JP4616648B2 - Thermal barrier coating and method of applying such a coating - Google Patents

Thermal barrier coating and method of applying such a coating Download PDF

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JP4616648B2
JP4616648B2 JP2004539704A JP2004539704A JP4616648B2 JP 4616648 B2 JP4616648 B2 JP 4616648B2 JP 2004539704 A JP2004539704 A JP 2004539704A JP 2004539704 A JP2004539704 A JP 2004539704A JP 4616648 B2 JP4616648 B2 JP 4616648B2
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tbc
powder particles
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ウィグレン，ヤン
ハンッソン，マッツ−オロヴ
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ボルボ エアロ コーポレイション
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    • 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
    • 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
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F01D5/288—Protective coatings for blades
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23R—GENERATING COMBUSTION PRODUCTS OF HIGH PRESSURE OR HIGH VELOCITY, e.g. GAS-TURBINE COMBUSTION CHAMBERS
    • F23R3/00—Continuous combustion chambers using liquid or gaseous fuel
    • F23R3/007—Continuous combustion chambers using liquid or gaseous fuel constructed mainly of ceramic components
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23M—CASINGS, LININGS, WALLS OR DOORS SPECIALLY ADAPTED FOR COMBUSTION CHAMBERS, e.g. FIREBRIDGES; DEVICES FOR DEFLECTING AIR, FLAMES OR COMBUSTION PRODUCTS IN COMBUSTION CHAMBERS; SAFETY ARRANGEMENTS SPECIALLY ADAPTED FOR COMBUSTION APPARATUS; DETAILS OF COMBUSTION CHAMBERS, NOT OTHERWISE PROVIDED FOR
    • F23M2900/00—Special features of, or arrangements for combustion chambers
    • F23M2900/05004—Special materials for walls or lining

Description

本発明は、金属基材自体またはそのような基材に被着された中間介在結合コーティングに直接的に被着され、そして付着されたセラミック遮熱コーティング（ＴＢＣ）に関するものである。   The present invention relates to a ceramic thermal barrier coating (TBC) deposited and deposited directly on the metal substrate itself or an intermediate intervening bond coating applied to such a substrate.

本発明は、また、基材の上にセラミック遮熱コーティング（ＴＢＣ）を適用する方法であって、該ＴＢＣが、好ましくは、該基材または結合コーティング上への前記ＴＢＣ粉末の熱溶射によって該基材または該基材と該ＴＢＣとの間の中間介在結合コーティングの上に適用される前記方法に関するものである。   The present invention is also a method of applying a ceramic thermal barrier coating (TBC) on a substrate, said TBC preferably by thermal spraying of said TBC powder onto said substrate or bond coating. It relates to said method applied on a substrate or an intermediate intervening bond coating between the substrate and the TBC.

本発明は、また、そのようなセラミックＴＢＣで被覆された金属基材または物品にも関するものである。特に、前記の基材または物品は、例えばガスタービンエンジンのタービン羽根や焼却室のような高温環境で作動する構造要素である。   The invention also relates to a metal substrate or article coated with such ceramic TBC. In particular, the substrate or article is a structural element that operates in a high temperature environment, such as a turbine blade or an incineration chamber of a gas turbine engine.

ガスタービンエンジンにおける上昇する運転温度の要求が、例えば、そのような高温に非常に曝されるタービン羽根などの金属部分に被着されるセラミック遮熱コーティング（ＴＢＣ）材料の開発を導いてきた。ＴＢＣの材料に課せられた仕事は、金属部分を熱的に絶縁して、それらの実用寿命を長引かせ、それらを厳しい運転条件によって急速に劣化しないようにすることである。   The increasing operating temperature requirements in gas turbine engines have led to the development of ceramic thermal barrier coating (TBC) materials that are applied to metal parts such as, for example, turbine blades that are very exposed to such high temperatures. The task imposed on the TBC material is to thermally insulate the metal parts to prolong their service life so that they do not deteriorate rapidly under severe operating conditions.

通常、例えばＭＣｒＡｌＹ−コーティングなどの中間介在結合コーティングは、該ＴＢＣと該金属基材との効果的な結合を促進するために該金属基材に適用される。次いで、該ＴＢＣが、例えば熱（好ましくはプラズマ）溶射、物理的蒸着（ＰＶＤ）または化学蒸着（ＣＶＤ）などの適当な被着技術によって該結合コーティングの上に適用される。   Usually, an intermediate intervening bond coating such as, for example, MCrAlY-coating is applied to the metal substrate to promote effective bonding between the TBC and the metal substrate. The TBC is then applied over the bond coating by a suitable deposition technique such as, for example, thermal (preferably plasma) spraying, physical vapor deposition (PVD) or chemical vapor deposition (CVD).

該ＴＢＣは、同時に、例えば熱衝撃および熱サイクルの耐性などの十分な熱的−機械的性質を示しながら、最も低い可能な熱伝導率を持たなければならないし、また、重さと空間を節約するために薄くなければならない。   The TBC must at the same time have the lowest possible thermal conductivity while exhibiting sufficient thermal-mechanical properties such as thermal shock and thermal cycle resistance, and also saves weight and space In order to be thin.

本発明の目的は、低い熱伝導性、十分な機械的強度、および低い重量の特性を兼備するコーティングを生成するセラミック遮熱コーティングおよびそのようなコーティングを適用する方法を提供することである。   It is an object of the present invention to provide a ceramic thermal barrier coating that produces a coating that combines low thermal conductivity, sufficient mechanical strength, and low weight properties and a method of applying such a coating.

そのようなコーティングを適用するまたは被着する方法は、複雑ではなく、容易に繰り返すことができ、工業規模（実験室スケールだけではなく）での被覆された基材の効率的生産を促進するものでなければならない。   The method of applying or depositing such a coating is not complicated and can be easily repeated, facilitating the efficient production of coated substrates on an industrial scale (not just laboratory scale) Must.

遮熱コーティングは、厳しい熱的な条件において運転する金属の構造要素、典型的には例えばタービン羽根または燃焼室などのガスタービンエンジンのそのような金属構造要素の上の温度絶縁材料として適当なものでなければならない。   Thermal barrier coatings are suitable as temperature insulating materials on metal structural elements that operate in severe thermal conditions, typically such metal structural elements of gas turbine engines such as turbine blades or combustion chambers. Must.

本発明の目的は、該ＴＢＣが、少なくとも２つの層を含み、該基材または結合コーティングに直接的に付着されている第１の内側のＴＢＣ層が、第２の外側のＴＢＣ層と異なるミクロ構造を呈することを特徴とする、最初に定義されたセラミック遮熱コーティングによって達成される。これは、コーティング被着パラメータを変更することによって達成することができる。本発明は、好ましい被着法を提案し、それは、後に記載されるだろう。   It is an object of the present invention that the TBC comprises at least two layers, wherein the first inner TBC layer directly attached to the substrate or bond coating is different from the second outer TBC layer. This is achieved by an initially defined ceramic thermal barrier coating characterized by exhibiting a structure. This can be achieved by changing the coating deposition parameters. The present invention proposes a preferred deposition method, which will be described later.

好ましい実施態様によると、異なるミクロ構造は、第２の層と比べて、第１の層において異なった割合、分布または配向の細孔を含んでいる。最も好ましくは、第１の層は、第２の層より少ない細孔率、すなわち少ない比率の細孔しか与えない。   According to a preferred embodiment, the different microstructures contain different proportions, distributions or orientations of pores in the first layer compared to the second layer. Most preferably, the first layer provides less porosity, i.e. a lower proportion of pores, than the second layer.

第１の層は、第２の層より高い強度、すなわち、ミクロ構造における相違から導かれる高い強度を有しているが、第２の層は、第１の層より低い熱伝導率、すなわち、ミクロ構造の相違から導かれるより低い熱伝導率を有する。第１の層に課せられた仕事は、下にある材料への十分な機械的強度と接着力をセラミックＴＢＣに与えることである。その高められた細孔率のため、第２の層は、それ自体ではＴＢＣの機械的強度に対して十分な寄与を示さない。他方では、その高められた細孔率のおかげで、第２の層は、非常に低い熱伝導率を保証する。好ましくは、第２のＴＢＣ層は、その環境に直接さらされる外側の層を決める。   The first layer has a higher strength than the second layer, i.e. a higher strength derived from the difference in the microstructure, but the second layer has a lower thermal conductivity than the first layer, i.e. It has a lower thermal conductivity derived from the difference in microstructure. The task imposed on the first layer is to give the ceramic TBC sufficient mechanical strength and adhesion to the underlying material. Due to its increased porosity, the second layer by itself does not make a sufficient contribution to the mechanical strength of the TBC. On the other hand, thanks to its increased porosity, the second layer ensures a very low thermal conductivity. Preferably, the second TBC layer defines an outer layer that is directly exposed to the environment.

本発明の好ましい実施態様によると、第１および第２の層は、同じ化学的組成を有する。
例えばジルコニアおよびジスポロシアなどの実質的に同じ主成分または元素を「同一発明」と称する。ＴＢＣ層の元素の正確な比率は、第１と第２の層の間で異なるかもしれないが、好ましくは、また、該比率は、２つの層について同じである。 According to a preferred embodiment of the invention, the first and second layers have the same chemical composition.
For example, substantially the same main components or elements such as zirconia and dysporusia are referred to as “same invention”. The exact ratio of elements in the TBC layer may differ between the first and second layers, but preferably the ratio is also the same for the two layers.

好ましくは、該ＴＢＣは、ＺｒＯ2として表される安定化されたジルコニア、すなわち、通常の正方晶または立方晶の安定なジルコニアを含む。ジルコニアの安定化は、エルビア、ネオジミア、ガドリニア、イットリア、カルシア、マグネシア、インジア、スカンジア、イッテルビア、およびそれらの混合物からなる群から選ばれる金属酸化物などの現状技術の範囲内でよく知られているいずれかの安定剤によって得ることができる。 Preferably, the TBC comprises stabilized zirconia represented as ZrO 2 , ie normal tetragonal or cubic stable zirconia. The stabilization of zirconia is well known within the state of the art such as metal oxides selected from the group consisting of elbia, neodymia, gadolinia, yttria, calcia, magnesia, india, scandia, ytterbia, and mixtures thereof. It can be obtained with any stabilizer.

該ＴＢＣ組成物は、また、二酸化ハフニウム、二酸化セリウム、二酸化ウラン、およびそれらの混合物からなる群から選ばれる四価金属イオンを含有する金属酸化物を含むことができる。   The TBC composition can also include a metal oxide containing a tetravalent metal ion selected from the group consisting of hafnium dioxide, cerium dioxide, uranium dioxide, and mixtures thereof.

ＴＢＣ組成物は、また、ニッケル酸化物、コバルト酸化物、またはクロム酸化物からなる群から選ばれるいずれかの金属酸化物を含むこともできる。   The TBC composition can also include any metal oxide selected from the group consisting of nickel oxide, cobalt oxide, or chromium oxide.

しかしながら、好ましくは、ジルコニアは、ジスプロシア（ＤｙＯ2）によって安定化される。典型的には、ジスプロシアの比率は、２〜３０重量％、好ましくは１０〜２０重量％である。 However, preferably zirconia is stabilized by dysprosia (DyO 2 ). Typically, the proportion of dysprosia is 2-30% by weight, preferably 10-20% by weight.

第２の層の厚さは、第１の層の厚さより厚くなければならない。第１の層の厚さは、１０〜１００のマイクロメーター、好ましくは４０〜７５マイクロメーターであるべきである。   The thickness of the second layer must be greater than the thickness of the first layer. The thickness of the first layer should be 10-100 micrometers, preferably 40-75 micrometers.

本発明は、また、本発明によるセラミック遮熱コーティングを含むことを特徴とする、被覆された金属基材に関するものである。   The invention also relates to a coated metal substrate, characterized in that it comprises a ceramic thermal barrier coating according to the invention.

該金属基材と該ＴＢＣの間に、結合コーティングが挟まれることがあることも理解されなければならない。そのような結合コーティングは、金属基材の上の金属酸化物、好ましくはアルミナの層を含むことができる。また、結合コーティングは、金属基材の上のアルミナイド、白金アルミナイド、ＭＣｒＡｌＹ合金または他のアルミニウム含有合金のコーティングおよび、場合によっては、その上に被着された金属酸化物、好ましくはアルミナの層を含むことができる。   It should also be understood that a bond coating may be sandwiched between the metal substrate and the TBC. Such bond coatings can include a layer of metal oxide, preferably alumina, on a metal substrate. The bond coating may also comprise a coating of aluminide, platinum aluminide, MCrAlY alloy or other aluminum-containing alloy on a metal substrate, and optionally a layer of metal oxide, preferably alumina, deposited thereon. Can be included.

典型的には、金属基材は、ニッケル超合金またはコバルト超合金である。   Typically, the metal substrate is a nickel superalloy or a cobalt superalloy.

本発明の目的は、また、セラミックＴＢＣの少なくとも２つの層が、該基材または結合コーティングに適用されること、そして、該基材または結合コーティングに隣接する第１のＴＢＣ層を適用するために使用される粉末粒子が、その被覆された基材の上にその後に第２のＴＢＣ層を適用するために使用される粉末粒子と異なるミクロ構造を与えることを特徴とする、最初に定義された方法によって達成される。   It is also an object of the present invention to apply at least two layers of ceramic TBC to the substrate or bond coating and to apply a first TBC layer adjacent to the substrate or bond coating. First defined, characterized in that the powder particles used give a different microstructure than the powder particles used to subsequently apply a second TBC layer on the coated substrate Achieved by the method.

好ましくは、第１のＴＢＣ層を適用される粉末粒子は、その被覆された基材の上にその後に第２のＴＢＣ層を適用するために使用される粉末粒子より少ない細孔率を与える。   Preferably, the powder particles to which the first TBC layer is applied give less porosity than the powder particles that are subsequently used to apply the second TBC layer on the coated substrate.

本発明の好ましい実施態様によると、第１のＴＢＣ層を適用するために使用される粉末粒子は、緻密な焼結構造を与える。そのような構造を実現するためには、本発明の方法は、好ましくは粉粒の塊状物を焼結して前記の粉末粒子を形成するステップを含む。   According to a preferred embodiment of the present invention, the powder particles used to apply the first TBC layer give a dense sintered structure. In order to realize such a structure, the method of the present invention preferably comprises the step of sintering a mass of granules to form said powder particles.

好ましくは、第２のＴＢＣ層を適用するために使用される粉末粒子は、多孔質構造を与える。各粉末粒子が、溶融された粉末材料の殻または皮膜によって囲まれた粉粒の塊状物を含む場合に有利であることが判明した。そのようなミクロ構造は、該方法が、粉粒の塊状物をＨＯＳＰ−処理して前記の粉末粒子を形成するステップを含むことによって達成され得る。   Preferably, the powder particles used to apply the second TBC layer provide a porous structure. It has been found to be advantageous if each powder particle comprises a lump of powder surrounded by a shell or coating of molten powder material. Such a microstructure can be achieved by the method comprising the step of HOSP-treating the agglomerates of granules to form said powder particles.

焼結されるか、またはＨＯＳＰ処理される粉粒の塊状物は、例えば０．５〜５マイクロメーター、好ましくは１〜２マイクロメーターの粒径を有する粉末のバッチを、バインダーを含有する液状混合物中に導入し、その後、液体が除去されて１０〜１５０マイクロメーターの典型的な直径を有する塊状物が形成されるような条件下で乾燥させるプロセスを通して通常は製造される。   Sintered or HOSP treated granulate mass is a batch of powder having a particle size of eg 0.5-5 micrometers, preferably 1-2 micrometers, a liquid mixture containing a binder It is usually manufactured through a process of introducing into and then drying under conditions such that the liquid is removed and a mass having a typical diameter of 10-150 micrometers is formed.

本発明のさらなる特徴と利点を、以下の詳細な説明において記述する。   Additional features and advantages of the invention will be described in the detailed description that follows.

添付図面を参照して、以下に本発明を更に詳細に説明する。   The present invention will be described in more detail below with reference to the accompanying drawings.

図１に示された機械の物品は、超合金で作られた金属基材２の上に本発明の方法によって被着されたセラミック遮熱コーティング（ＴＢＣ）１を含む。基材２は、また、技術的によく知られた方法（ＰＶＤ、ＣＶＤ、熱溶射など）によって基材２の上に被着された中間介在金属下層または結合コーティング３によって被覆されている。   The machine article shown in FIG. 1 includes a ceramic thermal barrier coating (TBC) 1 deposited by a method of the present invention on a metal substrate 2 made of a superalloy. The substrate 2 is also covered by an intermediate intervening metal underlayer or bond coating 3 deposited on the substrate 2 by methods well known in the art (PVD, CVD, thermal spraying, etc.).

結合コーティング３は、ＭＣｒＡｌＹ（Ｍ＝Ｎｉ、および／またはＣｏおよび／またはＦｅ）タイプあるいはニッケルまたはコバルトアルミナイドの酸化物耐蝕性アルミノ形成合金であり得るが、場合によっては、それらは、クロムおよび／またはプラチナ、パラジウム、ルテニウム、イリジウム、オスミウム、およびロジウムから選ばれる１種またはそれ以上の貴金属の添加により変性されていてもよい。   The bond coating 3 can be of the MCrAlY (M = Ni and / or Co and / or Fe) type or an oxide corrosion resistant aluminoforming alloy of nickel or cobalt aluminide, but in some cases they are chromium and / or It may be modified by the addition of one or more precious metals selected from platinum, palladium, ruthenium, iridium, osmium, and rhodium.

該セラミックＴＢＣは、ジルコニアを安定化させ、セラミックの熱伝導率を低下させるために、ジルコニアベースおよびジスプロシウム酸化物からなる。また、熱伝導率をさらに減少させるために、セラミックは、ジルコニウムイオンの原子質量より大きな原子質量を有する４価の金属イオンを含む追加の酸化物を含有していてもよい。その４価の金属イオンは、セリウム、ハフニウム、ウラニウムであり得る。   The ceramic TBC consists of a zirconia base and a dysprosium oxide in order to stabilize zirconia and reduce the thermal conductivity of the ceramic. In order to further reduce the thermal conductivity, the ceramic may contain an additional oxide containing a tetravalent metal ion having an atomic mass greater than that of the zirconium ion. The tetravalent metal ion can be cerium, hafnium, uranium.

該セラミックＴＢＣは、実質的に同じ化学的な組成の２つの個々の層に細分化される。第１の層４は、結合コーティング３に付着しており、第２の外側の層５は、第１の層に付着している。第１の層は、相対的に緻密であり、それによって結合コーティングへよく接着し、第２の層５より高い機械的な強度を与える。   The ceramic TBC is subdivided into two individual layers of substantially the same chemical composition. The first layer 4 is attached to the bond coating 3 and the second outer layer 5 is attached to the first layer. The first layer is relatively dense and thereby adheres well to the bond coating and provides a higher mechanical strength than the second layer 5.

第２の層５は、第１の層４より多くの開口の多孔性構造を与える。その多孔性構造に基づき、第２の層は、そうでない場合より、さらに減少した熱伝導性を有する。しかしながら、改良された伝導率の特性の代償として、第１の層４のそれより著しく低い、減少された熱衝撃または熱サイクルの耐性しか有さない。   The second layer 5 provides a more porous structure than the first layer 4. Based on its porous structure, the second layer has a further reduced thermal conductivity than otherwise. However, at the cost of improved conductivity properties, it has only reduced thermal shock or thermal cycle resistance, significantly lower than that of the first layer 4.

それらの異なるミクロ構造の結果として、第１および第２の層は、それぞれ機械的強度および低い熱伝導性へのそれらの個々の寄与を互いに補足する。   As a result of their different microstructures, the first and second layers complement each other with their individual contributions to mechanical strength and low thermal conductivity.

言い換えれば、第１の粉末は、第１の層４を形成するセラミックによって形成され、そして、第２の粉末は、第２の層５を形成するセラミックによって形成される。   In other words, the first powder is formed by the ceramic forming the first layer 4, and the second powder is formed by the ceramic forming the second layer 5.

該セラミックＴＢＣは、プラズマ溶射によって被着される。プラズマ溶射装置６は、図２に図式的に示される。装置６は、陰極８を取り囲んで、ガスのノズルを形成する陽極７を含んでいるが、この種類の装置は、現状の技術でよく知られており、さらに詳細な説明は必要ない。電気アークとプラズマジェット９は、陽極７、陰極８、およびノズルを通して流れるガス類によって生成される。装置は、さらに粉末粒子１２の流れをプラズマジェット９に導入するための手段１０を含んでいる。ジェット９は、基材１３に向けられ、同時に前記の粒子１２の少なくとも一部を溶融しながら粉末粒子１２を基材１３に向かって流送するだろう。   The ceramic TBC is deposited by plasma spraying. The plasma spraying device 6 is shown schematically in FIG. Device 6 includes an anode 7 that surrounds cathode 8 and forms a gas nozzle, but this type of device is well known in the state of the art and does not require further detailed description. The electric arc and plasma jet 9 are generated by gases flowing through the anode 7, the cathode 8, and the nozzle. The apparatus further comprises means 10 for introducing a flow of powder particles 12 into the plasma jet 9. The jet 9 will be directed toward the substrate 13 and will simultaneously flow the powder particles 12 towards the substrate 13 while melting at least a portion of the particles 12.

本発明によれば、相対的に緻密な予備焼結された粉末粒子１２をジェット９の中に導入することによって、第１のＴＢＣ層４が基材２の上、またはさらに正確には基材２を被覆している結合コーティング３の上に形成される。第１の層４を生成するために使用される粉末粒子１２は、本明細書でより前に記述されたプロセスによって、すなわち塊状化および焼結方法を通して形成される。   According to the present invention, by introducing relatively dense pre-sintered powder particles 12 into the jet 9, the first TBC layer 4 is on the substrate 2 or more precisely the substrate. 2 is formed on the bond coating 3 covering 2. The powder particles 12 used to produce the first layer 4 are formed by the process described earlier in this specification, ie through the agglomeration and sintering method.

第１の層４を生成するための粒子１２、または少なくとも実質的な、または好ましくはその主要な部分は、基材２／結合コーティング３を打ちつけながら完全に、またはほとんど完全に溶融され、緻密で多孔質でない膜４を形成するだろう。緻密とは、２００倍以下の光学顕微鏡で多孔率が５％より少ないことを称する。   The particles 12, or at least substantially or preferably the main part thereof, for producing the first layer 4 are completely or almost completely melted and compacted while striking the substrate 2 / bonding coating 3. A non-porous membrane 4 will be formed. Dense means that the porosity is less than 5% with an optical microscope of 200 times or less.

そして、第２の層５は、次いでそれ以前のものと異なるミクロ構造を有する粉末粒子１２を導入する第１の粉末の導入によって形成される。第２の層を生成するための粉末粒子は、第１の粉末粒子より、多くの開口の多孔性構造を有している。好ましくは、それらは、本明細書においてより前に記載された方法、すなわち集塊化／ＨＯＳＰプロセスによって生成され、このＨＯＳＰプロセスとは、現状の技術でよく知られた均質オーブン球形粉体プロセス（Homogeneous Oven Spherical Powder process）と称されるものである。   The second layer 5 is then formed by the introduction of the first powder, which then introduces the powder particles 12 having a different microstructure than the previous one. The powder particles for producing the second layer have a porous structure with more openings than the first powder particles. Preferably, they are produced by the method described earlier herein, namely the agglomeration / HOSP process, which is a homogeneous oven spherical powder process well known in the state of the art ( Homogeneous Oven Spherical Powder process).

第２の層５を生成するための粉末粒子１２は、第１の層４またはその下にある材料（それが何であろうとも）に衝突するときに単に一部だけが溶融されるだろう。好ましくは、塊状化された粉末粒子を取り囲んだ、以前に形成された殻または皮膜は、主に、または僅かにジェット９によって溶融される。その結果、多孔性の第２の層５が、形成される。多孔性は、主に層状であり、したがって、細孔は、下にある材料２，３，４の平面に対して一般的に平行な面に平らに伸ばされている。多孔率は、５％より少ない多孔率を有する第１の層に対比して、５％より多い。   The powder particles 12 for producing the second layer 5 will only be partially melted when impacting the first layer 4 or the underlying material (whatever it is). Preferably, the previously formed shell or film surrounding the agglomerated powder particles is melted mainly or slightly by the jet 9. As a result, a porous second layer 5 is formed. The porosity is mainly lamellar, so that the pores are stretched flat in a plane generally parallel to the plane of the underlying material 2, 3, 4. The porosity is greater than 5% compared to a first layer having a porosity of less than 5%.

前記のステップを実行するためには、異なる溶射パラメータが、正確に調整される必要がある。そのようなパラメータは、電流（電圧）、ガス流、粉末供給速度、粉末温度、粉末速度、粉末径、粉末導入位置（ジェットおよび基材に対する距離に関連して）、基材温度を含む。   In order to perform the above steps, the different spray parameters need to be adjusted precisely. Such parameters include current (voltage), gas flow, powder feed rate, powder temperature, powder velocity, powder diameter, powder introduction position (relative to distance to jet and substrate), substrate temperature.

前記のパラメータは、ミクロ構造、硬度、強度、応力などのコーティング特性に影響を与え、ひいては、それらが、セラミックＴＢＣおよび被覆された金属基材、すなわち物品２の性能および実用寿命に影響を与えるだろう。   The above parameters will affect the coating properties such as microstructure, hardness, strength, stress, etc., which in turn will affect the performance and useful life of ceramic TBC and coated metal substrate, ie article 2. Let's go.

本発明の前記の説明は、例としてなされたものであり、代替の実施態様は、当業者にとって明白であることが理解されるべきである。しかしながら、請求される保護の範囲は、説明および付属の図面によって支持される特許請求の範囲で限定される。   It should be understood that the foregoing description of the invention has been made by way of example and that alternative embodiments will be apparent to those skilled in the art. However, the scope of protection claimed is limited by the claims supported by the description and the accompanying drawings.

本発明によって形成されたセラミック遮熱コーティングを含む機械の超合金物品の拡大された倍率による図式的な断面図である。1 is a schematic cross-sectional view of a mechanical superalloy article including a ceramic thermal barrier coating formed according to the present invention at an enlarged magnification. FIG. 本発明によるコーティングの被着のための装置および本発明の方法に従った作動状態の図式的な断面図である。Figure 2 is a schematic cross-sectional view of an apparatus for coating application according to the present invention and an operating state according to the method of the present invention;

Claims (11)

セラミック遮熱コーティング（１）（ＴＢＣ）を、基材（２）またはその基材（２）の上に適用されたＴＢＣあるいは基材（２）と該ＴＢＣとの間の中間介在結合コーティング（３）の上に、基材（２）または結合コーティング（３）上への前記ＴＢＣ粉末の熱溶射によって適用する方法であって、セラミックＴＢＣの少なくとも２つの層（４，５）が、基材（２）または結合コーティング（３）に適用され、そして第１のＴＢＣ層（４）を生成するために使用される粉末粒子は、被覆された基材（２）の上に第２のＴＢＣ層（５）をその後に生成するために使用される粉末粒子と異なるミクロ構造を与える方法において、第１のＴＢＣ層（４）を生成するために使用される粉末粒子が、その後に被覆された基材（２）の上に第２のＴＢＣ層（５）を生成するために使用される粉末粒子より低い多孔率を与え、
第１の内側のＴＢＣ層（４）と第２の外側のＴＢＣ層（５）とが異なるミクロ構造に成るように、両ＴＢＣ層（４，５）は互いに異なる形成方法が採用されており、
前記第１のＴＢＣ層（４）は、略完全に溶融した粉末粒子を堆積することで形成されており、
前記第２のＴＢＣ層（５）は、粉末粒子から構成された塊状物を堆積することで形成されており、前記塊状物は、溶融された粉末材料から成る殻体によって取り囲まれた多数粒の粉粒から構成されていることを特徴とする方法。Ceramic thermal barrier coating (1) (TBC) is applied to the substrate (2) or TBC applied on the substrate (2) or an intermediate intervening bond coating (3) between the substrate (2) and the TBC. ) By thermal spraying of said TBC powder onto a substrate (2) or bond coating (3), wherein at least two layers (4, 5) of ceramic TBC are applied to the substrate ( 2) or the powder particles applied to the bond coating (3) and used to produce the first TBC layer (4) are the second TBC layer (on the coated substrate (2)). 5) in a method to give a microstructure different from the powder particles used to subsequently produce the substrate on which the powder particles used to produce the first TBC layer (4) are subsequently coated. (2) on top of the second TBC layer 5) gave low porosity than the powder particles used to generate,
The TBC layers (4, 5) are formed differently from each other so that the first inner TBC layer (4) and the second outer TBC layer (5) have different microstructures.
The first TBC layer (4) is formed by depositing substantially completely molten powder particles;
The second TBC layer (5) is formed by depositing a lump made up of powder particles, the lump being made up of a number of grains surrounded by a shell made of molten powder material. A method comprising powder particles. 第１のＴＢＣ層（４）を適用するために使用される粉末粒子が、緻密な焼結された構造を与えることを特徴とする、請求項１に記載の方法。  2. A method according to claim 1, characterized in that the powder particles used to apply the first TBC layer (4) give a dense sintered structure. 前記の粉末粒子に粉粒の塊状物を焼結するステップを含むことを特徴とする、請求項１または２に記載の方法。  3. A method according to claim 1 or 2, characterized in that it comprises the step of sintering a mass of granules into said powder particles. 前記の粉末粒子を形成するために粉粒の塊状物をＨＯＳＰ−処理するステップを含むことを特徴とする、請求項１ないし３のいずれかに記載の方法。  4. A method according to any one of the preceding claims, characterized in that it comprises a HOSP-treatment of the powder mass to form said powder particles. 第１および第２のセラミックＴＢＣ層（４，５）は、同じ化学的な組成を有することを特徴とする、請求項１ないし４のいずれか１つに記載の方法。  The method according to any one of claims 1 to 4, characterized in that the first and second ceramic TBC layers (4, 5) have the same chemical composition. 該ＴＢＣが、安定化されたジルコニアを含むことを特徴とする、請求項１ないし５のいずれか１つに記載の方法。  6. A method according to any one of claims 1 to 5, characterized in that the TBC comprises stabilized zirconia. 該ＴＢＣが、ジスプロシアで安定化されたジルコニアを含むことを特徴とする、請求項１ないし６のいずれか１つに記載の方法。  7. A method according to any one of the preceding claims, characterized in that the TBC comprises dysprosia stabilized zirconia. 粉末粒子の直径が、１０〜１５０マイクロメーターであることを特徴とする、請求項１ないし７のいずれか１つに記載の方法。  The method according to any one of claims 1 to 7, wherein the diameter of the powder particles is 10 to 150 micrometers. 前記の粉末粒子を形成する粉粒の直径が、０．５〜５マイクロメーターであることを特徴とする、請求項１ないし８のいずれか１つに記載の方法。  The method according to any one of claims 1 to 8, wherein the diameter of the powder particles forming the powder particles is 0.5 to 5 micrometers. 前記の粉末粒子を形成する粉粒の直径が、１〜２マイクロメーターであることを特徴とする、請求項１ないし９のいずれか１つに記載の方法。  The method according to any one of claims 1 to 9, wherein the diameter of the powder particles forming the powder particles is 1 to 2 micrometers. 該ＴＢＣが、プラズマ溶射によって適用されることを特徴とする、請求項１ないし１０のいずれか１つに記載の方法。  11. A method according to any one of the preceding claims, characterized in that the TBC is applied by plasma spraying.
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