JP2001348655A - Thermal barrier coating material, gas turbine member applied with the same and gas turbine - Google Patents
Thermal barrier coating material, gas turbine member applied with the same and gas turbineInfo
- Publication number
- JP2001348655A JP2001348655A JP2000173399A JP2000173399A JP2001348655A JP 2001348655 A JP2001348655 A JP 2001348655A JP 2000173399 A JP2000173399 A JP 2000173399A JP 2000173399 A JP2000173399 A JP 2000173399A JP 2001348655 A JP2001348655 A JP 2001348655A
- Authority
- JP
- Japan
- Prior art keywords
- ceramic layer
- gas turbine
- strength
- toughness
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 87
- 239000012720 thermal barrier coating Substances 0.000 title claims abstract description 48
- 239000000919 ceramic Substances 0.000 claims abstract description 187
- 239000002184 metal Substances 0.000 claims description 63
- 229910052751 metal Inorganic materials 0.000 claims description 63
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 7
- 229910002078 fully stabilized zirconia Inorganic materials 0.000 claims description 4
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 abstract description 10
- 229910045601 alloy Inorganic materials 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 230000000704 physical effect Effects 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 abstract description 3
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 abstract 2
- 230000004888 barrier function Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 219
- 239000007789 gas Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 28
- 238000007750 plasma spraying Methods 0.000 description 26
- 238000005328 electron beam physical vapour deposition Methods 0.000 description 22
- 238000012360 testing method Methods 0.000 description 16
- 239000003381 stabilizer Substances 0.000 description 14
- 238000012937 correction Methods 0.000 description 12
- 230000008646 thermal stress Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000567 combustion gas Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 238000012916 structural analysis Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 102100033041 Carbonic anhydrase 13 Human genes 0.000 description 1
- 101000867860 Homo sapiens Carbonic anhydrase 13 Proteins 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- NPURPEXKKDAKIH-UHFFFAOYSA-N iodoimino(oxo)methane Chemical compound IN=C=O NPURPEXKKDAKIH-UHFFFAOYSA-N 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
- C23C28/3215—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer at least one MCrAlX layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/36—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including layers graded in composition or physical properties
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Coating By Spraying Or Casting (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、遮熱コーティング
材、ガスタービン部材およびガスタービンに関し、例え
ば産業用ガスタービンの動翼、静翼または燃焼器などの
高温環境下で使用される部品の遮熱コーティングに適用
して有用な技術に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal barrier coating material, a gas turbine member, and a gas turbine, and more particularly to the shielding of components used in a high-temperature environment such as a moving blade, a stationary blade, or a combustor of an industrial gas turbine. The present invention relates to a technique useful for applying to thermal coating.
【０００２】[0002]
【従来の技術】産業用ガスタービンの動翼や静翼、ある
いは燃焼器の内筒や尾筒などの高温部品は、高温環境下
にて使用されるため、一般に、その表面に遮熱コーティ
ングが施されている。図３は、従来の遮熱コーティング
膜の構成を示す断面図である。従来、遮熱コーティング
膜は、動翼等の母材１１上に金属結合層１２が積層さ
れ、さらにその上にセラミックス層１３が積層された構
成となっている。2. Description of the Related Art High-temperature components such as rotor blades and stator blades of industrial gas turbines, and inner and tail tubes of combustors are used in a high-temperature environment. It has been subjected. FIG. 3 is a cross-sectional view showing a configuration of a conventional thermal barrier coating film. Conventionally, the thermal barrier coating film has a configuration in which a metal bonding layer 12 is laminated on a base material 11 such as a moving blade, and a ceramic layer 13 is further laminated thereon.
【０００３】金属結合層１２は、母材１１とセラミック
ス層１３との熱膨張係数の差を小さくして熱応力の緩和
を図り、それによってセラミックス層１３が剥離するの
を防ぐために設けられる。金属結合層１２は、一般に、
高温での耐食性および耐酸化性に優れたＭＣｒＡｌＹ合
金系（Ｍは、ＮｉやＣｏやＦｅ等の単独元素または２種
類以上の元素の組み合わせ）により構成される。金属結
合層１２の積層方法として、低圧プラズマ溶射法または
電子ビーム物理蒸着法が用いられる。[0003] The metal bonding layer 12 is provided to reduce the difference in thermal expansion coefficient between the base material 11 and the ceramic layer 13 to relieve thermal stress and thereby prevent the ceramic layer 13 from peeling off. The metal bonding layer 12 generally comprises
It is composed of an MCrAlY alloy system (M is a single element such as Ni, Co or Fe or a combination of two or more elements) having excellent corrosion resistance and oxidation resistance at high temperatures. As a method for laminating the metal bonding layer 12, a low-pressure plasma spraying method or an electron beam physical vapor deposition method is used.
【０００４】セラミックス層１３は遮熱のために設けら
れる。セラミック層１３は、一般に、熱伝導率が低く、
かつ靭性が高い部分安定化ＺｒＯ2 系セラミックスで構
成される。安定化剤としてはＹ2 Ｏ3 が用いられる。つ
まり、セラミック層１３はＺｒＯ2 ・６〜８ｗｔ％Ｙ2
Ｏ3 でできている。セラミックス層３は大気圧プラズマ
溶射法または電子ビーム物理蒸着法により積層される。The ceramic layer 13 is provided for heat insulation. The ceramic layer 13 generally has low thermal conductivity,
It is composed of a partially stabilized ZrO 2 ceramic having high toughness. Y 2 O 3 is used as a stabilizer. That is, the ceramic layer 13 is ZrO 2 · 6~8wt% Y 2
Made of O 3 . The ceramic layer 3 is laminated by an atmospheric pressure plasma spraying method or an electron beam physical vapor deposition method.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、近時、
ガスタービンのタービン入口温度がより高温になってき
ており、そのため、次のような問題点が生じるおそれが
ある。すなわち、セラミックス層１３と母材１１との熱
膨張差に起因する繰り返し熱応力によりセラミックス層
１３にき裂が発生し、それが伝播していく。また、セラ
ミックス層１３の表層付近が著しい高温にさらされるこ
とによって相変態や焼結に起因する物性変化が起こり、
ヤング率の増大や線膨張係数の低下が起こる。それによ
って、熱応力がさらに増加し、き裂の発生および伝播が
加速されることになり、遮熱コーティングの寿命が短く
なってしまう。However, recently,
The turbine inlet temperature of the gas turbine has become higher, which may cause the following problems. That is, a crack is generated in the ceramic layer 13 due to repeated thermal stress caused by a difference in thermal expansion between the ceramic layer 13 and the base material 11, and the crack propagates. In addition, when the vicinity of the surface layer of the ceramic layer 13 is exposed to a remarkably high temperature, physical properties change due to phase transformation and sintering occurs,
The Young's modulus increases and the linear expansion coefficient decreases. This further increases thermal stress, which accelerates crack initiation and propagation, and shortens the life of the thermal barrier coating.
【０００６】本発明は、上記問題点を解決するためにな
されたもので、より耐熱性に優れ、より高温での耐久性
に優れた遮熱コーティング材を提供することを目的とす
る。また、本発明の他の目的は、より耐熱性に優れ、よ
り高温での耐久性に優れた遮熱コーティング材を適用し
たガスタービン部材を提供することである。The present invention has been made to solve the above problems, and an object of the present invention is to provide a thermal barrier coating material having more excellent heat resistance and excellent durability at higher temperatures. Another object of the present invention is to provide a gas turbine member to which a thermal barrier coating material having excellent heat resistance and excellent durability at higher temperatures is applied.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
に、本発明者は、遮熱コーティング膜の最外層に、高温
での相安定性に優れる高温相安定セラミックス層を配置
し、その下に、強度および靭性の高い高強度・高靭性セ
ラミックス層を配置して熱応力を緩和する構成とすれ
ば、高温で十分な耐久性が得られると考えた。また、安
定化剤としてＤｙ 2 Ｏ3 を用いたセラミックスを用いれ
ば、より耐熱性に優れ、より高温で十分な耐久性が得ら
れると考え、鋭意研究を重ねた結果、本発明の完成に至
った。[MEANS FOR SOLVING THE PROBLEMS] To achieve the above object
In addition, the present inventor has proposed that the outermost layer
High-temperature phase-stable ceramic layer with excellent phase stability
Below that, a high-strength, high-toughness
Laminate layer to reduce thermal stress
It was thought that sufficient durability could be obtained at high temperatures. Also, cheap
Dy as a stabilizing agent TwoOThreeUsing ceramics
Better heat resistance and sufficient durability at higher temperatures.
As a result of intensive research, the present invention was completed.
Was.
【０００８】すなわち、本発明にかかる遮熱コーティン
グ材は、母材の上に金属結合層を積層し、前記金属結合
層の上に高強度・高靭性セラミックス層を積層し、前記
高強度・高靭性セラミックス層の上に高温相安定セラミ
ックス層を積層したことを特徴とする。この発明におい
て、前記高強度・高靭性セラミックス層は、Ｙ2 Ｏ3で
安定化させた部分安定化ジルコニアにより構成されてい
てもよいし、また、高温相安定セラミックス層は、Ｙ2
Ｏ3 で安定化させた完全安定化ジルコニアにより構成さ
れていてもよい。あるいは、前記高強度・高靭性セラミ
ックス層は、Ｄｙ2 Ｏ3 で安定化させた部分安定化ジル
コニアにより構成されていてもよいし、また、高温相安
定セラミックス層は、Ｄｙ2 Ｏ3 で安定化させた完全安
定化ジルコニアにより構成されていてもよい。That is, in the thermal barrier coating material according to the present invention, a metal bonding layer is laminated on a base material, and a high-strength and high-toughness ceramic layer is laminated on the metal bonding layer. A high-temperature phase-stable ceramic layer is laminated on a tough ceramic layer. In the present invention, the high strength and high toughness ceramic layer may be composed of partially stabilized zirconia stabilized with Y 2 O 3, also high temperature phase stability ceramic layer is Y 2
It may be composed of fully stabilized zirconia stabilized with O 3 . Alternatively, the high strength and high toughness ceramic layer may be composed of stabilized was partially stabilized zirconia Dy 2 O 3, also high temperature phase stability ceramic layer is stabilized with Dy 2 O 3 It may be made of completely stabilized zirconia.
【０００９】この遮熱コーティング材によれば、最外層
に高温相安定セラミックス層が設けられるため、高温環
境下での遮熱コーティング材の劣化が抑制される。ま
た、高温相安定セラミックス層と母材との間に高強度・
高靭性セラミックス層が設けられることにより、母材と
セラミックス層の線膨張係数差に起因する熱応力に耐え
ることができるので、セラミックス層の剥離が防止され
る。したがって、温度環境が従来よりも高温であっても
十分な耐久性が得られ、遮熱コーティング材の寿命が短
くなるのを防ぐことができる。さらに、セラミックス材
の安定化剤としてＤｙ2 Ｏ3 を用いた場合、Ｄｙ2 Ｏ 3
はＹ2 Ｏ3 よりも熱伝導率が低いため、より耐熱性に優
れるとともに、より高温であっても十分な耐久性が得ら
れる。According to this thermal barrier coating material, the outermost layer
Is provided with a high-temperature phase-stable ceramic layer.
Deterioration of the thermal barrier coating material under the environment is suppressed. Ma
In addition, high strength and high strength
By providing a high toughness ceramic layer,
Resists thermal stress caused by difference in coefficient of linear expansion of ceramics layer
To prevent the ceramic layer from peeling off.
You. Therefore, even if the temperature environment is higher than before
Sufficient durability and short life of thermal barrier coating
Can be prevented. Furthermore, ceramic materials
Dy as a stabilizer forTwoOThreeWhen Dy is used,TwoO Three
Is YTwoOThreeLower thermal conductivity than heat resistance
And have sufficient durability even at higher temperatures.
It is.
【００１０】また、本発明にかかるガスタービン部材
は、母材の上に金属結合層が積層され、前記金属結合層
の上に高強度・高靭性セラミックス層が積層され、前記
高強度・高靭性セラミックス層の上に高温相安定セラミ
ックス層が積層されてなる遮熱コーティング膜で被覆さ
れていることを特徴とする。この発明において、前記高
強度・高靭性セラミックス層は、Ｙ2 Ｏ3 で安定化させ
た部分安定化ジルコニアにより構成されていてもよい
し、また、高温相安定セラミックス層は、Ｙ2 Ｏ3で安
定化させた完全安定化ジルコニアにより構成されていて
もよい。あるいは、前記高強度・高靭性セラミックス層
は、Ｄｙ2 Ｏ3 で安定化させた部分安定化ジルコニアに
より構成されていてもよいし、また、高温相安定セラミ
ックス層は、Ｄｙ2 Ｏ3 で安定化させた完全安定化ジル
コニアにより構成されていてもよい。In the gas turbine member according to the present invention, a metal bonding layer is laminated on a base material, and a high-strength and high-toughness ceramic layer is laminated on the metal bonding layer. It is characterized by being covered with a thermal barrier coating film formed by laminating a high-temperature phase-stable ceramic layer on a ceramic layer. In the present invention, the high strength and high toughness ceramic layer may be composed of stabilized was partially stabilized zirconia Y 2 O 3, also high temperature phase stability ceramic layer is a Y 2 O 3 It may be composed of stabilized fully stabilized zirconia. Alternatively, the high strength and high toughness ceramic layer may be composed of stabilized was partially stabilized zirconia Dy 2 O 3, also high temperature phase stability ceramic layer is stabilized with Dy 2 O 3 It may be made of completely stabilized zirconia.
【００１１】このガスタービン部材によれば、遮熱コー
ティング膜の最外層に高温相安定セラミックス層が設け
られるため、高温環境下での遮熱コーティング膜の劣化
が抑制される。また、高温相安定セラミックス層と母材
との間に高強度・高靭性セラミックス層が設けられるこ
とにより、母材とセラミックス層の線膨張係数差に起因
する熱応力に耐えることができるので、遮熱コーティン
グ膜のセラミックス層の剥離が防止される。したがっ
て、温度環境が従来よりも高温であっても十分な耐久性
を有するガスタービン部材を得ることができる。さら
に、セラミックス材の安定化剤としてＤｙ2 Ｏ3 を用い
た場合、Ｄｙ2 Ｏ 3 はＹ2 Ｏ3 よりも熱伝導率が低いた
め、より耐熱性に優れるとともに、より高温であっても
十分な耐久性を有するガスタービン部材を得ることがで
きる。According to this gas turbine member, the heat shield coat
High-temperature phase-stable ceramic layer is provided as the outermost layer of the coating film
Deterioration of the thermal barrier coating film in a high temperature environment
Is suppressed. In addition, a high-temperature phase-stable ceramic layer and a base material
A high-strength, high-toughness ceramic layer
Due to the difference in linear expansion coefficient between the base material and the ceramic layer
Heat-shielding coating
The peeling of the ceramic layer of the metal film is prevented. Accordingly
Sufficient durability even when the temperature environment is higher than before
Can be obtained. Further
Dy as a stabilizer for ceramic materialsTwoOThreeUsing
DyTwoO ThreeIs YTwoOThreeHas lower thermal conductivity than
Because of its excellent heat resistance, even at higher temperatures
It is possible to obtain gas turbine components with sufficient durability.
Wear.
【００１２】[0012]
【発明の実施の形態】本発明にかかる遮熱コーティング
の実施の形態について説明する。図１は、本発明にかか
る遮熱コーティング材を適用した遮熱コーティング膜の
構成を示す断面図である。遮熱コーティング膜は、ガス
タービンの動翼等を構成する母材２１の上に、耐食性お
よび耐酸化性に優れた金属結合層２２、強度および靭性
は高いが１１００℃以上の温度で相変態や焼結を生じて
物性が変化する可能性のある高強度・高靭性セラミック
ス層２３を順次積層し、最外層に強度および靭性は低い
が高温での相安定性に優れる高温相安定セラミックス層
２４を積層した構成となっている。DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the thermal barrier coating according to the present invention will be described. FIG. 1 is a cross-sectional view showing a configuration of a thermal barrier coating film to which the thermal barrier coating material according to the present invention is applied. The thermal barrier coating film is formed on a base material 21 constituting a blade or the like of a gas turbine, a metal bonding layer 22 having excellent corrosion resistance and oxidation resistance, and having a high strength and toughness but having a phase transformation at a temperature of 1100 ° C. or more. A high-strength and high-toughness ceramic layer 23 which may change its physical properties due to sintering is sequentially laminated, and a high-temperature phase-stable ceramic layer 24 having low strength and toughness but excellent in phase stability at high temperatures is formed on the outermost layer. It has a laminated configuration.
【００１３】金属結合層２２は、母材２１とセラミック
ス層２３，２４との熱膨張係数の差を小さくして熱応力
を緩和する機能を有し、セラミックス層２３，２４が母
材２１から剥離するのを防いでいる。金属結合層２２
は、従来同様、ＭＣｒＡｌＹ合金系（Ｍは、ＮｉやＣｏ
やＦｅ等の単独元素または２種類以上の元素の組み合わ
せ）により構成される。金属結合層２２の厚さは、０．
０１〜０．３ｍｍであるのが適当である。その理由は、
母材とセラミックス層との線膨張係数差を緩和するた
め、および母材に耐酸化性を付与するためである。The metal bonding layer 22 has a function of reducing the difference in coefficient of thermal expansion between the base material 21 and the ceramic layers 23 and 24 to relieve thermal stress, and the ceramic layers 23 and 24 are separated from the base material 21. To prevent Metal bonding layer 22
Is a conventional MCrAlY alloy (M is Ni or Co
Or a single element such as Fe or a combination of two or more elements). The thickness of the metal bonding layer 22 is set to 0.
Suitably, it is between 0.01 and 0.3 mm. The reason is,
This is for reducing the difference in linear expansion coefficient between the base material and the ceramic layer and for imparting oxidation resistance to the base material.
【００１４】高強度・高靭性セラミックス層２３は部分
安定化ＺｒＯ2 系セラミックスで構成される。安定化剤
としてＹ2 Ｏ3 を用いる場合には、高強度・高靭性セラ
ミックス層２３はＺｒＯ2 ・６〜１２ｗｔ％Ｙ2 Ｏ3 で
できている。Ｙ2 Ｏ3 の割合が６〜１２ｗｔ％である理
由は、この範囲の安定化剤の添加量の場合には、結晶構
造が準安定正方晶となり、この場合、ＺｒＯ2 セラミッ
クスは高い強度と靭性を有することが知られているから
である。この場合、高強度・高靭性セラミックス層２３
の厚さは、０．０５〜０．４５ｍｍであるのが適当であ
る。その理由は、比較的温度が低く、かつ、線膨張係数
差による歪みが大きいと考えられる領域に、この高強
度、高靭性セラミックスを配置し、セラミックス層の剥
離を防止するためである。The high-strength and high-toughness ceramic layer 23 is made of a partially stabilized ZrO 2 ceramic. When Y 2 O 3 is used as a stabilizer, the high-strength and high-toughness ceramic layer 23 is made of ZrO 2 .6 to 12 wt% Y 2 O 3 . The reason that the proportion of Y 2 O 3 is 6 to 12 wt% is that when the amount of the stabilizer added is in this range, the crystal structure becomes a metastable tetragonal crystal. In this case, the ZrO 2 ceramic has high strength and toughness. It is because it is known to have. In this case, the high strength / high toughness ceramic layer 23
Is suitably from 0.05 to 0.45 mm. The reason is that this high-strength, high-toughness ceramic is arranged in a region where the temperature is relatively low and the distortion due to the difference in linear expansion coefficient is considered to be large, to prevent the ceramic layer from peeling off.
【００１５】部分安定化ＺｒＯ2 系セラミックスの安定
化剤としてＤｙ2 Ｏ3 を用いる場合には、高強度・高靭
性セラミックス層２３はＺｒＯ2 ・８〜１６ｗｔ％Ｄｙ
2 Ｏ 3 でできている。Ｄｙ2 Ｏ3 の割合が８〜１６ｗｔ
％である理由は、この範囲の安定化剤の添加量の場合に
は、結晶構造が準安定正方晶となり、この場合、ＺｒＯ
2 セラミックスは高い強度と靭性を有することが知られ
ているからである。この場合、高強度・高靭性セラミッ
クス層２３の厚さは、０．０５〜０．４５ｍｍであるの
が適当である。その理由は、比較的温度が低く、かつ、
線膨張係数差による歪みが大きいと考えられる領域に、
この高強度、高靭性セラミックスを配置し、セラミック
ス層の剥離を防止するためである。Partially stabilized ZrOTwoOf ceramics
Dy as an agentTwoOThreeWhen using high strength and high toughness
Ceramic layer 23 is made of ZrOTwo・ 8 to 16 wt% Dy
TwoO ThreeIt is made of DyTwoOThree8 to 16 wt%
The reason is that the amount of stabilizer added in this range
Shows that the crystal structure becomes metastable tetragonal, in which case ZrO
TwoCeramics are known to have high strength and toughness
Because it is. In this case, high strength and high toughness ceramic
The thickness of the layer 23 is 0.05 to 0.45 mm.
Is appropriate. The reason is that the temperature is relatively low and
In the region where the distortion due to the difference in linear expansion coefficient is considered to be large,
This high-strength, high-toughness ceramic is placed
This is for preventing peeling of the layer.
【００１６】高温相安定セラミックス層２４は完全安定
化ＺｒＯ2 系セラミックスで構成される。安定化剤とし
てＹ2 Ｏ3 を用いる場合には、高温相安定セラミックス
層２４はＺｒＯ2 ・１５〜２０ｗｔ％Ｙ2 Ｏ3 でできて
いる。Ｙ2 Ｏ3 の割合が１５〜２０ｗｔ％である理由
は、この範囲の安定剤の添加量の場合には、結晶構造が
立方晶となり、この場合、ＺｒＯ2 セラミックスは高温
でも安定なものとなることが知られているからである。
この場合、高温相安定セラミックス層２４の厚さは、
０．０５〜０．４５ｍｍであるのが適当である。その理
由は、最も温度が高くなる最表層部に、この高温相安定
セラミックスを配置し、表面付近の物性変化を防止する
ためである。The high-temperature phase-stable ceramic layer 24 is made of a completely stabilized ZrO 2 ceramic. When Y 2 O 3 is used as a stabilizer, the high-temperature phase-stable ceramic layer 24 is made of ZrO 2 .15 to 20 wt% Y 2 O 3 . The reason that the ratio of Y 2 O 3 is 15 to 20 wt% is that when the amount of the stabilizer added in this range is used, the crystal structure becomes cubic, and in this case, the ZrO 2 ceramic becomes stable even at a high temperature. Because it is known.
In this case, the thickness of the high-temperature phase-stable ceramics layer 24 is
Suitably, it is between 0.05 and 0.45 mm. The reason is that this high-temperature phase-stable ceramic is disposed in the outermost layer portion where the temperature is highest, so as to prevent a change in physical properties near the surface.
【００１７】完全安定化ＺｒＯ2 系セラミックスの安定
化剤としてＤｙ2 Ｏ3 を用いる場合には、高温相安定セ
ラミックス層２４はＺｒＯ2 ・１６〜２０ｗｔ％Ｄｙ2
Ｏ3でできている。Ｄｙ2 Ｏ3 の割合が１６〜２０ｗｔ
％である理由は、この範囲の安定剤の添加量の場合に
は、結晶構造が立方晶となり、この場合、ＺｒＯ2 セラ
ミックスは高温でも安定なものとなることが知られてい
るからである。この場合、高温相安定セラミックス層２
４の厚さは、０．０５〜０．４５ｍｍであるのが適当で
ある。その理由は、最も温度が高くなる最表層部に、こ
の高温相安定セラミックスを配置し、表面付近の物性変
化を防止するためである。When Dy 2 O 3 is used as a stabilizer for the fully stabilized ZrO 2 -based ceramic, the high-temperature phase-stable ceramic layer 24 is made of ZrO 2 .16 to 20 wt% Dy 2
Made of O 3 . Dy 2 O 3 ratio of 16 to 20 wt.
The reason for the percentage is that when the amount of the stabilizer added is in this range, the crystal structure becomes cubic, and in this case, the ZrO 2 ceramic is known to be stable even at high temperatures. In this case, the high-temperature phase-stable ceramic layer 2
Suitably, the thickness of 4 is 0.05 to 0.45 mm. The reason is that this high-temperature phase-stable ceramic is disposed in the outermost layer portion where the temperature is highest, so as to prevent a change in physical properties near the surface.
【００１８】金属結合層２２は低圧プラズマ溶射法また
は電子ビーム物理蒸着法により積層される。高強度・高
靭性セラミックス層２３および高温相安定セラミックス
層２４は大気圧プラズマ溶射法または電子ビーム物理蒸
着法により積層される。The metal bonding layer 22 is laminated by low pressure plasma spraying or electron beam physical vapor deposition. The high-strength and high-toughness ceramic layer 23 and the high-temperature phase-stable ceramic layer 24 are stacked by atmospheric pressure plasma spraying or electron beam physical vapor deposition.
【００１９】上述した構成の遮熱コーティング材は、産
業用ガスタービンの動翼や静翼、あるいは燃焼器の内筒
や尾筒、分割環などの高温部品に適用して有用である。
また、産業用ガスタービンに限らず、車やジェット機な
どのエンジンの高温部品の遮熱コーティング膜にも適用
できる。The thermal barrier coating material having the above-described structure is useful when applied to high-temperature parts such as a moving blade and a stationary blade of an industrial gas turbine, an inner cylinder and a transition piece of a combustor, and a split ring.
Further, the present invention can be applied not only to industrial gas turbines but also to thermal barrier coating films for high-temperature parts of engines such as cars and jets.
【００２０】図４および図５は、それぞれ上述した実施
の形態にかかる遮熱部材を適用可能なタービン翼を示す
斜視図である。図４に示すガスタービン動翼４は、デイ
スク側に固定されるダブテイル４１、プラットフォーム
４２、翼部４３等を備えている。また、図５に示すガス
タービン静翼５は、内シュラウド５１、外シュラウド５
２、翼部５３等を備えており、翼部５３には、シールフ
ィン冷却孔５４、スリット５５等が形成されている。こ
れらガスタービン動翼４およびガスタービン静翼５は、
いずれも図６に示すガスタービンに適用可能なものであ
る。FIGS. 4 and 5 are perspective views showing turbine blades to which the heat shield according to the above-described embodiment can be applied. The gas turbine rotor blade 4 shown in FIG. 4 includes a dovetail 41 fixed to the disk side, a platform 42, a blade portion 43, and the like. The gas turbine stationary blade 5 shown in FIG. 5 has an inner shroud 51 and an outer shroud 5.
2. The wing portion 53 is provided with a seal fin cooling hole 54, a slit 55, and the like. These gas turbine rotor blades 4 and gas turbine stationary blades 5
Each of them is applicable to the gas turbine shown in FIG.
【００２１】図６に示すガスタービンについて簡単に説
明する。このガスタービン６は、互いに直結された圧縮
機６１とタービン６２とを備える。圧縮機６１は例えば
軸流圧縮機として構成されており、大気または所定のガ
スを吸込口から作動流体として吸い込んで昇圧させる。
この圧縮機６１の吐出口には、燃焼器６３が接続されて
おり、圧縮機６１から吐出された作動流体は、燃焼器６
３によって所定のタービン入口温度まで加熱される。そ
して所定温度まで昇温された作動流体は、タービン６２
に供給される。図６に示すように、タービン６２のケー
シング内部には、上述したガスタービン静翼４が数段
（図では４段）固定されている。また、上述したガスタ
ービン動翼５が各静翼４と一組の段を形成するように主
軸６４に取り付けられている。主軸６４の一端は、圧縮
機６１の回転軸６５に接続されており、その他端には、
図示しない発電機の回転軸に接続されている。The gas turbine shown in FIG. 6 will be briefly described. The gas turbine 6 includes a compressor 61 and a turbine 62 directly connected to each other. The compressor 61 is configured as, for example, an axial compressor, and sucks air or a predetermined gas as a working fluid from a suction port to increase the pressure.
A combustor 63 is connected to a discharge port of the compressor 61, and a working fluid discharged from the compressor 61 is supplied to the combustor 6.
3 heats up to a predetermined turbine inlet temperature. The working fluid heated to the predetermined temperature is supplied to the turbine 62
Supplied to As shown in FIG. 6, several stages (four stages in the figure) of the gas turbine stationary blades 4 are fixed inside the casing of the turbine 62. Further, the above-described gas turbine rotor blades 5 are attached to the main shaft 64 so as to form a set of stages with each of the stationary blades 4. One end of the main shaft 64 is connected to the rotation shaft 65 of the compressor 61, and the other end is
It is connected to the rotating shaft of a generator (not shown).
【００２２】このような構成により、燃焼器６３からタ
ービン６２のケーシング内に高温高圧の作動流体を供給
すれば、ケーシング内で作動流体が膨張することによ
り、主軸６４が回転し、図示しない発電機が駆動され
る。すなわち、ケーシングに固定されている各静翼４に
よって圧力降下させられ、これにより発生した運動エネ
ルギは、主軸６５に取付けられた各動翼５を介して回転
トルクに変換される。そして、発生した回転トルクは、
主軸６４に伝達され、発電機が駆動される。With such a configuration, when a high-temperature and high-pressure working fluid is supplied from the combustor 63 into the casing of the turbine 62, the working fluid expands in the casing, whereby the main shaft 64 rotates and a generator (not shown) Is driven. That is, the pressure is reduced by each stationary blade 4 fixed to the casing, and the generated kinetic energy is converted into rotational torque via each moving blade 5 attached to the main shaft 65. And the generated rotational torque is
The power is transmitted to the main shaft 64 and the generator is driven.
【００２３】一般に、ガスタービン動翼に用いられる材
料は、耐熱合金（たとえば、ＣＭ２４７ＬＣ＝キャノン
マスケゴン社の市販の合金材料）であり、ガスタービ
ン静翼に用いられる材料は、同様に耐熱合金（たとえば
ＩＮ９３９＝インコ社の市販の合金材料）である。すな
わち、タービン翼を構成する材料は、本発明による遮熱
部材において基材として採用可能な耐熱合金が使用され
ている。したがって、本発明による遮熱部材をタービン
翼へ被覆すれば、遮熱効果と耐剥離性の高いタービン翼
を得ることができ、温度環境をより高くしかも耐久性の
良いものとなり、ロングライフ化が可能となる。また、
作動流体の温度を高めることにより、ガスタービン効率
を向上させることも可能となる。Generally, the material used for the gas turbine blade is a heat-resistant alloy (for example, CM247LC = a commercially available alloy material of Canon Muskegon), and the material used for the gas turbine stationary blade is similarly a heat-resistant alloy (for example, IN939 = commercially available alloy material from INCO). That is, the material constituting the turbine blade is a heat-resistant alloy that can be used as a base material in the heat shield member according to the present invention. Therefore, if the heat shielding member according to the present invention is coated on the turbine blade, a turbine blade having high heat shielding effect and high peeling resistance can be obtained, the temperature environment becomes higher and the durability becomes longer, and a longer life can be achieved. It becomes possible. Also,
Increasing the temperature of the working fluid can also improve gas turbine efficiency.
【００２４】上述した実施の形態によれば、最外層に高
温相安定セラミックス層２４が設けられ、その下に高強
度・高靭性セラミックス層２３が設けられているため、
高温環境下で遮熱コーティング材が劣化するのが抑制さ
れるとともに、母材とセラミックス相の線膨張係数差に
起因する熱応力に耐えることができることから、セラミ
ックス層２３，２４の剥離が防止される。したがって、
温度環境が従来よりも高温であっても十分な耐久性が得
られ、遮熱コーティング材の寿命が短くなるのを防ぐこ
とができる。また、セラミックスの安定化剤として、Ｙ
2 Ｏ3 よりも熱伝導率が低いＤｙ2 Ｏ3 を用いた場合に
は、より耐熱性に優れるという効果が得られる。また、
ガスタービンの高温部品をこの遮熱コーティング材で被
覆することによって、温度環境が従来よりも高温であっ
ても十分な耐久性を有するガスタービン部材を得ること
ができる。According to the above-described embodiment, the high-temperature phase-stable ceramic layer 24 is provided as the outermost layer, and the high-strength and high-toughness ceramic layer 23 is provided thereunder.
Deterioration of the thermal barrier coating material in a high temperature environment is suppressed, and thermal stress caused by a difference in linear expansion coefficient between the base material and the ceramic phase can be withheld. Therefore, peeling of the ceramic layers 23 and 24 is prevented. You. Therefore,
Even if the temperature environment is higher than before, sufficient durability can be obtained, and the life of the thermal barrier coating material can be prevented from being shortened. Further, as a stabilizer for ceramics, Y
When the thermal conductivity than 2 O 3 was used lower Dy 2 O 3, the effect is obtained that more excellent heat resistance. Also,
By coating a high-temperature component of the gas turbine with the thermal barrier coating material, a gas turbine member having sufficient durability can be obtained even when the temperature environment is higher than before.
【００２５】[0025]
【実施例】以下に、実施例および比較例を挙げて本発明
の特徴とするところを明らかとする。以下の各実施例お
よび各比較例では、母材である耐熱合金としてＮｉ基合
金（Ｎｉ−１６Ｃｒ−８．５Ｃｏ−１．７Ｍｏ−２．６
Ｗ−１．７Ｔａ−０．９Ｎｂ−３．４Ａｌ−３．４Ｔ
ｉ）を用いた。母材のサイズは３０ｍｍ角で厚さ５ｍｍ
とした。また、金属結合層はＣｏＮｉＣｒＡｌＹ（Ｃｏ
−３２Ｎｉ−２１Ｃｒ−８Ａｌ−０．５Ｙ）とした。EXAMPLES The features of the present invention will be clarified below with reference to examples and comparative examples. In each of the following Examples and Comparative Examples, a Ni-based alloy (Ni-16Cr-8.5Co-1.7Mo-2.6) was used as a heat-resistant alloy as a base material.
W-1.7Ta-0.9Nb-3.4Al-3.4T
i) was used. The base material is 30mm square and 5mm thick
And The metal bonding layer is made of CoNiCrAlY (Co
-32Ni-21Cr-8Al-0.5Y).
【００２６】実施例１．以下に示すＮｏ．１〜１６の試
料を作製した。Ｎｏ．１〜１６の試料では、高強度・高
靭性セラミックス層はＺｒＯ2 ・８ｗｔ％Ｙ2 Ｏ3 と
し、高温相安定セラミックス層はＺｒＯ2 ・１７ｗｔ％
Ｙ2 Ｏ3 とした。Embodiment 1 FIG. No. shown below. 1 to 16 samples were prepared. No. In the samples Nos. 1 to 16, the high-strength and high-toughness ceramic layer was ZrO 2 .8 wt% Y 2 O 3 , and the high-temperature phase-stable ceramic layer was ZrO 2 .17 wt%.
Y 2 O 3 was used.
【００２７】（試料Ｎｏ．１）母材の表面をＡｌ2 Ｏ3
粒でグリッドブラスト処理して、低圧プラズマ溶射に適
した状態にした。ついで、金属結合層を低圧プラズマ溶
射法により０．１ｍｍの厚さで成膜した。ついで、高強
度・高靭性セラミックス層を大気圧プラズマ溶射法によ
り０．１ｍｍの厚さで成膜した。最後に、高温相安定セ
ラミックス層を大気圧プラズマ溶射法により０．４ｍｍ
の厚さで成膜した。 （試料Ｎｏ．２）Ｎｏ．１の試料と同様にして、母材上
に厚さ０．１ｍｍの金属結合層、厚さ０．２ｍｍの高強
度・高靭性セラミックス層、厚さ０．３ｍｍの高温相安
定セラミックス層を順次積層した。(Sample No. 1) The surface of the base material was made of Al 2 O 3
The particles were grid blasted to a state suitable for low pressure plasma spraying. Next, a metal bonding layer was formed to a thickness of 0.1 mm by low-pressure plasma spraying. Next, a high-strength, high-toughness ceramic layer was formed to a thickness of 0.1 mm by atmospheric pressure plasma spraying. Finally, the high-temperature phase-stable ceramics layer is 0.4 mm thick by atmospheric pressure plasma spraying.
The thickness was formed as follows. (Sample No. 2) In the same manner as in the sample 1, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.2 mm, and a high-temperature phase-stable ceramic layer having a thickness of 0.3 mm were sequentially laminated on the base material. did.
【００２８】（試料Ｎｏ．３）Ｎｏ．１の試料と同様に
して、母材上に厚さ０．１ｍｍの金属結合層、厚さ０．
３ｍｍの高強度・高靭性セラミックス層、厚さ０．２ｍ
ｍの高温相安定セラミックス層を順次積層した。 （試料Ｎｏ．４）Ｎｏ．１の試料と同様にして、母材上
に厚さ０．１ｍｍの金属結合層、厚さ０．４ｍｍの高強
度・高靭性セラミックス層、厚さ０．１ｍｍの高温相安
定セラミックス層を順次積層した。(Sample No. 3) In the same manner as in the sample No. 1, a metal bonding layer having a thickness of 0.1 mm was formed on the base material.
3mm high strength and high toughness ceramic layer, 0.2m thick
m high-temperature phase-stable ceramic layers were sequentially laminated. (Sample No. 4) In the same manner as in Sample 1, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.4 mm, and a high-temperature phase-stable ceramic layer having a thickness of 0.1 mm were sequentially laminated on the base material. did.
【００２９】（試料Ｎｏ．５）母材の表面をＡｌ2 Ｏ3
粒でグリッドブラスト処理して、低圧プラズマ溶射に適
した状態にした。ついで、金属結合層を低圧プラズマ溶
射法により０．１ｍｍの厚さで成膜した。ついで、金属
結合層の表面を研磨して電子ビーム物理蒸着に適した状
態にした後、高強度・高靭性セラミックス層を電子ビー
ム物理蒸着法により０．１ｍｍの厚さで成膜した。最後
に、高温相安定セラミックス層を電子ビーム物理蒸着法
により０．４ｍｍの厚さで成膜した。 （試料Ｎｏ．６）Ｎｏ．５の試料と同様にして、母材上
に厚さ０．１ｍｍの金属結合層、厚さ０．２ｍｍの高強
度・高靭性セラミックス層、厚さ０．３ｍｍの高温相安
定セラミックス層を順次積層した。(Sample No. 5) The surface of the base material was made of Al 2 O 3
The particles were grid blasted to a state suitable for low pressure plasma spraying. Next, a metal bonding layer was formed to a thickness of 0.1 mm by low-pressure plasma spraying. Next, after the surface of the metal bonding layer was polished to a state suitable for electron beam physical vapor deposition, a high-strength and high-toughness ceramic layer was formed to a thickness of 0.1 mm by electron beam physical vapor deposition. Finally, a high-temperature phase-stable ceramic layer was formed to a thickness of 0.4 mm by an electron beam physical vapor deposition method. (Sample No. 6) In the same manner as the sample of No. 5, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.2 mm, and a high-temperature phase-stable ceramic layer having a thickness of 0.3 mm were sequentially laminated on the base material. did.
【００３０】（試料Ｎｏ．７）Ｎｏ．５の試料と同様に
して、母材上に厚さ０．１ｍｍの金属結合層、厚さ０．
３ｍｍの高強度・高靭性セラミックス層、厚さ０．２ｍ
ｍの高温相安定セラミックス層を順次積層した。 （試料Ｎｏ．８）Ｎｏ．５の試料と同様にして、母材上
に厚さ０．１ｍｍの金属結合層、厚さ０．４ｍｍの高強
度・高靭性セラミックス層、厚さ０．１ｍｍの高温相安
定セラミックス層を順次積層した。(Sample No. 7) In the same manner as the sample of No. 5, a metal bonding layer having a thickness of 0.1 mm was formed on the base material.
3mm high strength and high toughness ceramic layer, 0.2m thick
m high-temperature phase-stable ceramic layers were sequentially laminated. (Sample No. 8) In the same manner as in the sample No. 5, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.4 mm, and a high-temperature phase-stable ceramic layer having a thickness of 0.1 mm were sequentially laminated on the base material. did.
【００３１】（試料Ｎｏ．９）母材の表面を研磨して電
子ビーム物理蒸着に適した状態にした。ついで、金属結
合層を電子ビーム物理蒸着法により０．１ｍｍの厚さで
成膜した。ついで、高強度・高靭性セラミックス層を大
気圧プラズマ溶射法により０．１ｍｍの厚さで成膜し
た。最後に、高温相安定セラミックス層を大気圧プラズ
マ溶射法により０．４ｍｍの厚さで成膜した。 （試料Ｎｏ．１０）Ｎｏ．９の試料と同様にして、母材
上に厚さ０．１ｍｍの金属結合層、厚さ０．２ｍｍの高
強度・高靭性セラミックス層、厚さ０．３ｍｍの高温相
安定セラミックス層を順次積層した。(Sample No. 9) The surface of the base material was polished to a state suitable for electron beam physical vapor deposition. Next, a metal bonding layer was formed to a thickness of 0.1 mm by electron beam physical vapor deposition. Next, a high-strength, high-toughness ceramic layer was formed to a thickness of 0.1 mm by atmospheric pressure plasma spraying. Finally, a high-temperature phase-stable ceramics layer was formed to a thickness of 0.4 mm by an atmospheric pressure plasma spraying method. (Sample No. 10) In the same manner as in the sample No. 9, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.2 mm, and a high-temperature phase-stable ceramic layer having a thickness of 0.3 mm were sequentially laminated on the base material. did.
【００３２】（試料Ｎｏ．１１）Ｎｏ．９の試料と同様
にして、母材上に厚さ０．１ｍｍの金属結合層、厚さ
０．３ｍｍの高強度・高靭性セラミックス層、厚さ０．
２ｍｍの高温相安定セラミックス層を順次積層した。 （試料Ｎｏ．１２）Ｎｏ．９の試料と同様にして、母材
上に厚さ０．１ｍｍの金属結合層、厚さ０．４ｍｍの高
強度・高靭性セラミックス層、厚さ０．１ｍｍの高温相
安定セラミックス層を順次積層した。(Sample No. 11) Similarly to the sample No. 9, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.3 mm, and a thickness of 0.1 mm were formed on the base material.
High-temperature phase-stable ceramic layers of 2 mm were sequentially laminated. (Sample No. 12) In the same manner as the sample No. 9, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.4 mm, and a high-temperature phase-stable ceramic layer having a thickness of 0.1 mm are sequentially laminated on the base material. did.
【００３３】（試料Ｎｏ．１３）母材の表面を研磨して
電子ビーム物理蒸着に適した状態にした。ついで、金属
結合層を電子ビーム物理蒸着法により０．１ｍｍの厚さ
で成膜した。ついで、高強度・高靭性セラミックス層を
電子ビーム物理蒸着法により０．１ｍｍの厚さで成膜し
た。最後に、高温相安定セラミックス層を電子ビーム物
理蒸着法により０．４ｍｍの厚さで成膜した。 （試料Ｎｏ．１４）Ｎｏ．１３の試料と同様にして、母
材上に厚さ０．１ｍｍの金属結合層、厚さ０．２ｍｍの
高強度・高靭性セラミックス層、厚さ０．３ｍｍの高温
相安定セラミックス層を順次積層した。(Sample No. 13) The surface of the base material was polished to a state suitable for electron beam physical vapor deposition. Next, a metal bonding layer was formed to a thickness of 0.1 mm by electron beam physical vapor deposition. Next, a high-strength and high-toughness ceramic layer was formed to a thickness of 0.1 mm by electron beam physical vapor deposition. Finally, a high-temperature phase-stable ceramic layer was formed to a thickness of 0.4 mm by an electron beam physical vapor deposition method. (Sample No. 14) In the same manner as in the sample No. 13, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.2 mm, and a high-temperature phase-stable ceramic layer having a thickness of 0.3 mm were sequentially laminated on the base material. did.
【００３４】（試料Ｎｏ．１５）Ｎｏ．１３の試料と同
様にして、母材上に厚さ０．１ｍｍの金属結合層、厚さ
０．３ｍｍの高強度・高靭性セラミックス層、厚さ０．
２ｍｍの高温相安定セラミックス層を順次積層した。 （試料Ｎｏ．１６）Ｎｏ．１３の試料と同様にして、母
材上に厚さ０．１ｍｍの金属結合層、厚さ０．４ｍｍの
高強度・高靭性セラミックス層、厚さ０．１ｍｍの高温
相安定セラミックス層を順次積層した。(Sample No. 15) As in the case of the sample No. 13, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.3 mm, and a thickness of 0.1 mm were formed on the base material.
High-temperature phase-stable ceramic layers of 2 mm were sequentially laminated. (Sample No. 16) In the same manner as in the sample No. 13, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.4 mm, and a high-temperature phase-stable ceramic layer having a thickness of 0.1 mm were sequentially laminated on the base material. did.
【００３５】比較例１．比較として、つぎのＮｏ．１７
〜１８の試料を作製した。Ｎｏ．１７〜１８の試料で
は、高強度・高靭性セラミックス層はＺｒＯ2 ・８ｗｔ
％Ｙ2 Ｏ3 とし、高温相安定セラミックス層はＺｒＯ2
・１７ｗｔ％Ｙ2 Ｏ3 とした。Ｎｏ．１７の試料は従来
の遮熱コーティング膜と同じ構成である。Comparative Example 1 For comparison, the following Nos. 17
~ 18 samples were prepared. No. In samples 17 to 18, high strength and high toughness ceramic layer is ZrO 2 · 8 wt
% Y 2 O 3 and the high-temperature phase-stable ceramic layer is ZrO 2
- was 17wt% Y 2 O 3. No. The sample No. 17 has the same configuration as the conventional thermal barrier coating film.
【００３６】（試料Ｎｏ．１７）母材上に金属結合層を
低圧プラズマ溶射法により０．１ｍｍの厚さで成膜し
た。ついで、高強度・高靭性セラミックス層を大気圧プ
ラズマ溶射法により０．５ｍｍの厚さで成膜した。 （試料Ｎｏ．１８）母材上に金属結合層を低圧プラズマ
溶射法により０．１ｍｍの厚さで成膜した。ついで、高
温相安定セラミックス層を大気圧プラズマ溶射法により
０．５ｍｍの厚さで成膜した。(Sample No. 17) A metal bonding layer was formed on the base material to a thickness of 0.1 mm by low-pressure plasma spraying. Next, a high-strength, high-toughness ceramic layer was formed to a thickness of 0.5 mm by atmospheric pressure plasma spraying. (Sample No. 18) A metal bonding layer was formed on the base material to a thickness of 0.1 mm by low-pressure plasma spraying. Next, a high-temperature phase-stable ceramic layer was formed to a thickness of 0.5 mm by an atmospheric pressure plasma spraying method.
【００３７】上述したＮｏ．１〜１８の試料の金属結合
層、高強度・高靭性セラミックス層および高温相安定セ
ラミックス層の材質、積層方法および厚さを表１に示
す。The above No. Table 1 shows the materials, lamination methods, and thicknesses of the metal bonding layer, the high-strength / high-toughness ceramic layer, and the high-temperature phase-stable ceramic layer of the samples Nos. 1 to 18.
【表１】 [Table 1]
【００３８】つぎに、上述したＮｏ．１〜１８の試料に
ついて、図２に示す燃焼ガス式熱サイクル試験による耐
久性評価試験を実施した。この装置では、燃焼ガスバー
ナ３１により試験片３２の遮熱コーティング膜３３の表
面を約１２００℃以上に加熱するとともに、金属結合層
と高強度・高靭性セラミックス層との界面の温度を８０
０〜９００℃と、実機ガスタービンと同様の温度条件に
設定することができる。Next, the above-mentioned No. A durability evaluation test by a combustion gas type heat cycle test shown in FIG. In this apparatus, the surface of the thermal barrier coating film 33 of the test piece 32 is heated to about 1200 ° C. or more by the combustion gas burner 31 and the temperature of the interface between the metal bonding layer and the high-strength and high-toughness ceramic layer is raised to 80 ° C.
The temperature condition can be set to 0 to 900 ° C., which is the same as that of the actual gas turbine.
【００３９】耐久性評価試験では、各試料について、遮
熱コーティング膜３３の表面温度を１４００℃とし、金
属結合層と高強度・高靭性セラミックス層との界面温度
を９００℃に設定した。加熱パターンは、室温から１４
００℃まで５分間で昇温させ、１４００℃で５分間保持
し、その後、燃焼ガスを止めて１０分間冷却するパター
ンを１サイクルとした。冷却時の試験片の温度は１００
℃以下である。この熱サイクル試験でセラミックス層に
剥離が生じるまでの回数により耐久性を評価した。ま
た、耐久性評価試験の前後に、Ｘ線回折法により、遮熱
コーティング膜３３の表面のセラミックス層の構造解析
を行った。In the durability evaluation test, the surface temperature of the thermal barrier coating film 33 was set to 1400 ° C., and the interface temperature between the metal bonding layer and the high strength / high toughness ceramic layer was set to 900 ° C. for each sample. Heating pattern from room temperature to 14
The temperature was raised to 00 ° C. in 5 minutes, the temperature was maintained at 1400 ° C. for 5 minutes, then the combustion gas was stopped and the pattern was cooled for 10 minutes. The temperature of the specimen during cooling was 100
It is below ° C. In this heat cycle test, the durability was evaluated by the number of times until the ceramic layer peeled off. Before and after the durability evaluation test, the structure analysis of the ceramic layer on the surface of the thermal barrier coating film 33 was performed by the X-ray diffraction method.
【００４０】試験結果および構造解析結果を表２に示
す。Table 2 shows the test results and the structural analysis results.
【表２】 [Table 2]
【００４１】表２より明らかなように、実施例１の各試
料Ｎｏ．１〜１６は、いずれも１５００回の熱サイクル
では剥離しなかった。また、熱サイクル試験の前後の結
晶構造はいずれも１００％の立方晶であり、安定してい
ることが確認された。それに対して、比較例１の試料Ｎ
ｏ．１７は４７５回、試料Ｎｏ．１８は４００回の熱サ
イクルで剥離した。As is clear from Table 2, each of the sample Nos. All of Nos. 1 to 16 did not peel off after 1500 thermal cycles. In addition, the crystal structures before and after the heat cycle test were all 100% cubic, and were confirmed to be stable. On the other hand, the sample N of Comparative Example 1
o. Sample No. 17 was 475 times. No. 18 was peeled off by 400 heat cycles.
【００４２】実施例２．以下に示すＮｏ．１９〜３４の
試料を作製した。Ｎｏ．１９〜３４の試料では、高強度
・高靭性セラミックス層はＺｒＯ2 ・１０ｗｔ％Ｄｙ2
Ｏ3 とし、高温相安定セラミックス層はＺｒＯ2 ・２０
ｗｔ％Ｄｙ2 Ｏ3 とした。Embodiment 2 FIG. No. shown below. 19 to 34 samples were prepared. No. In the samples of Nos. 19 to 34, the high-strength and high-toughness ceramic layer was made of ZrO 2 .10 wt% Dy 2
O 3 , and the high-temperature phase-stable ceramic layer is ZrO 2 · 20
was wt% Dy 2 O 3.
【００４３】（試料Ｎｏ．１９）母材の表面をＡｌ2 Ｏ
3 粒でグリッドブラスト処理して、低圧プラズマ溶射に
適した状態にした。ついで、金属結合層を低圧プラズマ
溶射法により０．１ｍｍの厚さで成膜した。ついで、高
強度・高靭性セラミックス層を大気圧プラズマ溶射法に
より０．１ｍｍの厚さで成膜した。最後に、高温相安定
セラミックス層を大気圧プラズマ溶射法により０．４ｍ
ｍの厚さで成膜した。 （試料Ｎｏ．２０）Ｎｏ．１９の試料と同様にして、母
材上に厚さ０．１ｍｍの金属結合層、厚さ０．２ｍｍの
高強度・高靭性セラミックス層、厚さ０．３ｍｍの高温
相安定セラミックス層を順次積層した。(Sample No. 19) The surface of the base material was made of Al 2 O
Three grains were grid blasted to make them suitable for low pressure plasma spraying. Next, a metal bonding layer was formed to a thickness of 0.1 mm by low-pressure plasma spraying. Next, a high-strength, high-toughness ceramic layer was formed to a thickness of 0.1 mm by atmospheric pressure plasma spraying. Finally, the high-temperature phase-stable ceramics layer was formed by atmospheric plasma spraying to a thickness of 0.4 m.
m was formed. (Sample No. 20) In the same manner as in the 19th sample, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.2 mm, and a high-temperature phase-stable ceramic layer having a thickness of 0.3 mm were sequentially laminated on a base material. did.
【００４４】（試料Ｎｏ．２１）Ｎｏ．１９の試料と同
様にして、母材上に厚さ０．１ｍｍの金属結合層、厚さ
０．３ｍｍの高強度・高靭性セラミックス層、厚さ０．
２ｍｍの高温相安定セラミックス層を順次積層した。 （試料Ｎｏ．２２）Ｎｏ．１９の試料と同様にして、母
材上に厚さ０．１ｍｍの金属結合層、厚さ０．４ｍｍの
高強度・高靭性セラミックス層、厚さ０．１ｍｍの高温
相安定セラミックス層を順次積層した。(Sample No. 21) Similarly to the sample No. 19, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.3 mm, and a thickness of 0.1 mm were formed on a base material.
High-temperature phase-stable ceramic layers of 2 mm were sequentially laminated. (Sample No. 22) In the same manner as in the 19th sample, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.4 mm, and a high-temperature phase-stable ceramic layer having a thickness of 0.1 mm were sequentially laminated on a base material. did.
【００４５】（試料Ｎｏ．２３）母材の表面をＡｌ2 Ｏ
3 粒でグリッドブラスト処理して、低圧プラズマ溶射に
適した状態にした。ついで、金属結合層を低圧プラズマ
溶射法により０．１ｍｍの厚さで成膜した。ついで、金
属結合層の表面を研磨して電子ビーム物理蒸着に適した
状態にした後、高強度・高靭性セラミックス層を電子ビ
ーム物理蒸着法により０．１ｍｍの厚さで成膜した。最
後に、高温相安定セラミックス層を電子ビーム物理蒸着
法により０．４ｍｍの厚さで成膜した。 （試料Ｎｏ．２４）Ｎｏ．２３の試料と同様にして、母
材上に厚さ０．１ｍｍの金属結合層、厚さ０．２ｍｍの
高強度・高靭性セラミックス層、厚さ０．３ｍｍの高温
相安定セラミックス層を順次積層した。(Sample No. 23) The surface of the base material was made of Al 2 O
Three grains were grid blasted to make them suitable for low pressure plasma spraying. Next, a metal bonding layer was formed to a thickness of 0.1 mm by low-pressure plasma spraying. Next, after the surface of the metal bonding layer was polished to a state suitable for electron beam physical vapor deposition, a high-strength and high-toughness ceramic layer was formed to a thickness of 0.1 mm by electron beam physical vapor deposition. Finally, a high-temperature phase-stable ceramic layer was formed to a thickness of 0.4 mm by an electron beam physical vapor deposition method. (Sample No. 24) In the same manner as in the sample No. 23, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.2 mm, and a high-temperature phase-stable ceramic layer having a thickness of 0.3 mm were sequentially laminated on a base material. did.
【００４６】（試料Ｎｏ．２５）Ｎｏ．２３の試料と同
様にして、母材上に厚さ０．１ｍｍの金属結合層、厚さ
０．３ｍｍの高強度・高靭性セラミックス層、厚さ０．
２ｍｍの高温相安定セラミックス層を順次積層した。 （試料Ｎｏ．２６）Ｎｏ．２３の試料と同様にして、母
材上に厚さ０．１ｍｍの金属結合層、厚さ０．４ｍｍの
高強度・高靭性セラミックス層、厚さ０．１ｍｍの高温
相安定セラミックス層を順次積層した。(Sample No. 25) Similarly to the sample No. 23, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.3 mm, and a thickness of 0.3 mm were formed on a base material.
High-temperature phase-stable ceramic layers of 2 mm were sequentially laminated. (Sample No. 26) In the same manner as in the sample 23, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.4 mm, and a high-temperature phase-stable ceramic layer having a thickness of 0.1 mm were sequentially laminated on the base material. did.
【００４７】（試料Ｎｏ．２７）母材の表面を研磨して
電子ビーム物理蒸着に適した状態にした。ついで、金属
結合層を電子ビーム物理蒸着法により０．１ｍｍの厚さ
で成膜した。ついで、高強度・高靭性セラミックス層を
大気圧プラズマ溶射法により０．１ｍｍの厚さで成膜し
た。最後に、高温相安定セラミックス層を大気圧プラズ
マ溶射法により０．４ｍｍの厚さで成膜した。 （試料Ｎｏ．２８）Ｎｏ．２７の試料と同様にして、母
材上に厚さ０．１ｍｍの金属結合層、厚さ０．２ｍｍの
高強度・高靭性セラミックス層、厚さ０．３ｍｍの高温
相安定セラミックス層を順次積層した。(Sample No. 27) The surface of the base material was polished to a state suitable for electron beam physical vapor deposition. Next, a metal bonding layer was formed to a thickness of 0.1 mm by electron beam physical vapor deposition. Next, a high-strength, high-toughness ceramic layer was formed to a thickness of 0.1 mm by atmospheric pressure plasma spraying. Finally, a high-temperature phase-stable ceramics layer was formed to a thickness of 0.4 mm by an atmospheric pressure plasma spraying method. (Sample No. 28) In the same manner as in the sample No. 27, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.2 mm, and a high-temperature phase-stable ceramic layer having a thickness of 0.3 mm were sequentially laminated on a base material. did.
【００４８】（試料Ｎｏ．２９）Ｎｏ．２７の試料と同
様にして、母材上に厚さ０．１ｍｍの金属結合層、厚さ
０．３ｍｍの高強度・高靭性セラミックス層、厚さ０．
２ｍｍの高温相安定セラミックス層を順次積層した。 （試料Ｎｏ．３０）Ｎｏ．２７の試料と同様にして、母
材上に厚さ０．１ｍｍの金属結合層、厚さ０．４ｍｍの
高強度・高靭性セラミックス層、厚さ０．１ｍｍの高温
相安定セラミックス層を順次積層した。(Sample No. 29) Similarly to the sample No. 27, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.3 mm and a thickness of 0.3 mm were formed on a base material.
High-temperature phase-stable ceramic layers of 2 mm were sequentially laminated. (Sample No. 30) Similarly to the sample 27, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.4 mm, and a high-temperature phase-stable ceramic layer having a thickness of 0.1 mm are sequentially laminated on a base material. did.
【００４９】（試料Ｎｏ．３１）母材の表面を研磨して
電子ビーム物理蒸着に適した状態にした。ついで、金属
結合層を電子ビーム物理蒸着法により０．１ｍｍの厚さ
で成膜した。ついで、高強度・高靭性セラミックス層を
電子ビーム物理蒸着法により０．１ｍｍの厚さで成膜し
た。最後に、高温相安定セラミックス層を電子ビーム物
理蒸着法により０．４ｍｍの厚さで成膜した。 （試料Ｎｏ．３２）Ｎｏ．３１の試料と同様にして、母
材上に厚さ０．１ｍｍの金属結合層、厚さ０．２ｍｍの
高強度・高靭性セラミックス層、厚さ０．３ｍｍの高温
相安定セラミックス層を順次積層した。(Sample No. 31) The surface of the base material was polished to a state suitable for electron beam physical vapor deposition. Next, a metal bonding layer was formed to a thickness of 0.1 mm by electron beam physical vapor deposition. Next, a high-strength and high-toughness ceramic layer was formed to a thickness of 0.1 mm by electron beam physical vapor deposition. Finally, a high-temperature phase-stable ceramic layer was formed to a thickness of 0.4 mm by an electron beam physical vapor deposition method. (Sample No. 32) In the same manner as in the sample No. 31, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.2 mm, and a high-temperature phase-stable ceramic layer having a thickness of 0.3 mm were sequentially laminated on a base material. did.
【００５０】（試料Ｎｏ．３３）Ｎｏ．３１の試料と同
様にして、母材上に厚さ０．１ｍｍの金属結合層、厚さ
０．３ｍｍの高強度・高靭性セラミックス層、厚さ０．
２ｍｍの高温相安定セラミックス層を順次積層した。 （試料Ｎｏ．３４）Ｎｏ．３１の試料と同様にして、母
材上に厚さ０．１ｍｍの金属結合層、厚さ０．４ｍｍの
高強度・高靭性セラミックス層、厚さ０．１ｍｍの高温
相安定セラミックス層を順次積層した。(Sample No. 33) As in the case of the sample No. 31, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.3 mm and a thickness of 0.3 mm were formed on the base material.
High-temperature phase-stable ceramic layers of 2 mm were sequentially laminated. (Sample No. 34) In the same manner as in the sample No. 31, a metal bonding layer having a thickness of 0.1 mm, a high-strength and high-toughness ceramic layer having a thickness of 0.4 mm, and a high-temperature phase-stable ceramic layer having a thickness of 0.1 mm are sequentially laminated on the base material. did.
【００５１】比較例２．比較として、つぎのＮｏ．３５
の試料を作製した。このＮｏ．３５の試料は従来の遮熱
コーティング膜と同じ構成である。 （試料Ｎｏ．３５）母材上に金属結合層を低圧プラズマ
溶射法により０．１ｍｍの厚さで成膜した。ついで、高
強度・高靭性セラミックス層としてＺｒＯ2 ・８ｗｔ％
Ｙ2 Ｏ3 を大気圧プラズマ溶射法により０．５ｍｍの厚
さで成膜した。Comparative Example 2 For comparison, the following Nos. 35
Was prepared. This No. The sample No. 35 has the same configuration as the conventional thermal barrier coating film. (Sample No. 35) A metal bonding layer was formed on the base material to a thickness of 0.1 mm by low-pressure plasma spraying. Next, as a high-strength and high-toughness ceramic layer, ZrO 2 .8 wt%
Y 2 O 3 was formed to a thickness of 0.5 mm by atmospheric pressure plasma spraying.
【００５２】上述したＮｏ．１９〜３５の試料の金属結
合層、高強度・高靭性セラミックス層および高温相安定
セラミックス層の材質、積層方法および厚さを表３に示
す。The above No. Table 3 shows the materials, lamination methods, and thicknesses of the metal bonding layer, the high-strength / high-toughness ceramic layer, and the high-temperature phase-stable ceramic layer of the samples Nos. 19 to 35.
【表３】 [Table 3]
【００５３】つぎに、上述したＮｏ．１９〜３５の試料
について、図２に示す燃焼ガス式熱サイクル試験による
耐久性評価試験を実施例１と同じ条件で実施した。ま
た、実施例１と同様に、耐久性評価試験の前後に、Ｘ線
回折法により、遮熱コーティング膜３３の表面のセラミ
ックス層の構造解析を行った。Next, the above-mentioned No. For the samples 19 to 35, a durability evaluation test by a combustion gas type heat cycle test shown in FIG. 2 was performed under the same conditions as in Example 1. Further, similarly to Example 1, before and after the durability evaluation test, the structure analysis of the ceramic layer on the surface of the thermal barrier coating film 33 was performed by the X-ray diffraction method.
【００５４】試験結果および構造解析結果を表４に示
す。Table 4 shows the test results and the structural analysis results.
【表４】 [Table 4]
【００５５】表４より明らかなように、実施例２の各試
料Ｎｏ．１９〜３４は、いずれも１５００回の熱サイク
ルでは剥離しなかった。また、熱サイクル試験の前後の
結晶構造はいずれも１００％の立方晶であり、安定して
いることが確認された。それに対して、比較例２の試料
Ｎｏ．３５は、４７５回の熱サイクルで剥離した。As is clear from Table 4, each of the sample Nos. All of Nos. 19 to 34 did not peel off after 1500 heat cycles. In addition, the crystal structures before and after the heat cycle test were all 100% cubic, and were confirmed to be stable. On the other hand, the sample No. No. 35 peeled off after 475 thermal cycles.
【００５６】[0056]
【発明の効果】本発明にかかる遮熱コーティング材によ
れば、最外層に高温相安定セラミックス層が設けられ、
その下に高強度・高靭性セラミックス層が設けられてい
るため、高温環境下で遮熱コーティング材が劣化するの
が抑制されるとともに、母材とセラミックス層との線膨
張係数差に起因する熱応力に耐えることができることに
よりセラミックス層の剥離が防止される。したがって、
温度環境が従来よりも高温であっても十分な耐久性が得
られ、遮熱コーティング材の寿命が短くなるのを防ぐこ
とができる。また、セラミックスの安定化剤として、Ｙ
2 Ｏ3 よりも熱伝導率が低いＤｙ2Ｏ3 を用いた場合に
は、より耐熱性に優れるという効果が得られる。According to the thermal barrier coating material of the present invention, the outermost layer is provided with a high-temperature phase-stable ceramic layer,
The high-strength, high-toughness ceramic layer is provided underneath, so that the thermal barrier coating material is prevented from deteriorating in a high-temperature environment, and the thermal expansion caused by the difference in linear expansion coefficient between the base material and the ceramic layer. The ability to withstand the stress prevents peeling of the ceramic layer. Therefore,
Even if the temperature environment is higher than before, sufficient durability can be obtained, and the life of the thermal barrier coating material can be prevented from being shortened. Further, as a stabilizer for ceramics, Y
When the thermal conductivity than 2 O 3 was used lower Dy 2 O 3, the effect is obtained that more excellent heat resistance.
【００５７】また、本発明にかかるガスタービン部材に
よれば、遮熱コーティング膜の最外層に高温相安定セラ
ミックス層が設けられ、その下に高強度・高靭性セラミ
ックス層が設けられているため、高温環境下で遮熱コー
ティング膜が劣化するのが抑制されるとともに、熱応力
の緩和により遮熱コーティング膜のセラミックス層の剥
離が防止される。したがって、温度環境が従来よりも高
温であっても十分な耐久性を有するガスタービン部材を
得ることができる。また、セラミックスの安定化剤とし
て、Ｙ2 Ｏ3 よりも熱伝導率が低いＤｙ2Ｏ3 を用いた
場合には、より耐熱性に優れるという効果が得られる。According to the gas turbine member of the present invention, the high-temperature phase-stable ceramic layer is provided as the outermost layer of the thermal barrier coating film, and the high-strength and high-toughness ceramic layer is provided thereunder. Deterioration of the thermal barrier coating film in a high temperature environment is suppressed, and peeling of the ceramic layer of the thermal barrier coating film is prevented by relaxation of thermal stress. Therefore, a gas turbine member having sufficient durability can be obtained even when the temperature environment is higher than before. When Dy 2 O 3 having a lower thermal conductivity than Y 2 O 3 is used as a ceramic stabilizer, an effect of more excellent heat resistance can be obtained.
【図１】本発明にかかる遮熱コーティング膜の構成を示
す断面図である。FIG. 1 is a cross-sectional view illustrating a configuration of a thermal barrier coating film according to the present invention.
【図２】実施例および比較例について実施した燃焼ガス
式熱サイクル試験の概略を示す図である。FIG. 2 is a diagram showing an outline of a combustion gas type heat cycle test performed on Examples and Comparative Examples.
【図３】従来の遮熱コーティング膜の構成を示す断面図
である。FIG. 3 is a cross-sectional view showing a configuration of a conventional thermal barrier coating film.
【図４】本発明にかかる遮熱コーティング膜を適用した
ガスタービン動翼の斜視図である。FIG. 4 is a perspective view of a gas turbine blade to which a thermal barrier coating according to the present invention is applied.
【図５】本発明にかかる遮熱コーティング膜を適用した
ガスタービン静翼の斜視図である。FIG. 5 is a perspective view of a gas turbine stationary blade to which the thermal barrier coating according to the present invention is applied.
【図６】本発明にかかる遮熱コーティング膜を適用した
ガスタービンを示す概略構成図である。FIG. 6 is a schematic configuration diagram showing a gas turbine to which the thermal barrier coating according to the present invention is applied.
２１ 母材 ２２ 金属結合層 ２３ 高強度・高靭性セラミックス層 ２４ 高温相安定セラミックス層 ４ 静翼 ５ 動翼 ６ ガスタービン ６１ 圧縮機 ６２ タービン ６３ 燃焼器 Reference Signs List 21 base material 22 metal bonding layer 23 high-strength and high-toughness ceramic layer 24 high-temperature phase-stable ceramic layer 4 stationary blade 5 moving blade 6 gas turbine 61 compressor 62 turbine 63 combustor
【手続補正書】[Procedure amendment]
【提出日】平成１２年６月１２日（２０００．６．１
２）[Submission date] June 12, 2000 (2006.1.
2)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３７[Correction target item name] 0037
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００３７】上述したＮｏ．１〜１８の試料の金属結合
層、高強度・高靭性セラミックス層および高温相安定セ
ラミックス層の材質、積層方法および厚さを表１に示
す。The above No. Table 1 shows the materials, lamination methods, and thicknesses of the metal bonding layer, the high-strength / high-toughness ceramic layer, and the high-temperature phase-stable ceramic layer of the samples Nos. 1 to 18.
【表１】 [ Table 1 ]
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４０[Correction target item name] 0040
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００４０】試験結果および構造解析結果を表２に示
す。Table 2 shows the test results and the structural analysis results.
【表２】 [ Table 2 ]
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００５２[Correction target item name] 0052
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００５２】上述したＮｏ．１９〜３５の試料の金属結
合層、高強度・高靭性セラミックス層および高温相安定
セラミックス層の材質、積層方法および厚さを表３に示
す。The above No. Table 3 shows the materials, lamination methods, and thicknesses of the metal bonding layer, the high-strength / high-toughness ceramic layer, and the high-temperature phase-stable ceramic layer of the samples Nos. 19 to 35.
【表３】 [ Table 3 ]
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００５４[Correction target item name] 0054
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００５４】試験結果および構造解析結果を表４に示
す。Table 4 shows the test results and the structural analysis results.
【表４】 [ Table 4 ]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｆ０２Ｃ 7/00 Ｆ０２Ｃ 7/00 Ｃ Ｆ２３Ｒ 3/42 Ｆ２３Ｒ 3/42 Ｃ (72)発明者 岡田 郁生 兵庫県高砂市荒井町新浜２丁目１番１号 三菱重工業株式会社高砂研究所内 (72)発明者 高橋 孝二 兵庫県高砂市荒井町新浜２丁目１番１号 三菱重工業株式会社高砂製作所内 (72)発明者 大原 稔 兵庫県高砂市荒井町新浜２丁目１番１号 三菱重工業株式会社高砂製作所内 Ｆターム(参考） 3G002 EA05 EA08 GA10 GB00 4K031 AA02 AA08 AB02 AB03 AB04 AB08 CB07 CB11 CB14 CB42 DA04 4K044 AA06 AB10 BA06 BA12 BB04 BC07 BC11 CA11 CA13 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) F02C 7/00 F02C 7/00 C F23R 3/42 F23R 3/42 C (72) Inventor Ikuo Okada Hyogo 2-1-1, Niihama, Arai-machi, Takasago-shi Mitsubishi Heavy Industries, Ltd. Takasago Research Laboratory (72) Inventor Koji Takahashi 2-1-1, Arai-machi, Niihama, Takasago-shi, Hyogo Mitsubishi Heavy Industries, Ltd. Takasago Factory (72) Minoru Ohara 2-1-1 Shinama, Arai-machi, Takasago-shi, Hyogo F-term in Takasago Works, Mitsubishi Heavy Industries, Ltd. (reference) 3G002 EA05 EA08 GA10 GB00 4K031 AA02 AA08 AB02 AB03 AB04 AB08 CB07 CB11 CB14 CB42 DA04 4K044 AA06 AB10 BA07 BC12 CA13
Claims (11)
属結合層の上に高強度・高靭性セラミックス層を積層
し、前記高強度・高靭性セラミックス層の上に高温相安
定セラミックス層を積層したことを特徴とする遮熱コー
ティング材。1. A metal bonding layer is laminated on a base material, a high-strength and high-toughness ceramic layer is laminated on the metal bonding layer, and a high-temperature phase-stable ceramic is laminated on the high-strength and high-toughness ceramic layer. Thermal barrier coating material characterized by laminated layers.
Ｙ2 Ｏ3 で安定化させた部分安定化ジルコニアよりなる
ことを特徴とする請求項１に記載の遮熱コーティング
材。2. The high strength / high toughness ceramic layer,
Thermal barrier coating material according to claim 1, characterized in that Y consists of stabilized was partially stabilized zirconia 2 O 3.
で安定化させた完全安定化ジルコニアよりなることを特
徴とする請求項１または２に記載の遮熱コーティング
材。3. The high-temperature phase-stable ceramic layer is made of Y 2 O 3
The thermal barrier coating material according to claim 1, wherein the thermal barrier coating material is made of completely stabilized zirconia stabilized by:
Ｄｙ2 Ｏ3 で安定化させた部分安定化ジルコニアよりな
ることを特徴とする請求項１に記載の遮熱コーティング
材。4. The high strength and high toughness ceramic layer,
Thermal barrier coating material according to claim 1, characterized in that Dy consisting stabilized was partially stabilized zirconia 2 O 3.
3 で安定化させた完全安定化ジルコニアよりなることを
特徴とする請求項１または２に記載の遮熱コーティング
材。5. The high-temperature phase-stable ceramic layer is made of Dy 2 O.
The thermal barrier coating material according to claim 1, wherein the thermal barrier coating material is made of fully stabilized zirconia stabilized in 3 .
金属結合層の上に高強度・高靭性セラミックス層が積層
され、前記高強度・高靭性セラミックス層の上に高温相
安定セラミックス層が積層されてなる遮熱コーティング
膜で被覆されていることを特徴とするガスタービン部
材。6. A metal bonding layer is laminated on a base material, a high-strength and high-toughness ceramic layer is laminated on the metal bonding layer, and a high-temperature phase-stable ceramic is laminated on the high-strength and high-toughness ceramic layer. A gas turbine member, wherein the gas turbine member is covered with a thermal barrier coating film formed by stacking layers.
Ｙ2 Ｏ3 で安定化させた部分安定化ジルコニアよりなる
ことを特徴とする請求項６に記載のガスタービン部材。7. The high strength and high toughness ceramic layer,
Gas turbine component according to claim 6, characterized in that consists of stabilized was partially stabilized zirconia Y 2 O 3.
で安定化させた完全安定化ジルコニアよりなることを特
徴とする請求項６または７に記載のガスタービン部材。8. The high-temperature phase-stable ceramic layer is made of Y 2 O 3
The gas turbine member according to claim 6, wherein the gas turbine member is made of completely stabilized zirconia stabilized by:
Ｄｙ2 Ｏ3 で安定化させた部分安定化ジルコニアよりな
ることを特徴とする請求項６に記載のガスタービン部
材。9. The high strength / high toughness ceramic layer,
Gas turbine component according to claim 6, characterized in that consisting of partially stabilized zirconia stabilized with Dy 2 O 3.
Ｏ3 で安定化させた完全安定化ジルコニアよりなること
を特徴とする請求項６または９に記載のガスタービン部
材。10. The high-temperature phase-stable ceramic layer is made of Dy 2
The gas turbine member according to claim 6, wherein the gas turbine member is made of fully stabilized zirconia stabilized with O 3 .
させた流体をタービンの静翼と動翼とで膨張させること
によって動力を発生するガスタービンにおいて、請求項
６ないし請求項１０のいずれかに記載のガスタービン部
材を組み込んだことを特徴とするガスタービン。11. A gas turbine which generates power by expanding fluid between a stationary blade and a moving blade of a turbine after being compressed by a compressor and then combusted by a combustor. A gas turbine incorporating any one of the gas turbine members described above.
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| FR2858613A1 (en) * | 2003-08-07 | 2005-02-11 | Snecma Moteurs | THERMAL BARRIER COMPOSITION, SUPERALLY MECHANICAL PART WITH COATING HAVING SUCH COMPOSITION, CERAMIC COATING, AND COATING MANUFACTURING PROCESS |
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