blade fabricated from a superalloy. The bonding layer may be system is greater than a second emissivity difference betWeen
a MCrAlY alloy (Where M identi?es one or more of Fe, Ni, 25 the second substrate and the second coating system.
and Co), intermetallic aluminide, or other suitable material. A In various implementations, the ?rst coating system may
relatively thinner layer of alumina, on the order of about be less conductive (or more insulative) than the second coat
0.01 -0.1 mil (0.25-2.5 pm), is formed by oxidation on the ing system. The second coating system may be thicker than
bonding layer. Alternatively, the alumina layer may be the ?rst coating system. The ?rst and second substrates may
formed directly on the alloy Without utiliZing a bond coat. The 30 be essentially identical (e.g., in composition, structure, shape,
TBC is then applied to the alumina layer by vapor deposition and siZe). The apparatus may be a gas turbine engine. The ?rst
or other suitable process in the form of individual columnar and second components may be subject to operating tempera
segments, each of Which is ?rmly bonded to the alumina layer tures in excess of 1350 C.
of the component, but not to one another. The underlying Another aspect of the disclosure involves an article having
metal and the ceramic TBC typically have different coef? 35 a metallic substrate having a ?rst emissivity. A TBC is atop
cients of thermal expansion. Accordingly, the gaps betWeen the substrate and includes means for limiting thermally-in
the columnar segments enable thermal expansion of the duced fatigue or creep in the substrate. This limitation may
underlying metal Without damaging the TBC. apply to instances both prior to and after Which the TBC has
US. Pat. No. 6,060,177 to Bornstein et al. (the disclosure spalled. The TBC may consist essentially of alumina and
of Which is incorporated by reference herein as if set forth at 40 chromia.
length) describes use of an overcoat of chromia and alumina The details of one or more embodiments are set forth in the
atop a yttria-stabiliZed Zirconia (Y SZ) TBC. Such an overcoat accompanying draWings and the description beloW. Other
may protect against sul?dation attack and oxidation and may features, objects, and advantages Will be apparent from the
signi?cantly extend the operational life of the component. description and draWings, and from the claims.
45
SUMMARY OF THE INVENTION BRIEF DESCRIPTION OF THE DRAWINGS

One aspect of the disclosure involves an article including a FIG. 1 is a vieW of a gas turbine engine combustor panel.
metallic substrate having a ?rst emissivity. A TBC is atop the FIG. 2 is a partially schematic cross-sectional vieW of a
substrate and has an emissivity at least 70% of the ?rst emis 50 coating system on the panel of FIG. 1.
sivity, in Whole or part over the Wavelengths of concern to FIG. 3 is a partially schematic cross-sectional vieW of a ?rst
gray or blackbody radiation, including infrared Wavelengths. alternate coating system on the panel of FIG. 1.
In various implementations, the TBC may consist essen FIG. 4 is a partially schematic cross-sectional vieW of a
tially of alumina and chromia. The TBC may consist in major second alternate coating system on the panel of FIG. 1.
part of a combination of alumina and chromia. The TBC may 55 FIG. 5 is a partially schematic cross-sectional vieW of a
include a layer consisting in major part of alumina and chro third alternate coating system on the panel of FIG. 1.
mia. The layer may have a thickness in excess of 250 um. The Like reference numbers and designations in the various
thickness may be betWeen 250 um and 640 pm. The thickness draWings indicate like elements.
may be betWeen 280 um and 430 pm. The layer may have a
thermal conductivity of 5-20 BTU inch/(hr-sqft-F). The layer 60 DETAILED DESCRIPTION
may be an outermost layer and there may be a bondcoat layer
betWeen the outermost layer and the substrate. The substrate FIG. 1 shoWs a turbine engine combustor panel 20 Which
may consist essentially of or comprise a nickel- or cobalt may be formed having a body 21 shaped as a generally frus
based superalloy, a refractory metal-based alloy, a ceramic toconical segment having inboard and outboard surfaces 22
matrix, or another composite. The article may be used as one 65 and 24. The exemplary panel is con?gured for use in an
of a gas turbine engine combustor panel (e.g., heat shield or annular combustor circumscribing the engine centerline. In
liner), turbine blade or vane, turbine exhaust case fairing or the exemplary panel, the inboard surface 22 forms an interior
 US 8,216,687 B2
3 4
surface (i.e., facing the combustor interior) so that the panel is deposited by air plasma spraying as disclosed in Bornstein et
an outboard panel. For an inboard panel, the inboard surface al. The exemplary characteristic thickness for the alumina
Would be the exterior surface. Accordingly, mounting fea chromia TBC 66 is preferably at least 10 mil (250 pm). For
tures such as studs 26 extend from the outboard surface for example, it may be 10-30 mil (250-760 pm), more narroWly,
securing the panel relative to the engine. The exemplary panel 10-25 mil (250-640 um), and yet more narroWly, 11-17 mil
further includes an upstream/leading edge 28, a doWnstream/ (280-430 um). Exemplary alumina-chromia coatings may
trailing edge 30 and lateral edges 32 and 34. Along the edges consist essentially of the alumina and chromia or have up to
or elseWhere, the panel may include rails or standoffs 36 30 Weight percent other components. For the former, exem
extending from the exterior surface 24 for engaging a com plary chromia contents are 55-93% and alumina 7-45%. The
bustor shell (not shoWn). The exemplary panel includes a alumina-chromia coating in a multi-layer system may pro
circumferential array of large apertures 40 for the introduc vide an exemplary at least 50% of the insulative capacity of
tion of process air. Smaller apertures (not shoWn) may be the coating system. It may represent at least 50% of the
provided for ?lm cooling. Moreover, select panels may thickness of the system. More narroWly, it may represent
accommodate other openings for spark plug or igniter place 60-95% of the insulative capacity and 60-80% of the thick
ment. ness.
With conventional TBC systems, We have observed certain Alternative TBCs may include silicon carbide or other
failure modes in regions 50 (schematically shoWn) doWn coatings providing a good emissivity match for the exposed
stream of the holes 40 or other large ori?ces. Other failure post-spalling surface (i.e., the bond coat, metallic coating, or
regions are: (1) upstream and about the circumference of substrate exposed folloWing spalling). For example, the effec
holes; (2) near the panel edges; and (3) various other local 20 tive coating emissivity may be at least 40% that of the post
regions about the combustor Which see streaks of combustion spalling surface, more advantageously, at least 70%, 80%, or
products Which, due to their luminosity and/ or temperature, 90% (e.g., coating emissivity of 0.5-0.8 or more) contrasted
impart locally high-levels or radiation loading to the parts. With about 30% for a light TBC.
The failures are characterized by cracking of the panel sub The foregoing principles may be applied in the remanufac
strate (e.g., Ni- or Co-based superalloy) shortly after a 25 turing of a gas turbine engine or the reengineering of an
delamination or spalling of the TBC in the vicinity of the engine con?guration. The remanufacturing or reengineering
region of failure or, in some cases, Without incident of coating may replace one or more original components With one or
failure. It is believed the cracking results from thermal fatigue more replacement components. Each original component
and creep due to high temperature gradients and local tem may have a ?rst superalloy substrate With a ?rst coating
peratures in the substrate betWeen regions of lost TBC and 30 system. Each replacement component may have a second
regions of intact TBC or beloW the TBC surface. The gradi superalloy substrate With a second coating system. Other
ents may result from a combination of: increased heat transfer components (including similarly coated components) may
to the area that has lost the TBC; and differential optical or remain unchanged in the reengineering or remanufacturing.
radiative loading attributed to the higher emissivity of the The emissivity difference betWeen the second substrate and
exposed substrate relative to the intact TBC. For example, a 35 the second coating system may be smaller than that of the
substrate may have an emissivity in the vicinity of 0.8-0.9 ?rst. Where the ?rst and second substrates are essentially
(broadly over Wavelengths driving radiative heat transfer identical, and the ?rst coating emissivity is less than the ?rst
(e. g., 1-10 um)) Whereas the TBC may have an emissivity in substrate emissivity, the second coating emissivity may be
the range of 0.2-0.5. In operation, these can lead to tempera greater than the ?rst coating emissivity. Although the second
ture differences in the vicinity of 100-150 C over relatively 40 coating system may possibly be more insulative than the ?rst
short distances of 20-50 mm (e.g., When exposed to tempera coating system, the bene?ts of emissivity compatibility
tures in excess of900 C or even in excess of 1350 C). Accord potentially justify use even Where the second coating system
ingly, a modi?ed TBC With an increased emissivity (i.e., a is less insulative than the ?rst coating system. For example,
darker TBC) may reduce the post-spalling differential optical the ?rst coating system may be 1.5 to ten times more insula
or radiative load and inherent thermal gradients and, thereby, 45 tive than the second. Thus, although the second substrate may
may delay component damage and subsequent failure. One operate overall hotter than the ?rst, it may suffer loWer levels
possible high emissivity TBC involves an alumina-chromia of spatial and/or temporal temperature ?uctuations.
combination such as is used in Bomstein et al. as an overcoat. FIG. 3 shoWs an alternate coating system 80. In an area or
Accordingly, the disclosure of Bomstein et al. is incorporated region 82 of expected high thermal loading (e.g., the region
by reference herein as if set forth at length to the extent it 50 50), the system includes a loW-emissivity (light) TBC 84
describes coating methods and compositions. (e.g., an emissivity of 02-05). An exemplary light TBC 84
FIG. 2 shoWs a coating system 60 atop a superalloy sub may beYSZ and may be associated With an alumina layer 86
strate 62. The system may include a bondcoat 64 atop the atop the bondcoat 64 (e.g., as disclosed in Bornstein et al.)
substrate 62 and a TBC 66 atop the bondcoat 64. In an exem Additional coating layers atop the TBC 84 may also be pos
plary process, the bondcoat 64 is deposited atop the substrate 55 sible (e.g., as disclosed in Bomstein et al.). In a loWer thermal
surface 68. One exemplary bondcoat is a MCrAlY Which may loading area or region 88, a dark TBC 90 may be applied atop
be deposited by a thermal spray process (e.g., air plasma the bondcoat 64 (e. g., in similar compositions, and the like as
spray) or by an electron beam physical vapor deposition the TBC 66). On yet other areas of the substrate (not shoWn)
(EBPVD) process such as described in Strangman. An alter subject to yet less heating or thermal loading, there may be no
native bondcoat is a diffusion aluminide deposited by vapor 60 TBC or a yet reduced TBC.
phase aluminiZing (VPA) as in Us. Pat. No. 6,572,981 of While intact, the light TBC 84 helps keep the region 82
Spitsberg. An exemplary characteristic (e.g., mean or cooler than in the system 60. This helps reduce differential
median) bondcoat thicknesses 4-9 mil (100-230 um). thermal loading in the substrate and may help further delay
In an exemplary embodiment, the TBC 66 is deposited spalling. HoWever, once spalling occurs it Will essentially be
directly atop the exposed surface 70 of the bondcoat 64. An 65 limited to loss of the light TBC 84 and not the dark TBC 90.
exemplary TBC comprises chromia and alumina. For Clearly, the limit of spalling need not be exactly along the
example, a solid solution of chromia and alumina may be boundary betWeen the TBCs 84 and 90. The limit may be on
 US 8,216,687 B2
5 6
either side or may cross the boundary. This leaves a similar 5. The article of claim 1 Wherein:
emissivity balance between spalled and unspalled regions as the substrate has a ?rst emissivity at 1350 C;
does the embodiment of FIG. 2. To apply the tWo distinct the coating system is a ?rst coating system on a ?rst region
TBCs, one of the tWo regions could be masked While one of of the substrate and having a second emissivity at 1350
the TBCs is applied to the other region. Thereafter, after C of least 70% of the ?rst emissivity; and
demasking, the other region could be masked While the other along a second region of the substrate, the article comprises
TBC is applied and the second mask removed. In the ?gures, a second coating system having a third emissivity at
a relatively sharp demarcation is shoWn betWeen the TBC’s 1350 C of 20-50% of the ?rst emissivity.
and/or their layers for purposes of illustration. However, a 6. The article of claim 1 Wherein:
variety of engineering and/or manufacturing considerations the coating system is a ?rst thermal barrier coating essen
may cause more gradual transitions.
tially in a relatively loW thermal load region of the sub
FIG. 4 shoWs a system 100 in Which one of the tWo masking
steps associated With the exemplary application of the system strate; and
80 is avoided. The exemplary system 100 includes a dark a second coating system is in a relatively high load region
TBC 102 similar to the dark TBC 66 and applied over both the of the substrate and having a loWer emissivity than the
higher load region 82 and the adjacent loWer load region 88. ?rst coating system.
Essentially limited to the high load region, a light TBC 104 7. The article of claim 1 Wherein:
(e.g., similar to light TBC 84) may be applied atop (e.g., the alumina-chromia layer consists essentially of 55-93%
directly atop or With an intervening layer) the dark TBC 102 chromia and 7-45% alumina by Weight.
(e.g., similar to the TBC 66). Thus, masking is not required 20 8. The article of claim 1 Wherein:
during the application of the dark TBC 102 but may be the alumina-chromia layer consists in majority mass part of
applied in the region 88 during application of the light TBC a combination of alumina and chromia.
104. As With the system 80, the system 100 provides prefer 9. The article of claim 1 Wherein:
ential heat rejection along the region 82 in pre- spalling opera a median thicknesses of the alumina-chromia layer is in
tion. Spalling may involve loss of both the light TBC 104 and 25 excess of 250 um.
the portion of the dark TBC 102 immediately therebeloW 10. The article of claim 1 Wherein:
(either in a single spalling event or a staged spalling event). the alumina-chromia layer has a thermal conductivity of
After such spalling, the essentially intact dark TBC 102 in the 5-20 BTU-inch/(hr-sqft-F).
region 88 provides similar advantages as does that of the 11. The article of claim 1 Wherein:
systems 60 and 80. 30 the substrate comprises a nickel- or cobalt-based superal
FIG. 5 shoWs an alternate coating system 120 reversing the loy.
situation relative to the system 100. A light TBC 122 (and 12. The article of claim 1 used as one of:
optional alumina layer 124) are applied over both the regions a gas turbine engine combustor panel;
82 and 88. Thereafter, the region 82 is masked and a dark TBC gas turbine engine turbine exhaust case component; or
126 is applied over the region 88. Pre-spalling, the exposed 35 gas turbine engine turbine noZZle component.
light TBC in the high load region 82 offers preferential heat 13. The article of claim 1 Wherein:
rejection similar to that of the systems 80 and 100. The the alumina-chromia layer has a uniform composition over
spalling may essentially entail loss of that exposed portion of a thickness span starting at least 10% beloW an outer
the light TBC 122, leaving the dark TBC 126 essentially surface and extending to at least 50%.
intact. 40 14. A method for manufacturing the article of claim 1, the
One or more embodiments have been described. Neverthe method comprising:
less, it Will be understood that various modi?cations may be providing the metallic substrate;
made. For example, details of any particular application may applying the bondcoat over a surface of the substrate; and
in?uence details of any particular implementation. Accord applying the alumina-chromia layer over the bondcoat, the
ingly, other embodiments are Within the scope of the folloW 45 alumina-chromia layer having a thickness in excess of
ing claims. 250 um.
15. The method of claim 14 Wherein the bondcoat layer has
What is claimed is: a thickness of less than said thickness of the alumina-chromia
1. An article comprising: layer.
a metallic substrate; and 50 16. The method of claim 14 forming the substrate by at
a coating system atop the substrate and comprising: least one of casting and machining of a nickel- or cobalt
an alumina-chromia layer having: based superalloy.
a thickness at least 50% of a total thickness of the 17. An article comprising:
system; and a metallic substrate; and
a bondcoat betWeen the substrate and the alumina 55 a thermal barrier coating atop the substrate and comprising
chromia layer. means for limiting post-spalling thermal fatigue.
2. The article of claim 1 Wherein: 18. The article of claim 17 Wherein:
a median thicknesses of the bondcoat is 100-230 um; and the thermal barrier coating consists essentially of alumina
a median thicknesses of the alumina-chromia layer is 280 and chromia.
430 pm. 60 19. The article of claim 17 Wherein the means further
3. The article of claim 1 Wherein: provides pre-spalling preferential heat rejection from a high
the alumina-chromia layer provides 60-95% of an insula load region relative to a loW load region.
tive capacity of the coating system and 60-80% of a 20. The article of claim 17 Wherein the means comprises:
thickness of the coating system. a ?rst thermal barrier coating layer over a relatively high
4. The article of claim 1 Wherein: load region but not a relatively loW load region; and
the coating system consists essentially of the alumina a second thermal barrier coating layer over the relatively
chromia layer and the bondcoat. loW load region but not the relatively high load region,
 US 8,216,687 B2
7 8
the second thermal barrier coating layer being relatively 22. The article of claim 17 Wherein the means comprises:
darker compared to the ?rst thermal barrier coating a ?rst thermal barrier coating layer across both a high load
layer. region and a loW load region; and
21. The article of claim 17 Wherein the means comprises: a second thermal barrier coating layer atop the ?rst thermal
a ?rst thermal barrier coating layer across both a high load 5 barrier coating layer along the loW load region but not
region and a loW load region; and the high load region, the second thermal barrier coating
a second thermal barrier coating layer atop the ?rst thermal layer being relatively dark compared to the ?rst thermal
barrier coating layer along the high load region but not barrier coating layer.
the loW load region, the ?rst thermal barrier coating layer
being relatively dark compared to the second thermal
barrier coating layer.