CN1546719A - Novel heat barrier coating material - Google Patents
Novel heat barrier coating material Download PDFInfo
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- CN1546719A CN1546719A CNA2003101159341A CN200310115934A CN1546719A CN 1546719 A CN1546719 A CN 1546719A CN A2003101159341 A CNA2003101159341 A CN A2003101159341A CN 200310115934 A CN200310115934 A CN 200310115934A CN 1546719 A CN1546719 A CN 1546719A
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- heat barrier
- deposition techniques
- powdered sample
- coating
- barrier coat
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- Other Surface Treatments For Metallic Materials (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
Abstract
The invention relates to a series of ceramic materials used as high temperature thermal barrier coating materials and their use, wherein the chemical constitution of the ceramic material being A2ZrxCe(1-x)2O7, wherein 0<=x<=0.9, an is one or combination of two of Nd, Sm, Eu, Gd and Tb. The ceramic material has high coefficient of thermal expansion, thus can be designed into thermal barrier coating material, whose application temperature interval is between room temperature to 1400 deg. C.
Description
Technical field
The invention belongs to high-temp heat barrier coating technology and related coatings material.
Background technology
Along with the development of Aeronautics and Astronautics and civilian technology, the use temperature of turbine engine hot-end component requires more and more high, and superalloy and monocrystalline have reached the ultimate limit state of material.In this case, consider that another kind of the possible technique----Thermal Barrier Coating Technologies that reduces the engine blade working temperature has obtained using widely from the angle of material.
The comparative study of NASA shows, ZrO
2Over-all properties comparatively superior.In the time of 1000 ℃, ZrO
2Thermal expansivity be 11 * 10
-6K
-1, near the thermal expansivity of matrix alloy, and thermal conductivity only is 2.1-2.2WM
-1k
-1But pure ZrO
2In common use temperature scope, the martensitic transformation of cubic phase (t) to monocline phase (m) can take place, adapt to thermal cycling Working environment under the high temperature and the life-span of improving coating in order to make coating, usually at ZrO
2The generation of this class phase transformation is controlled, is reduced in the agent of middle interpolation few stable.United States Patent (USP) 5,789 has been reported at ZrO among 330 (Kondo, the et al)
2Middle various phase stabilizers of doping 0.1wt%-40wt% such as Y2O3, CaO, MgO, Sc2O3, the heat barrier coat material that obtains behind the rare earth oxide etc.Behind the material sintering in the system monocline account for 25-75% mutually, the maximum surperficial heat resisting temperature of the life-time service of coated material is about 1200 ℃, along with the further raising of temperature, serious structural instability appears in coating.United States Patent (USP) 6,231 has been reported a kind of material with pyrochlore constitution, particularly La in 991
2Zr
2O
7(Lanthnum Zirconate) as heat barrier coat material, and the character of its uniqueness is as lower thermal conductivity, in anneal to 1400 ℃, still keeps the phase steady state.But La
2Zr
2O
7Thermal expansivity is little than YSZ, differs bigger with the thermal expansivity of matrix alloy, will more serious because of the expand coating internal stress that is caused that do not match of elevated temperature heat, and coating cycle life is lacked.
Summary of the invention
The purpose of this invention is to provide a kind of novel heat barrier coat material.
Another object of the present invention provides a kind of application of heat barrier coat material.
The basic design philosophy of thermal barrier coating is exactly to utilize high heat resistance, erosion resistance and the low heat conductivity of pottery, realizes the protection to matrix.Therefore, the selection of thermal barrier coating ceramic surface layer material need be followed certain principle: 1, no phase transformation 3 between high-melting-point 2, room temperature and service temperature, low-thermal conductivity 4, chemical reaction inertia 5, higher coefficient of thermal expansion 6, good thermal shock resistance 7, lower sintering rate.
In isolator such as pottery, the heat-conduction coefficient of material depends on the lattice vibrations usually.Atom in material is formed by heavier or bigger atom, and its heat-conduction coefficient can corresponding reduction.The atomic mass difference is big more, and heat-conduction coefficient reduces big more.The atomic mass of Ce atom and radius are all big far beyond Zr, so when Ce replaced Zr, the heat-conduction coefficient of material can reduce accordingly.In addition, CeO
2Be a kind of fluorite structure oxide compound, and its heat-conduction coefficient is little than 8YSZ, and thermal expansivity is big than 8YSZ.Therefore the present invention estimates to work as A
2Zr
2O
7Middle Zr is that A was Nd after Ce replaced, Sm, and Eu, Gd, one or more combination among the Tb, the thermal expansivity of resulting novel material will increase, and heat-conduction coefficient is for reducing.
Stupalith of the present invention has following chemical constitution A
2(Zr
xCe
(1-x))
2O
7, 0＜=X＜=0.9, A is Nd, Sm, Eu, Gd, one or more combination among the Tb.
The application of heat barrier coat material is as follows: at first, obtain metal base, metal base is by parts Ni-based or that cobalt base superalloy is formed in the turbine engine; At metal substrate surface or a certain position deposition layer of metal tack coat, metal bonding coating is the MCrAlY alloy then, and wherein M is one or more combinations among Ni, Co or the Fe, and Y is a kind of among Y, La or the Hf; At last, at tie layer surface ceramic deposition surface layer, the ceramic topcoats chemical constitution is A
2(Zr
xCe
(1-x))
2O
7, 0＜=X＜=0.9, A is Nd, Sm, Eu, Gd, one or more combinations among the Tb.
Heat barrier coat material has high thermal expansion coefficient among the present invention, and its thermal expansivity has reached 10-15 * 10
-6K
-1, be better than the heat barrier coat material of present widespread usage, after handling, 1400 ℃ of following long term annealings still keep the phase steady state.Utilize these characteristics, this material can be designed to heat barrier coat material, the interval room temperature to 1400 of Applicable temperature ℃.Heat barrier coat material can deposit by following approach among the present invention: plasma spray degree, electro beam physics vapour deposition, HVOF, D-gun technology etc.
Fig. 1 has provided Ce and has replaced Nd fully
2Zr
2O
7The novel material Nd that obtains behind the middle Zr
2Ce
2O
7XRD spectra, show Nd among the figure
2Ce
2O
7Fluorite structure with distortion, wherein 1/8 0 occupied by the hole.
Fig. 2 has provided Nd
2Ce
2O
7Thermal expansivity under room temperature to 1400 ℃ shows among the figure that this stupalith has high thermal expansivity, has reached 12-15 * 10 at high-temperature zone 900-1400 ℃ of its thermal expansivity
-6K
-1, be better than the heat barrier coat material of present widespread usage.
Fig. 3 provides Nd
2Ce
2O
7The XRD spectra that after 1400 ℃ of following long term annealings are handled, obtains, the as can be seen from the figure XRD spectra that after anneal, still is consistent of each sample, this shows that long term annealing does not have phase transformation to take place in handling.
Gained heat barrier coat material thermal coefficient of expansion of the present invention is bigger, with engine thermal end pieces base The height temperature alloy is the most approaching, thereby is deposited gained coating internal heat gravitation very with this material Little, thermal cycle life is long; Market is easy to get; Coating production is simple, and equipment is easy to get.
Embodiment
Embodiment 1: preparation powdered sample Nd
2Ce
2O
7(Nd
2O
3+ 2CeO
2), obtain the spray-dried processing of powdered sample and make the high workability powder.The Nd of the about 300 μ m of plasma spray degree deposition techniques one bed thickness is used then by the thick NiCrAlY metal bonding coating of the about 220 μ m of electro beam physics vapour deposition deposition techniques one deck in the nickel base superalloy surface in tie layer surface
2Ce
2O
7Ceramic topcoats, final gained thermal barrier coating system as shown in Figure 4.
Embodiment 2: preparation powdered sample Nd
2(Zr
0.9Ce
0.1)
2O
7, obtain the spray-dried processing of powdered sample and make the high workability powder.The Nd of the about 250 μ m of plasma spray degree deposition techniques one bed thickness is used then by the thick CoCrAlY metal bonding coating of the about 250 μ m of electro beam physics vapour deposition deposition techniques one deck in the nickel base superalloy surface in tie layer surface
2z(Zr
0.9Ce
0.1)
2O
7Ceramic topcoats.
Embodiment 3: preparation powdered sample Nd
2(Zr
0.5Ce
0.5)
2O
7, obtain the spray-dried processing of powdered sample and make the high workability powder.The Nd of the about 250 μ m of plasma spray degree deposition techniques one bed thickness is used then by the thick FeCrAlY metal bonding coating of the about 250 μ m of electro beam physics vapour deposition deposition techniques one deck in the cobalt base superalloy surface in tie layer surface
2z(Zr
0.9Ce
0.1)
2O
7Ceramic topcoats.
Embodiment 4: preparation powdered sample Sm
2Ce
2O
7, obtain the spray-dried processing of powdered sample and make the high workability powder.The Nd of the about 300 μ m of plasma spray degree deposition techniques one bed thickness is used then by the thick NiCrAlY metal bonding coating of the about 225 μ m of electro beam physics vapour deposition deposition techniques one deck in the nickel base superalloy surface in tie layer surface
2Ce
2O
7Ceramic topcoats.
Embodiment 5: preparation powdered sample Sm
2(Zr
0.9Ce
0.1)
2O
7, obtain the spray-dried processing of powdered sample and make the high workability powder.The Sm of the about 300 μ m of plasma spray degree deposition techniques one bed thickness is used then by the thick FeCrAlY metal bonding coating of the about 250 μ m of electro beam physics vapour deposition deposition techniques one deck in the nickel base superalloy surface in tie layer surface
2(Zr
0.9Ce
0.1)
2O
7Ceramic topcoats.
Embodiment 6: preparation powdered sample Sm
2(Zr
0.5Ce
0.5)
2O
7, obtain the spray-dried processing of powdered sample and make the high workability powder.The Nd of the about 250 μ m of plasma spray degree deposition techniques one bed thickness is used then by the thick CoCrAlY metal bonding coating of the about 250 μ m of electro beam physics vapour deposition deposition techniques one deck in the cobalt base superalloy surface in tie layer surface
2z(Zr
0.9Ce
0.1)
2O
7Ceramic topcoats.
Embodiment 7: preparation powdered sample Eu
2Ce
2O
7, obtain the spray-dried processing of powdered sample and make the high workability powder.The Eu of the about 350 μ m of plasma spray degree deposition techniques one bed thickness is used then by the thick NiCrAlY metal bonding coating of the about 220 μ m of electro beam physics vapour deposition deposition techniques one deck in the nickel base superalloy surface in tie layer surface
2Ce
2O
7Ceramic topcoats.
Embodiment 8: preparation powdered sample Eu
2(Zr
0.9Ce
0.1)
2O
7, obtain the spray-dried processing of powdered sample and make the high workability powder.The Eu of the about 300 μ m of plasma spray degree deposition techniques one bed thickness is used then by the thick FeCrAlY metal bonding coating of the about 250 μ m of electro beam physics vapour deposition deposition techniques one deck in the nickel base superalloy surface in tie layer surface
2(Zr
0.9Ce
0.1)
2O
7Ceramic topcoats.
Embodiment 9: preparation powdered sample Eu
2(Zr
0.5Ce
0.5)
2O
7, obtain the spray-dried processing of powdered sample and make the high workability powder.The Eu of the about 250 μ m of plasma spray degree deposition techniques one bed thickness is used then by the thick CoCrAlY metal bonding coating of the about 250 μ m of electro beam physics vapour deposition deposition techniques one deck in the cobalt base superalloy surface in tie layer surface
2(Zr
0.5Ce
0.5)
2O
7Ceramic topcoats.
Embodiment 10: preparation powdered sample Gd
2Ce
2O
7, obtain the spray-dried processing of powdered sample and make the high workability powder.The Gd of the about 300 μ m of plasma spray degree deposition techniques one bed thickness is used then by the thick NiCrAlY metal bonding coating of the about 220 μ m of electro beam physics vapour deposition deposition techniques one deck in the nickel base superalloy surface in tie layer surface
2Ce
2O
7Ceramic topcoats.
Embodiment 11: preparation powdered sample Gd
2(Zr
0.9Ce
0.1)
2O
7, obtain the spray-dried processing of powdered sample and make the high workability powder.The Gd of the about 300 μ m of plasma spray degree deposition techniques one bed thickness is used then by the thick FeCrAlY metal bonding coating of the about 250 μ m of electro beam physics vapour deposition deposition techniques one deck in the nickel base superalloy surface in tie layer surface
2(Zr
0.9Ce
0.1)
2O
7Ceramic topcoats.
Embodiment 12: preparation powdered sample Gd
2(Zr
0.5Ce
0.5)
2O
7, obtain the spray-dried processing of powdered sample and make the high workability powder.The Gd of the about 250 μ m of plasma spray degree deposition techniques one bed thickness is used then by the thick CoCrAlY metal bonding coating of the about 250 μ m of electro beam physics vapour deposition deposition techniques one deck in the cobalt base superalloy surface in tie layer surface
2(Zr
0.5Ce
0.5)
2O
7Ceramic topcoats.
Embodiment 13: preparation powdered sample Tb
2Ce
2O
7, obtain the spray-dried processing of powdered sample and make the high workability powder.The Tb of the about 300 μ m of plasma spray degree deposition techniques one bed thickness is used then by the thick NiCrAlY metal bonding coating of the about 220 μ m of electro beam physics vapour deposition deposition techniques one deck in the nickel base superalloy surface in tie layer surface
2Ce
2O
7Ceramic topcoats.
Embodiment 14: preparation powdered sample Tb
2(Zr
0.9Ce
0.1)
2O
7, obtain the spray-dried processing of powdered sample and make the high workability powder.The Tb of the about 300 μ m of plasma spray degree deposition techniques one bed thickness is used then by the thick FeCrAlY metal bonding coating of the about 250 μ m of electro beam physics vapour deposition deposition techniques one deck in the nickel base superalloy surface in tie layer surface
2(Zr
0.9Ce
0.1)
2O
7Ceramic topcoats.
Embodiment 15: preparation powdered sample Tb
2(Zr
0.5Ce
0.5)
2O
7, obtain the spray-dried processing of powdered sample and make the high workability powder.The Tb of the about 250 μ m of plasma spray degree deposition techniques one bed thickness is used then by the thick CoCrAlY metal bonding coating of the about 200 μ m of electro beam physics vapour deposition deposition techniques one deck in the cobalt base superalloy surface in tie layer surface
2(Zr
0.5Ce
0.5)
2O
7Ceramic topcoats.
Claims (4)
1, a kind of heat barrier coat material, chemical constitution are A
2(Zr
xCe
(1-x))
2O
7, 0＜=X＜=0.9, A is Nd, Sm, Eu, Gd, the combination of one or more among the Tb.
2, electro beam physics vapour deposition or plasma spraying technology are adopted in the application of heat barrier coat material as claimed in claim 1, it is characterized in that the coating use temperature is interval to be room temperature to 1400 ℃.
3, the application of heat barrier coat material as claimed in claim 2 is characterized in that, metal base is by parts Ni-based or that cobalt base superalloy is formed.
4, the application of heat barrier coat material as claimed in claim 2 is characterized in that, metal bonding coating is the MCrAlY alloy, and wherein M is one or more the combination among Ni, Co or the Fe, and Y is a kind of among Y, La or the Hf.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101159341A CN1329551C (en) | 2003-12-16 | 2003-12-16 | Novel heat barrier coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101159341A CN1329551C (en) | 2003-12-16 | 2003-12-16 | Novel heat barrier coating material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1546719A true CN1546719A (en) | 2004-11-17 |
| CN1329551C CN1329551C (en) | 2007-08-01 |
Family
ID=34337453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101159341A Expired - Fee Related CN1329551C (en) | 2003-12-16 | 2003-12-16 | Novel heat barrier coating material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1329551C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101522949B (en) * | 2006-10-02 | 2011-12-21 | 西门子公司 | Pyrochlore materials and a thermal barrier coating with these pyrochlore materials |
| CN103304236A (en) * | 2013-06-09 | 2013-09-18 | 渤海大学 | Three-phase nano thermal barrier coating material in pyrochlore structure and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034132C (en) * | 1994-10-29 | 1997-02-26 | 华南理工大学 | Method of raising thermal barrier ceramic coating performance |
| US6258467B1 (en) * | 2000-08-17 | 2001-07-10 | Siemens Westinghouse Power Corporation | Thermal barrier coating having high phase stability |
-
2003
- 2003-12-16 CN CNB2003101159341A patent/CN1329551C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101522949B (en) * | 2006-10-02 | 2011-12-21 | 西门子公司 | Pyrochlore materials and a thermal barrier coating with these pyrochlore materials |
| CN103304236A (en) * | 2013-06-09 | 2013-09-18 | 渤海大学 | Three-phase nano thermal barrier coating material in pyrochlore structure and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1329551C (en) | 2007-08-01 |
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Granted publication date: 20070801 Termination date: 20100118 |