JP4045697B2 - Oxidation resistant thermal insulation film and method for forming the same - Google Patents

Oxidation resistant thermal insulation film and method for forming the same Download PDF

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JP4045697B2
JP4045697B2 JP23367699A JP23367699A JP4045697B2 JP 4045697 B2 JP4045697 B2 JP 4045697B2 JP 23367699 A JP23367699 A JP 23367699A JP 23367699 A JP23367699 A JP 23367699A JP 4045697 B2 JP4045697 B2 JP 4045697B2
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nicraly
mosi
forming
oxidation
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JP2001059188A (en
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啓嗣 園家
省吾 戸部
繁 北原
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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
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    • 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
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    • 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
    • C23C28/325—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with layers graded in composition or in physical properties
    • 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
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    • 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
    • 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
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    • 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
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    • 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
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    • 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
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Description

【０００１】
【発明の属する技術分野】
本発明は、航空機用エンジン、ガスタービン用エンジン、ゴミ処理装置等のような、非常に高温且つ高い酸化性の雰囲気で使用される構造材を保護するための耐酸化性断熱皮膜及びその形成方法に関するものである。
【０００２】
【従来の技術】
溶射によって構造材の表面に皮膜を形成する技術は、耐熱性、断熱性、耐摩耗性、耐腐食性等が要求される箇所に幅広く用いられている。溶射によって形成された皮膜は、断熱部材として作用し、これによって構造材である基材の温度を低下させることができ、よって基材の使用限界温度を上昇させることができる。
【０００３】
中でも、プラズマ溶射によって形成されるジルコニアＺｒＯ2系セラミックスの皮膜は、航空機用ジェットエンジン、発電用等のガスタービンエンジンの燃焼室内壁等に利用されており、エンジンの高出力化に重要な役割を果たしている。
【０００４】
近年、こうしたエンジン等は、その出力増加、変換効率の向上、ひいては環境汚染低減を目指して稼動温度の高温化が進められており、ジルコニアＺｒＯ2を用いた断熱皮膜は、こうした高温部の断熱を行って基材を保護する上で不可欠なものとなっている。
【０００５】
通常のジルコニア断熱皮膜は、基材の表面に溶射によって形成したＮｉＣｒＡｌＹ層（ボンドコート）の上にジルコニアＺｒＯ2を溶射することにより、ＺｒＯ2−Ｙ2Ｏ3の形、即ち部分安定化ジルコニア層（ＰＳＺ）として成膜される。
【０００６】
従来のジルコニア断熱皮膜は、図５に示すように、まず、基材１の表面に、ＮｉＣｒＡｌＹを低真空中でプラズマ溶射することにより、約１００μ前後の厚さでＮｉＣｒＡｌＹ層２（ボンドコート）を形成する。このとき、ＮｉＣｒＡｌＹ層２は、酸化しないように真空吸引して減圧した状態で、不活性ガスを用いてプラズマ溶射される。このように低真空中でプラズマ溶射することを以下では減圧プラズマ溶射という。
【０００７】
減圧プラズマ溶射は、プラズマの形状が大気中より長くなり、なお且つ乱れないことが判明している。このため、減圧プラズマ溶射では、ノズルの先端より遠方まで温度が低下せず、また溶射粉末がノズルジェットの中での停留時間が長くなり、その分よく溶融することになる。これらの理由から、減圧プラズマ溶射された溶射皮膜は気孔が少なく、基材との接着力も強い。また、未溶融粒子も少なく密着効率も高いという利点を有している。
【０００８】
続いて、図５に示すように、上記によって形成されたＮｉＣｒＡｌＹ層２上に、ジルコニアＺｒＯ2を大気中プラズマ溶射することにより、約３５０μ前後の厚さの部分安定化ジルコニア層３（ＰＳＺ：トップコート）を形成する。この部分安定化ジルコニア層３の形成は、減圧プラズマ溶射によって行っても或いは大気中プラズマ溶射によって行ってもその性能には殆ど差異がない。このため、部分安定化ジルコニア層３の形成には、一般に安価で操作が容易な大気中プラズマ溶射が実施されている。
【０００９】
一方、ジルコニアＺｒＯ2は、非常に硬い金属であり、このために溶射によって形成された部分安定化ジルコニア層３には微細な無数の亀裂４（傷）が生成している。尚、この微細な亀裂４は、その存在によって熱歪みの緩和が図れるという作用を有している。
【００１０】
上記部分安定化ジルコニア層３は、機器作動中の熱応力や機械的応力、さらには燃焼ガスによる腐食損傷等を受けるため、その寿命は有限であることから長寿命化が求められており、種々の試みがなされている。
【００１１】
【発明が解決しようとする課題】
しかし、図５に示したような従来のＮｉＣｒＡｌＹ層２と部分安定化ジルコニア層３との２層によって形成される溶射断熱皮膜は、耐酸化性が弱く、疲労寿命も短いという問題を有していた。
【００１２】
即ち、部分安定化ジルコニア層３に形成されている微細な亀裂４を通して、外部の酸化性ガス（空気）が内部のＮｉＣｒＡｌＹ層２まで侵入し、これによってＮｉＣｒＡｌＹ層２が酸化し、この酸化によってＮｉＣｒＡｌＹ層２内を疲労亀裂が進展して遂には基材１まで達してしまい、基材１とＮｉＣｒＡｌＹ層２との間で剥離現象が生じるようになり、このような現象によって基材１が熱疲労を起こし、寿命が短縮されるという問題を有していた。
【００１３】
本発明は、かかる従来の問題点を解決すべくなしたもので、部分安定化ジルコニア層からの酸化性ガスの侵入防止と疲労亀裂の進展防止とを達成して、高い断熱性能を保持できるようにした耐酸化性断熱皮膜及びその形成方法を提供することを目的としている。
【００１４】
【課題を解決するための手段】
本発明は、基材に形成されたＮｉＣｒＡｌＹ層上に、ＭｏＳｉ2−ＮｉＣｒＡｌＹ層を挟んで部分安定化ジルコニア層が形成されていることを特徴とする耐酸化性断熱皮膜、に係るものである。
【００１５】
上記手段において、ＭｏＳｉ2−ＮｉＣｒＡｌＹ層におけるＭｏＳｉ2の含有割合が４０〜９０％、ＮｉＣｒＡｌＹの含有割合が１０〜６０％であってもよい。
【００１６】
本発明は、基材表面に、ＮｉＣｒＡｌＹを減圧プラズマ溶射することによりＮｉＣｒＡｌＹ層を形成し、ＮｉＣｒＡｌＹ層上に、ＭｏＳｉ2とＮｉＣｒＡｌＹとの混合物を減圧プラズマ溶射することによりＭｏＳｉ2−ＮｉＣｒＡｌＹ層を形成し、該ＭｏＳｉ2−ＮｉＣｒＡｌＹ層上に、ＺｒＯ2を大気中プラズマ溶射して部分安定化ジルコニア層を形成することを特徴とする耐酸化性断熱皮膜の形成方法、に係るものである。
【００１７】
上記手段において、ＭｏＳｉ2−ＮｉＣｒＡｌＹ層を形成するＭｏＳｉ2の混合割合が４０〜９０％、ＮｉＣｒＡｌＹの混合割合が１０〜６０％であってもよい。
【００１８】
本発明によれば、基材に形成されたＮｉＣｒＡｌＹ層上に、ＭｏＳｉ2−ＮｉＣｒＡｌＹ層を中間層として挟むように部分安定化ジルコニア層を形成しているので、最外側の部分安定化ジルコニア層の微細な亀裂を通して外部から酸化性ガスが侵入してきても、この酸化性ガスの侵入をＭｏＳｉ2−ＮｉＣｒＡｌＹ層で食い止めて、内側のＮｉＣｒＡｌＹ層の酸化、及びＮｉＣｒＡｌＹ層から基材への疲労亀裂の進展を防止できるので、部分安定化ジルコニア層による断熱効果が安定に維持され、よって基材の熱疲労が防止されて寿命が延長される。
【００１９】
【発明の実施の形態】
以下、本発明の好適な実施の形態を図面に基づいて説明する。
【００２０】
耐酸化性の断熱皮膜を形成するには、部分安定化ジルコニア層（ＰＳＺ）における微細な亀裂から侵入する酸化性ガスが、ＮｉＣｒＡｌＹ層に到達しないようにすることが有効である。
【００２１】
このため、上記したような酸化性ガスの侵入を防止できる作用を持つ金属について種々検討した。高融点金属シリサイドには、ＭｏＳｉ2，ＷＳｉ2，ＮｂＳｉ2，ＴａＳｉ2等が知られており、これらの金属シリサイドの中で、モリブデンシリサイドＭｏＳｉ2は、融点が２３０３Ｋと高く、しかも非常に優れた高温耐酸化性を示すことから、超高温用金属材料として有望視されている。
【００２２】
従って、上記モリブデンシリサイドＭｏＳｉ2を用いた層を、ＮｉＣｒＡｌＹ層と部分安定化ジルコニア層との中間に、中間層として形成することを考えた。
【００２３】
基材の表面に断熱皮膜を形成するために、先ず図２に示すように、真空吸引されている低真空容器５内において、プラズマ照射装置６を用いて、基材１上にＮｉＣｒＡｌＹを減圧プラズマ溶射（ＶＰＳ）することにより、約１００μ前後の厚さでＮｉＣｒＡｌＹ層２を形成する。
【００２４】
次に、図３に示すように、低真空容器５内において、上記によって形成されたＮｉＣｒＡｌＹ層２上に、モリブデンシリサイドＭｏＳｉ2とＮｉＣｒＡｌＹの混合物を減圧プラズマ溶射（ＶＰＳ）することにより、約１００μ前後の厚さのＭｏＳｉ2−ＮｉＣｒＡｌＹ層７を形成する。このとき、例えば図１の例では、モリブデンシリサイドＭｏＳｉ2の混合割合が７０％、ＮｉＣｒＡｌＹの混合割合が３０％の場合を例示しているが、モリブデンシリサイドＭｏＳｉ2の混合割合は約４０〜９０％、ＮｉＣｒＡｌＹの混合割合は約１０〜６０％の範囲で変化させて調整することができる。
【００２５】
上記ＭｏＳｉ2−ＮｉＣｒＡｌＹ層７は、全膜厚に亘ってモリブデンシリサイドＭｏＳｉ2とＮｉＣｒＡｌＹとの混合割合が均一となるように溶射してもよく、また、モリブデンシリサイドＭｏＳｉ2の割合が膜厚の厚さ方向に変化するように傾斜割合をもたせて溶射するようにしてもよい。
【００２６】
続いて、図４に示すように、上記によって形成されたＭｏＳｉ2−ＮｉＣｒＡｌＹ層７上に、ジルコニアＺｒＯ2を大気中プラズマ溶射（ＡＰＳ）することにより、約２００μ前後の厚さで部分安定化ジルコニア層３（ＰＳＺ）を形成する。
【００２７】
上記方法によれば、図１に示すように、基材１に形成されたＮｉＣｒＡｌＹ層２上に、ＭｏＳｉ2−ＮｉＣｒＡｌＹ層７を挟んで部分安定化ジルコニア層３が形成された３層構造の断熱皮膜が形成できる。
【００２８】
以下に、上記形態例の作用を説明する。
【００２９】
本発明の耐酸化性断熱皮膜を形成するに当たっては、先ず図２に示すように、基材１上にＮｉＣｒＡｌＹを減圧プラズマ溶射することによってＮｉＣｒＡｌＹ層２を形成する。
【００３０】
次に、モリブデンシリサイドＭｏＳｉ2の混合割合が約４０〜９０％、ＮｉＣｒＡｌＹの混合割合が約１０〜６０％になるように調整した混合物を、図３に示すように、ＮｉＣｒＡｌＹ層２上に減圧プラズマ溶射することによってＭｏＳｉ2−ＮｉＣｒＡｌＹ層７を形成する。
【００３１】
続いて、図４に示すように、ＭｏＳｉ2−ＮｉＣｒＡｌＹ層７上に、ジルコニアＺｒＯ2を大気中プラズマ溶射することにより部分安定化ジルコニア層３を形成する。
【００３２】
上記によれば、図１に示すように、基材１に形成されたＮｉＣｒＡｌＹ層２上に、ＭｏＳｉ2−ＮｉＣｒＡｌＹ層７を中間層として挟んで部分安定化ジルコニア層３が一体に形成された３層構造の断熱皮膜が得られる。
【００３３】
上記したようにＭｏＳｉ2−ＮｉＣｒＡｌＹ層７による中間層を備えると、ＭｏＳｉ2−ＮｉＣｒＡｌＹ層７のモリブデンシリサイドＭｏＳｉ2が、溶射皮膜中に発生した亀裂を高温下においてＳｉＯ2によって埋めて自然治癒させる挙動を現わし、このために、ＭｏＳｉ2−ＮｉＣｒＡｌＹ層７により耐酸化の機能が大幅に向上されるようになる。
【００３４】
即ち、最外側の部分安定化ジルコニア層３の微細な亀裂４を通して外部から酸化性ガスが侵入してきても、この酸化性ガスの侵入をＭｏＳｉ2−ＮｉＣｒＡｌＹ層７で食い止めて、内側のＮｉＣｒＡｌＹ層２が酸化されるのを防止し、更にＮｉＣｒＡｌＹ層２から基材１へ疲労亀裂が進展するのを防止する。
【００３５】
従って、部分安定化ジルコニア層による断熱効果が安定して維持されるようになり、よって基材の熱疲労が防止されて寿命が延長されることになる。
【００３６】
尚、本発明は上記形態例にのみ限定されるものではなく、本発明の要旨を逸脱しない範囲内において種々変更を加え得ることは勿論である。
【００３７】
【発明の効果】
本発明によれば、基材に形成されたＮｉＣｒＡｌＹ層上に、ＭｏＳｉ2−ＮｉＣｒＡｌＹ層を中間層として挟むように部分安定化ジルコニア層を形成しているので、最外側の部分安定化ジルコニア層の微細な亀裂を通して外部から酸化性ガスが侵入してきても、この酸化性ガスの侵入をＭｏＳｉ2−ＮｉＣｒＡｌＹ層で食い止めて、内側のＮｉＣｒＡｌＹ層の酸化、及びＮｉＣｒＡｌＹ層から基材への疲労亀裂の進展を防止できるので、部分安定化ジルコニア層による断熱効果が安定に維持され、よって基材の熱疲労を防止して寿命を延長できるという優れた効果を奏し得る。
【図面の簡単な説明】
【図１】本発明の耐酸化性断熱皮膜の一例を示す概略側面図である。
【図２】本発明の耐酸化性断熱皮膜の形成方法において、基材上に減圧プラズマ溶射によりＮｉＣｒＡｌＹ層を形成している状態を示す概略側面図である。
【図３】本発明の耐酸化性断熱皮膜の形成方法において、ＮｉＣｒＡｌＹ層上に、減圧プラズマ溶射によりＭｏＳｉ2−ＮｉＣｒＡｌＹ層を形成している状態を示す概略側面図である。
【図４】本発明の耐酸化性断熱皮膜の形成方法において、ＭｏＳｉ2−ＮｉＣｒＡｌＹ層上に、大気中プラズマ溶射により部分安定化ジルコニア層を形成している状態を示す概略側面図である。
【図５】従来の耐酸化性断熱皮膜の一例を示す概略側面図である。
【符号の説明】
１ 基材
２ ＮｉＣｒＡｌＹ層
３ 部分安定化ジルコニア層（ＰＳＺ）
７ ＭｏＳｉ2−ＮｉＣｒＡｌＹ層（中間層）[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an oxidation-resistant heat-insulating coating for protecting structural materials used in an atmosphere of very high temperature and high oxidation, such as an aircraft engine, a gas turbine engine, and a garbage disposal device, and a method for forming the same. It is about.
[0002]
[Prior art]
A technique for forming a film on the surface of a structural material by thermal spraying is widely used in places where heat resistance, heat insulation, wear resistance, corrosion resistance, and the like are required. The film formed by thermal spraying acts as a heat insulating member, thereby reducing the temperature of the base material, which is a structural material, and thus increasing the use limit temperature of the base material.
[0003]
Above all, the coating of zirconia ZrO 2 ceramics formed by plasma spraying is used on the combustion chamber walls of gas turbine engines for aircraft jet engines and power generation, and plays an important role in increasing engine output. Plays.
[0004]
In recent years, these engines and the like have been increased in operating temperature with the aim of increasing their output, improving conversion efficiency, and thus reducing environmental pollution. Thermal insulation coatings using zirconia ZrO 2 can insulate these high-temperature parts. It is indispensable to go and protect the substrate.
[0005]
A normal zirconia heat-insulating film is formed by spraying zirconia ZrO 2 on a NiCrAlY layer (bond coat) formed on the surface of a substrate by spraying, thereby forming a ZrO 2 —Y 2 O 3 form, ie, a partially stabilized zirconia layer. The film is formed as (PSZ).
[0006]
As shown in FIG. 5, the conventional zirconia heat insulating film is formed by first performing NiCrAlY plasma spraying on the surface of the substrate 1 in a low vacuum to form a NiCrAlY layer 2 (bond coat) with a thickness of about 100 μm. Form. At this time, the NiCrAlY layer 2 is plasma sprayed using an inert gas in a state where the pressure is reduced by vacuum suction so as not to oxidize. Such plasma spraying in a low vacuum is hereinafter referred to as reduced pressure plasma spraying.
[0007]
Low pressure plasma spraying has been found to have a plasma shape that is longer than in the atmosphere and is not disturbed. For this reason, in low-pressure plasma spraying, the temperature does not decrease farther from the tip of the nozzle, and the sprayed powder has a longer retention time in the nozzle jet and melts accordingly. For these reasons, the low-pressure plasma sprayed thermal spray coating has few pores and strong adhesion to the substrate. In addition, there is an advantage that the number of unmelted particles is small and the adhesion efficiency is high.
[0008]
Subsequently, as shown in FIG. 5, zirconia ZrO 2 is plasma sprayed in the air on the NiCrAlY layer 2 formed as described above, thereby partially stabilizing the zirconia layer 3 (PSZ: top) having a thickness of about 350 μm. Coat). The formation of the partially stabilized zirconia layer 3 has almost no difference in performance regardless of whether it is performed by low pressure plasma spraying or atmospheric plasma spraying. For this reason, in order to form the partially stabilized zirconia layer 3, plasma spraying in the air that is generally inexpensive and easy to operate is performed.
[0009]
On the other hand, zirconia ZrO 2 is a very hard metal. Therefore, innumerable fine cracks 4 (scratches) are generated in the partially stabilized zirconia layer 3 formed by thermal spraying. The fine crack 4 has the effect of mitigating thermal strain due to its presence.
[0010]
The partially stabilized zirconia layer 3 is subjected to thermal stress and mechanical stress during operation of the equipment, further corrosive damage due to combustion gas, etc., and its life is finite, so a long life is required. Attempts have been made.
[0011]
[Problems to be solved by the invention]
However, the thermal spray coating formed by two layers of the conventional NiCrAlY layer 2 and the partially stabilized zirconia layer 3 as shown in FIG. 5 has a problem that the oxidation resistance is weak and the fatigue life is short. It was.
[0012]
That is, an external oxidizing gas (air) penetrates into the internal NiCrAlY layer 2 through the fine crack 4 formed in the partially stabilized zirconia layer 3, thereby oxidizing the NiCrAlY layer 2, and this oxidation causes the NiCrAlY layer to oxidize. The fatigue crack progresses in the layer 2 and finally reaches the base material 1, and a peeling phenomenon occurs between the base material 1 and the NiCrAlY layer 2, and this phenomenon causes the base material 1 to be thermally fatigued. This has the problem of shortening the service life.
[0013]
The present invention has been made to solve such a conventional problem, and can achieve prevention of invasion of oxidizing gas from the partially stabilized zirconia layer and prevention of progress of fatigue cracks so that high heat insulation performance can be maintained. It is an object of the present invention to provide an oxidation-resistant heat insulating film and a method for forming the same.
[0014]
[Means for Solving the Problems]
The present invention relates to an oxidation resistant heat insulating film characterized in that a partially stabilized zirconia layer is formed on a NiCrAlY layer formed on a base material with a MoSi 2 —NiCrAlY layer interposed therebetween.
[0015]
In the above means, the content ratio of MoSi 2 in the MoSi 2 —NiCrAlY layer may be 40 to 90%, and the content ratio of NiCrAlY may be 10 to 60%.
[0016]
In the present invention, a NiCrAlY layer is formed on a substrate surface by subjecting NiCrAlY to low pressure plasma spraying, and a MoSi 2 —NiCrAlY layer is formed on the NiCrAlY layer by subjecting a mixture of MoSi 2 and NiCrAlY to low pressure plasma spraying. The present invention relates to a method for forming an oxidation-resistant heat-insulating film, which comprises forming a partially stabilized zirconia layer on the MoSi 2 —NiCrAlY layer by plasma spraying ZrO 2 in the atmosphere.
[0017]
In the above means, the mixing ratio of MoSi 2 forming the MoSi 2 —NiCrAlY layer may be 40 to 90%, and the mixing ratio of NiCrAlY may be 10 to 60%.
[0018]
According to the present invention, since the partially stabilized zirconia layer is formed on the NiCrAlY layer formed on the substrate so as to sandwich the MoSi 2 —NiCrAlY layer as an intermediate layer, the outermost partially stabilized zirconia layer is formed. Even if an oxidizing gas enters from the outside through fine cracks, the invasion of this oxidizing gas is stopped by the MoSi 2 —NiCrAlY layer, oxidation of the inner NiCrAlY layer, and the progress of fatigue cracks from the NiCrAlY layer to the substrate Therefore, the heat insulation effect by the partially stabilized zirconia layer is stably maintained, and thus thermal fatigue of the substrate is prevented and the life is extended.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of the invention will be described with reference to the drawings.
[0020]
In order to form an oxidation-resistant heat-insulating film, it is effective to prevent the oxidizing gas entering from the fine cracks in the partially stabilized zirconia layer (PSZ) from reaching the NiCrAlY layer.
[0021]
Therefore, various studies have been made on metals having an action capable of preventing the intrusion of the oxidizing gas as described above. MoSi 2 , WSi 2 , NbSi 2 , TaSi 2, etc. are known as refractory metal silicides. Among these metal silicides, molybdenum silicide MoSi 2 has a high melting point of 2303 K and is very excellent. Since it exhibits high-temperature oxidation resistance, it is regarded as a promising metal material for ultra-high temperatures.
[0022]
Therefore, it was considered that the layer using the molybdenum silicide MoSi 2 was formed as an intermediate layer between the NiCrAlY layer and the partially stabilized zirconia layer.
[0023]
In order to form a heat insulating film on the surface of the base material, as shown in FIG. 2, first, NiCrAlY is reduced in pressure on the base material 1 by using a plasma irradiation device 6 in a vacuumed vacuum container 5. By spraying (VPS), the NiCrAlY layer 2 is formed with a thickness of about 100 μm.
[0024]
Next, as shown in FIG. 3, a mixture of molybdenum silicide MoSi 2 and NiCrAlY is subjected to low pressure plasma spraying (VPS) on the NiCrAlY layer 2 formed as described above in the low-vacuum vessel 5 to be about 100 μm. A MoSi 2 —NiCrAlY layer 7 having a thickness of 5 mm is formed. At this time, for example, in the example of FIG. 1, the case where the mixing ratio of molybdenum silicide MoSi 2 is 70% and the mixing ratio of NiCrAlY is 30% is illustrated, but the mixing ratio of molybdenum silicide MoSi 2 is about 40 to 90%. The mixing ratio of NiCrAlY can be adjusted by changing in the range of about 10 to 60%.
[0025]
The MoSi 2 —NiCrAlY layer 7 may be sprayed so that the mixing ratio of molybdenum silicide MoSi 2 and NiCrAlY is uniform over the entire thickness, and the ratio of molybdenum silicide MoSi 2 is the thickness of the film. Thermal spraying may be performed with an inclination ratio so as to change in the vertical direction.
[0026]
Subsequently, as shown in FIG. 4, zirconia ZrO 2 is plasma sprayed (APS) in the atmosphere on the MoSi 2 —NiCrAlY layer 7 formed as described above, thereby partially stabilizing zirconia with a thickness of about 200 μm. Layer 3 (PSZ) is formed.
[0027]
According to the above method, as shown in FIG. 1, the heat insulation of the three-layer structure in which the partially stabilized zirconia layer 3 is formed on the NiCrAlY layer 2 formed on the substrate 1 with the MoSi 2 —NiCrAlY layer 7 interposed therebetween. A film can be formed.
[0028]
The operation of the above embodiment will be described below.
[0029]
In forming the oxidation resistant heat insulating film of the present invention, first, as shown in FIG. 2, NiCrAlY layer 2 is formed on substrate 1 by subjecting NiCrAlY to low-pressure plasma spraying.
[0030]
Next, a mixture prepared so that the mixing ratio of molybdenum silicide MoSi 2 is about 40 to 90% and the mixing ratio of NiCrAlY is about 10 to 60% is formed on the NiCrAlY layer 2 as shown in FIG. The MoSi 2 —NiCrAlY layer 7 is formed by thermal spraying.
[0031]
Subsequently, as shown in FIG. 4, the partially stabilized zirconia layer 3 is formed on the MoSi 2 —NiCrAlY layer 7 by plasma spraying zirconia ZrO 2 in the atmosphere.
[0032]
According to the above, as shown in FIG. 1, the partially stabilized zirconia layer 3 is integrally formed on the NiCrAlY layer 2 formed on the base material 1 with the MoSi 2 —NiCrAlY layer 7 sandwiched as an intermediate layer. A heat insulating film having a layer structure is obtained.
[0033]
When an intermediate layer by MoSi 2 -NiCrAlY layer 7 as described above, MoSi 2 -NiCrAlY layer 7 of molybdenum silicide MoSi 2 of, to natural healing filled by SiO 2 in crack high temperatures that occur during the thermal spray coating behavior Therefore, the oxidation resistance function is greatly improved by the MoSi 2 —NiCrAlY layer 7.
[0034]
That is, even if an oxidizing gas enters from the outside through the fine cracks 4 of the outermost partially stabilized zirconia layer 3, the MoSi 2 —NiCrAlY layer 7 prevents the oxidizing gas from entering, and the inner NiCrAlY layer 2 Is prevented from being oxidized, and further, fatigue cracks are prevented from progressing from the NiCrAlY layer 2 to the substrate 1.
[0035]
Accordingly, the heat insulation effect by the partially stabilized zirconia layer is stably maintained, and thus thermal fatigue of the base material is prevented and the life is extended.
[0036]
It should be noted that the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the scope of the present invention.
[0037]
【The invention's effect】
According to the present invention, since the partially stabilized zirconia layer is formed on the NiCrAlY layer formed on the substrate so as to sandwich the MoSi 2 —NiCrAlY layer as an intermediate layer, the outermost partially stabilized zirconia layer is formed. Even if an oxidizing gas enters from the outside through fine cracks, the invasion of this oxidizing gas is stopped by the MoSi 2 —NiCrAlY layer, oxidation of the inner NiCrAlY layer, and the progress of fatigue cracks from the NiCrAlY layer to the substrate Therefore, the heat insulation effect by the partially stabilized zirconia layer can be stably maintained, so that the excellent effect of preventing the thermal fatigue of the base material and extending the life can be obtained.
[Brief description of the drawings]
FIG. 1 is a schematic side view showing an example of an oxidation-resistant heat insulating film of the present invention.
FIG. 2 is a schematic side view showing a state in which a NiCrAlY layer is formed on a substrate by low-pressure plasma spraying in the method for forming an oxidation-resistant heat insulating film of the present invention.
FIG. 3 is a schematic side view showing a state in which a MoSi 2 —NiCrAlY layer is formed on a NiCrAlY layer by low-pressure plasma spraying in the method for forming an oxidation resistant thermal insulation film of the present invention.
FIG. 4 is a schematic side view showing a state in which a partially stabilized zirconia layer is formed on the MoSi 2 —NiCrAlY layer by atmospheric plasma spraying in the method for forming an oxidation resistant thermal insulation film of the present invention.
FIG. 5 is a schematic side view showing an example of a conventional oxidation-resistant heat insulating film.
[Explanation of symbols]
1 Substrate 2 NiCrAlY layer 3 Partially stabilized zirconia layer (PSZ)
7 MoSi 2 —NiCrAlY layer (intermediate layer)

Claims (4)

基材に形成されたＮｉＣｒＡｌＹ層上に、ＭｏＳｉ2−ＮｉＣｒＡｌＹ層を挟んで部分安定化ジルコニア層が形成されていることを特徴とする耐酸化性断熱皮膜。A partially stabilized zirconia layer is formed on a NiCrAlY layer formed on a base material with a MoSi 2 —NiCrAlY layer interposed therebetween. ＭｏＳｉ2−ＮｉＣｒＡｌＹ層におけるＭｏＳｉ2の含有割合が４０〜９０％、ＮｉＣｒＡｌＹの含有割合が１０〜６０％であることを特徴とする請求項１記載の耐酸化性断熱皮膜。 2. The oxidation-resistant heat-insulating coating according to claim 1, wherein the MoSi 2 —NiCrAlY layer has a MoSi 2 content of 40 to 90% and a NiCrAlY content of 10 to 60%. 基材表面に、ＮｉＣｒＡｌＹを減圧プラズマ溶射することによりＮｉＣｒＡｌＹ層を形成し、ＮｉＣｒＡｌＹ層上に、ＭｏＳｉ2とＮｉＣｒＡｌＹとの混合物を減圧プラズマ溶射することによりＭｏＳｉ2−ＮｉＣｒＡｌＹ層を形成し、該ＭｏＳｉ2−ＮｉＣｒＡｌＹ層上に、ＺｒＯ2を大気中プラズマ溶射して部分安定化ジルコニア層を形成することを特徴とする耐酸化性断熱皮膜の形成方法。The substrate surface to form a NiCrAlY layer by vacuum plasma spraying the NiCrAlY, on the NiCrAlY layer, forming a MoSi 2 -NiCrAlY layer by low pressure plasma spraying a mixture of MoSi 2 and NiCrAlY, the MoSi 2 A method for forming an oxidation-resistant heat-insulating film, wherein a partially stabilized zirconia layer is formed on a NiCrAlY layer by plasma spraying ZrO 2 in the air. ＭｏＳｉ2−ＮｉＣｒＡｌＹ層を形成するＭｏＳｉ2の混合割合が４０〜９０％、ＮｉＣｒＡｌＹの混合割合が１０〜６０％であることを特徴とする請求項３記載の耐酸化性断熱皮膜の形成方法。MoSi 2 mixing ratio of MoSi 2 to form a -NiCrAlY layer 40 to 90%, the method of forming the oxidation-resistant thermal barrier coating according to claim 3, wherein the mixing ratio of NiCrAlY is 10 60%.
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CN1948218B (en) * 2006-10-19 2010-05-12 宁夏东方钽业股份有限公司 High temperature anti oxidation material and high temperature antioxidation coating layer prepared from same
CN114015992B (en) * 2021-11-01 2022-05-20 重庆嘉陵特种装备有限公司 High-temperature oxidation resistant heat-insulating coating suitable for titanium alloy surface and preparation method thereof
CN114686797A (en) 2022-04-08 2022-07-01 长沙理工大学 Multilayer self-healing ceramic coating and preparation method thereof

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CN1518816B (en) * 2001-06-22 2010-04-28 欧姆龙株式会社 Safety network system and safety slave

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