JP5500676B2 - Heat-resistant alloy film forming method and composite powder used therefor - Google Patents
Heat-resistant alloy film forming method and composite powder used therefor Download PDFInfo
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Description
本発明は、耐熱部材の製造，補修のために、金属基体の表面上に耐熱合金皮膜を形成する方法と、それに用いる複合粉末に関する。 The present invention relates to a method for forming a heat-resistant alloy film on the surface of a metal substrate for manufacturing and repairing heat-resistant members, and a composite powder used therefor.
高温の燃焼ガスに曝されるガスタービンの耐熱部材（動翼，静翼，燃焼器等）には、主に高温強度に優れたニッケル基やコバルト基の各種耐熱合金が材料として用いられている。さらに、これら耐熱部材の表面には、高温での耐酸化性，耐食性を付与する目的から、ＭＣｒＡｌＸ合金（Ｍはニッケル，コバルト，鉄の何れか、及びその組合せ。ＸはＭ，Ｃｒ，Ａｌ以外の元素）がコーティングとして用いられている。中でも、ニッケル，コバルトのいずれか、または、両方を含むＭＣｒＡｌＸ合金が多用されている。このＭＣｒＡｌＸ合金のコーティング製造方法としては、主に減圧プラズマ溶射法（ＬＰＰＳ），大気プラズマ溶射法（ＡＰＳ），高速フレーム溶射法（ＨＶＯＦ）が用いられている。 Various heat-resistant alloys such as nickel-base and cobalt-base that are excellent in high-temperature strength are mainly used for heat-resistant members (moving blades, stationary blades, combustors, etc.) of gas turbines exposed to high-temperature combustion gas. . Further, for the purpose of imparting oxidation resistance and corrosion resistance at high temperatures to the surfaces of these heat-resistant members, MCrAlX alloy (M is any of nickel, cobalt, iron and a combination thereof. X is other than M, Cr, Al) Elements) are used as coatings. Among these, MCrAlX alloys containing either nickel or cobalt or both are frequently used. As the MCrAlX alloy coating manufacturing method, a low pressure plasma spraying method (LPPS), an atmospheric plasma spraying method (APS), and a high-speed flame spraying method (HVOF) are mainly used.
これら溶射法では、プラズマジェット（ＬＰＰＳ，ＡＰＳ），燃焼ガス（ＨＶＯＦ）といった非常に高温の熱源に粉末材料を投入して加熱し、溶融、または半溶融状態にして基材に吹き付け、堆積させることでコーティングを形成する。このため、基材の溶融や過熱を避けるために、熱源である溶射ガンと基材の距離をある程度離す必要があり、粉末の付着効率が低いという課題がある。 In these thermal spraying methods, a powder material is put into a very high-temperature heat source such as plasma jet (LPPS, APS) or combustion gas (HVOF), heated, melted or semi-molten, sprayed onto the substrate, and deposited. To form a coating. For this reason, in order to avoid melting and overheating of the base material, it is necessary to increase the distance between the thermal spray gun, which is a heat source, and the base material to some extent, and there is a problem that the adhesion efficiency of the powder is low.
一方、これらガスタービンの耐熱部材は、運転中において、高温高圧の燃焼ガスへの曝露と、高い熱応力や遠心応力が作用するため、運転時間の経過に伴い劣化・損傷が避けられない。従って、これらの耐熱部材は点検と補修を繰り返しながら使用される。この中で、亀裂，摩耗，酸化腐食減肉等の補修には、母材と同系の合金を肉盛溶接する方法が用いられている。 On the other hand, since the heat-resistant members of these gas turbines are exposed to high-temperature and high-pressure combustion gas and are subjected to high thermal stress and centrifugal stress during operation, deterioration and damage are inevitable with the passage of operation time. Therefore, these heat resistant members are used while repeating inspection and repair. Among them, a method of overlay welding an alloy similar to the base material is used for repairing cracks, wear, oxidation corrosion thinning, and the like.
しかし、ガスタービンの耐熱部材に用いられるニッケル基，コバルト基の耐熱合金は難溶接性であり、溶接肉盛補修では、溶接入熱の影響による、溶接金属や母材熱影響部の高温割れ，部材の熱変形等が問題となりやすい。このため、ティグ溶接法，プラズマ粉体溶接法，レーザー溶接法等の比較的低入熱の溶接方法が用いられるが、より低入熱で高信頼，低コストの肉盛補修技術の開発が望まれている。 However, nickel-base and cobalt-base heat-resistant alloys used for heat-resistant parts of gas turbines are difficult to weld, and in weld overlay repair, the weld metal and the base metal heat-affected zone are hot cracked due to the influence of welding heat input, Thermal deformation of the member tends to be a problem. For this reason, relatively low heat input welding methods such as TIG welding, plasma powder welding, and laser welding are used. However, development of overlay repair technology with lower heat input, high reliability, and low cost is desired. It is rare.
このように、ガスタービンの耐熱部材を製造，補修する際にはニッケル基やコバルト基の合金を、溶射や溶接といった高温熱源を利用して堆積させる方法が多く用いられているが、いずれも入熱の大きいことが問題となっている。これを改善する方法として、コールドスプレー法を用いてＭＣｒＡｌＸ合金をコーティングする方法が提案されている（特許文献１参照）。 As described above, when manufacturing and repairing heat-resistant members for gas turbines, nickel-based and cobalt-based alloys are often deposited using a high-temperature heat source such as thermal spraying or welding. High heat is a problem. As a method for improving this, a method of coating an MCrAlX alloy using a cold spray method has been proposed (see Patent Document 1).
コールドスプレー法は、合金粒子の融点より低い温度に粒子温度を保つことが可能なガス流温度を有する超音速ガス流を用い、粒子を超音速に加速して基材に衝突させ付着させる方法である。このため、基材への入熱が溶射法に比べて非常に低く、基材との距離を溶射法に比べ大幅に短縮することが可能で、一般に粉末の付着効率が高い。 The cold spray method uses a supersonic gas flow having a gas flow temperature that can maintain the particle temperature at a temperature lower than the melting point of the alloy particles, and accelerates the particles to a supersonic speed to cause them to collide with and adhere to the substrate. is there. For this reason, the heat input to the base material is very low as compared with the thermal spraying method, and the distance from the base material can be greatly shortened as compared with the thermal spraying method, and generally, the adhesion efficiency of the powder is high.
例えば、非特許文献１には、純銅，純ニッケルでは約８０％という非常に高い付着効率が得られることが示されている。一方で、非特許文献１には、純ニッケルで約８０％の付着効率が得られる成膜条件で、ＭＣｒＡｌＸ合金やニッケル基合金では約２０％の付着効率しか得られず、気孔率も増加して膜質も低下することが示されている。
For example, Non-Patent
コールドスプレー法の成膜原理については未解明の部分も多く、現時点でこの原因を特定することは困難であるが、コールドスプレー法では粒子を高速で基材に衝突させた際の塑性流動が成膜に寄与するため、塑性流動を生じやすい純ニッケルに対し、ニッケル基合金では合金化による固溶強化や析出強化が図られることで塑性流動が生じ難くなり、成膜に必要な粒子速度が上昇したと考えられる。 There are many unexplained parts about the film formation principle of the cold spray method, and it is difficult to determine the cause at this time. However, the cold spray method causes plastic flow when particles collide with the substrate at high speed. In contrast to pure nickel, which tends to cause plastic flow because it contributes to the film, the nickel-base alloy makes it difficult for plastic flow to occur due to solid solution strengthening and precipitation strengthening by alloying, and the particle velocity required for film formation increases. It is thought that.
従って、ニッケル基やコバルト基合金を効率良くコールドスプレーするためには、より高い粒子速度が必要となり、コールドスプレーの作動ガスとして最も高速が得られるヘリウムガスを用いることが必要となる。 Accordingly, in order to efficiently cold spray nickel-based and cobalt-based alloys, higher particle velocities are required, and it is necessary to use helium gas that provides the highest speed as the working gas for cold spray.
しかし、ヘリウムガスは高価であり、大量の作動ガスを消費するコールドスプレー法ではコストが非常に高くなってしまうという課題がある。 However, helium gas is expensive, and the cold spray method that consumes a large amount of working gas has a problem that the cost becomes very high.
本発明の目的は、ニッケル、およびコバルト基の耐熱合金をコールドスプレーによって高効率，低コストで成膜でき、低入熱，低コストの耐熱部材の製造及び補修が可能な耐熱合金皮膜の形成方法と、それに用いる複合粉末を提供することにある。 An object of the present invention is to form a heat-resistant alloy film that can form a heat-resistant nickel- and cobalt-based heat-resistant alloy with high efficiency and low cost by cold spraying, and can manufacture and repair a heat-resistant member with low heat input and low cost. And providing a composite powder used therefor.
本発明の耐熱合金皮膜の形成方法は、ニッケル、または、コバルト基の耐熱合金皮膜を金属基体の表面上に形成する方法であって、（ａ）前記耐熱合金を構成する元素の内から選択された組成を有し、かつ、その総和が前記耐熱合金の組成となるよう選択された、複数種類の金属粉末を選択する工程と、（ｂ）前記複数種類の金属粉末粒子が溶融しない温度に保たれた超音速ガス流を形成し、この超音速ガス流中に前記複数種類の金属粉末を投入し、粉末粒子を基体に超音速で衝突させて、金属基体上に、前記複数種類の金属粉末からなる混合皮膜を形成する工程と、（ｃ）前記複数種類の金属粉末からなる混合皮膜を形成した金属基体に熱処理を施し、混合皮膜を均質化，合金化して、前記耐熱合金の皮膜を得ると共に、金属基体と耐熱合金の皮膜との間で拡散を生じさせて、両者の密着を強固にする工程と、を有することを特徴とする。 The method for forming a heat-resistant alloy film of the present invention is a method of forming a nickel- or cobalt-based heat-resistant alloy film on the surface of a metal substrate, and is selected from (a) elements constituting the heat-resistant alloy. And a step of selecting a plurality of types of metal powders, the total of which is selected so as to be the composition of the heat-resistant alloy, and (b) a temperature at which the plurality of types of metal powder particles are not melted. A supersonic gas flow is formed, and the plurality of types of metal powders are introduced into the supersonic gas flow, and the powder particles are caused to collide with the substrate at a supersonic speed. (C) heat-treating the metal substrate on which the mixed film made of the plurality of types of metal powders is formed, and homogenizing and alloying the mixed film to obtain the heat-resistant alloy film Together with the metal substrate And cause diffusion between the coating, and having a step to strengthen both the adhesion of the.
本発明の耐熱合金皮膜の形成方法によれば、目的の耐熱合金を構成する元素の内から選択された組成を有する、複数の金属粉末を選択する工程で、コールドスプレーにおける成膜の容易な組成の粉末と、その他の合金組成を有する粉末に分離することが可能となる。 According to the method for forming a heat-resistant alloy film of the present invention, a composition that allows easy film formation in cold spray in a step of selecting a plurality of metal powders having a composition selected from elements constituting the target heat-resistant alloy. And powders having other alloy compositions can be separated.
そして、これらの粉末を同時にコールドスプレーで成膜することで、成膜が容易な粉末が結合材として機能し、成膜が困難な粉末粒子の堆積を支援する。このため、従来の均一な耐熱合金粉末を単独でコールドスプレーにて成膜する場合に比べて成膜が容易となり、高価なヘリウムガスを使用せずに、安価な窒素ガスや空気でも耐熱合金の成膜が可能となるという利点がある。コールドスプレーのままの皮膜は、複数種類の粉末粒子の混合皮膜であるが、これを熱処理によって、均質化，合金化することで、実質的に目的の耐熱合金の皮膜を得ることができる。 Then, these powders are simultaneously formed by cold spray, whereby the powder that is easy to form functions as a binder, and assists the deposition of powder particles that are difficult to form. For this reason, film formation becomes easier compared to the case where conventional uniform heat-resistant alloy powder is formed by cold spray alone, and it is possible to use heat-resistant alloy with inexpensive nitrogen gas or air without using expensive helium gas. There is an advantage that a film can be formed. The film as a cold spray is a mixed film of a plurality of types of powder particles. By homogenizing and alloying this by heat treatment, a film of the intended heat resistant alloy can be obtained substantially.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の耐熱合金皮膜の形成方法は、目的の耐熱合金を構成する元素の内から選択された組成を有し、かつ、その総和が目的の耐熱合金の組成となるよう選択された、複数種類の金属粉末を選択する工程と、前記複数種類の金属粉末粒子が溶融しない温度に保たれた超音速ガス流を形成し、このガス流中に前記複数種類の金属粉末を投入し、粉末粒子を基体に超音速で衝突させて、金属基体上に、前記複数種類の金属粉末からなる混合皮膜を形成する、いわゆるコールドスプレーの工程と、前記複数種類の金属粉末からなる混合皮膜を形成した金属基体に熱処理を施し、混合皮膜を均質化，合金化して、実質的に目的の耐熱合金皮膜を得ると共に、金属基体と耐熱合金皮膜との間で拡散を生じさせて、両者の密着を強固にする、熱処理の工程とを有することを最も主要な特徴とする。 The heat-resistant alloy film forming method of the present invention has a composition selected from among the elements constituting the target heat-resistant alloy, and a plurality of types selected so that the sum thereof becomes the composition of the target heat-resistant alloy Forming a supersonic gas flow maintained at a temperature at which the plurality of types of metal powder particles do not melt, and injecting the plurality of types of metal powder into the gas flow, A so-called cold spray process in which a mixed film made of the plurality of types of metal powder is formed on the metal substrate by colliding with the substrate at supersonic speed, and a metal substrate in which the mixed film made of the plurality of types of metal powder is formed. Heat treatment to homogenize and alloy the mixed film to obtain the desired heat-resistant alloy film, and also cause diffusion between the metal substrate and the heat-resistant alloy film to strengthen the adhesion between the two. , Heat treatment process The most important feature to have.
すなわち、本発明は、ニッケル、または、コバルト基の耐熱合金皮膜を金属基体の表面上に形成する方法であって、
（ａ）前記耐熱合金を構成する元素の内から選択された組成を有し、かつ、その総和が前記耐熱合金の組成となるよう選択された、複数種類の金属粉末を選択する工程と、
（ｂ）前記複数種類の金属粉末粒子が溶融しない温度に保たれた超音速ガス流を形成し、この超音速ガス流中に前記複数種類の金属粉末を投入し、粉末粒子を基体に超音速で衝突させて、金属基体上に、前記複数種類の金属粉末からなる混合皮膜を形成する工程と、
（ｃ）前記複数種類の金属粉末からなる混合皮膜を形成した金属基体に熱処理を施し、混合皮膜を均質化，合金化して、前記耐熱合金皮膜を得ると共に、金属基体と耐熱合金の皮膜との間で拡散を生じさせて、両者の密着を強固にする工程と、を有する。
That is, the present invention is a method of forming a nickel or cobalt-based heat-resistant alloy film on the surface of a metal substrate,
(A) selecting a plurality of types of metal powders having a composition selected from the elements constituting the heat-resistant alloy, and the sum of which is selected to be the composition of the heat-resistant alloy;
(B) forming a supersonic gas flow maintained at a temperature at which the plurality of types of metal powder particles do not melt, introducing the plurality of types of metal powders into the supersonic gas flow, and superposing the powder particles on a substrate; And forming a mixed film made of the plurality of types of metal powders on the metal substrate,
(C) A heat treatment is performed on the metal substrate on which the mixed film composed of the plurality of types of metal powders is formed, and the mixed film is homogenized and alloyed to obtain the heat-resistant alloy film, and between the metal substrate and the heat-resistant alloy film A step of causing diffusion between the two and strengthening the adhesion between them.
本発明に用いる、複数種類の金属粉末の少なくとも一つは、純金属のニッケルまたはコバルトであることが好ましい。純金属では、合金に比べ強化機構が作用しないため、比較的コールドスプレーによる成膜が容易な場合が多いためである。ニッケル基またはコバルト基の耐熱合金の場合は、母相であるニッケルまたはコバルトが５０％以上を占めることが多く、純金属として純ニッケル、または、純コバルトを選択することが好ましい。これら母相以外の元素を純金属として選択した場合、その含有率が小さいため、ほとんどの合金では堆積物の組成を目的の合金組成となるように、粉末の比率を調整することが困難になる。 At least one of the plurality of types of metal powders used in the present invention is preferably pure metal nickel or cobalt. This is because a pure metal does not act as a strengthening mechanism compared to an alloy, and film formation by cold spray is relatively easy in many cases. In the case of a nickel-based or cobalt-based heat-resistant alloy, nickel or cobalt as a parent phase often occupies 50% or more, and it is preferable to select pure nickel or pure cobalt as a pure metal. When an element other than the parent phase is selected as a pure metal, the content ratio is small, so it is difficult to adjust the powder ratio so that the composition of the deposit becomes the target alloy composition in most alloys. .
また、これら金属，合金粉末の平均粒径は３０μｍ以下であることが好ましい。平均粒径が３０μｍを超えると、コールドスプレーの際に超音速ガス流中における粉末の粒子速度が十分に得られず、成膜が困難になるためである。 The average particle diameter of these metal and alloy powders is preferably 30 μm or less. When the average particle size exceeds 30 μm, the particle velocity of the powder in the supersonic gas flow cannot be sufficiently obtained during the cold spray, and film formation becomes difficult.
本発明で、コールドスプレーの際に用いる超音速ガス流を形成するガスには、窒素または空気を用いることができる。ただし、目的の合金組成や成膜条件によっては、窒素ガスまたは空気では十分な粒子速度が得られない場合が生じる場合がある。このような場合は、窒素または空気にヘリウムを必要量加えた混合ガスを用いることも可能である。 In the present invention, nitrogen or air can be used as the gas forming the supersonic gas flow used in the cold spray. However, depending on the target alloy composition and film formation conditions, there may be a case where a sufficient particle velocity cannot be obtained with nitrogen gas or air. In such a case, it is also possible to use a mixed gas obtained by adding a necessary amount of helium to nitrogen or air.
なお、超音速ガス流を形成するガス温度は３００℃〜６００℃の範囲が好ましい。この範囲より低い温度では、ガスの膨張によるガス流速度の上昇が不十分となり、成膜に必要な粒子速度が得られない。また、この範囲より高い温度では、粒子温度が上昇することで成膜は容易になるが、６００℃を超える高温を実現するためには非常に強力なヒーターを準備するか、ガスの圧力を下げてガス流量を下げなければならず、効率的には不利となる。また、粉末粒子の酸化による、皮膜内への酸化物の混入も生じやすくなる。 In addition, the gas temperature which forms a supersonic gas flow has the preferable range of 300 to 600 degreeC. If the temperature is lower than this range, the increase in gas flow rate due to gas expansion is insufficient, and the particle velocity required for film formation cannot be obtained. If the temperature is higher than this range, film formation is facilitated by increasing the particle temperature, but in order to achieve a high temperature exceeding 600 ° C, a very powerful heater is prepared or the gas pressure is lowered. Therefore, the gas flow rate must be reduced, which is disadvantageous in terms of efficiency. In addition, oxides are easily mixed into the film due to oxidation of the powder particles.
さらに本発明では、コールドスプレーの際に超音速ガス流中に投入する金属粉末粒子の比率を、金属基体に超音速で衝突させて形成される混合皮膜の組成が所定の合金組成となるように選択することを特徴とする。この比率は、目的とする合金組成、選択した金属粉末組成のみならず、粉末の粒径分布、成膜条件等に依存するため予備成膜試験を行い決定することが好ましい。なお、超音速ガス流中に投入する複数の金属粉末は、混合皮膜中に偏在を生じないように十分に混合して投入することが好ましい。さらに、この目的には、予め、被覆，造粒等の方法によって、複合化された粉末粒子を用いることが最も好ましい。 Furthermore, in the present invention, the ratio of the metal powder particles introduced into the supersonic gas flow during the cold spray is set so that the composition of the mixed film formed by colliding with the metal substrate at the supersonic speed becomes a predetermined alloy composition. It is characterized by selecting. This ratio depends on not only the desired alloy composition and the selected metal powder composition, but also the particle size distribution of the powder, film formation conditions, etc., and therefore it is preferable to determine this ratio by conducting a preliminary film formation test. In addition, it is preferable that the plurality of metal powders introduced into the supersonic gas flow are sufficiently mixed and introduced so as not to cause uneven distribution in the mixed film. Furthermore, for this purpose, it is most preferable to use powder particles that have been combined in advance by a method such as coating or granulation.
図１に本発明の被覆による耐熱合金複合粉末の断面模式図を示す。これは、合金粉末粒子１の表面に、純金属被覆層２が形成された複合粉末で、純金属被覆層２は、めっき，蒸着等の適当な方法によって形成することが可能である。
FIG. 1 shows a schematic cross-sectional view of a heat resistant alloy composite powder according to the coating of the present invention. This is a composite powder in which the pure
図２に本発明の造粒による耐熱合金複合粉末の断面模式図を示す。これは、合金粉末粒子１の表面に、純金属粒子２を付着させた形態の複合粉末である。複合化の形態については、ここに示した形態以外の複合粉末を用いることも可能である。
FIG. 2 shows a schematic cross-sectional view of the heat-resistant alloy composite powder obtained by granulation according to the present invention. This is a composite powder in which
図３に本発明の方法に従って形成された、コールドスプレー法による耐熱合金皮膜の熱処理前の断面模式図を示す。耐熱合金基体１１上に、コールドスプレー法による皮膜１２が形成されている。熱処理前の段階において、皮膜１２は純金属粉末粒子１３と合金粉末粒子１４の混合皮膜であり、比較的、コールドスプレーにおける付着性が良い純金属粉末粒子１３がマトリックス（母相）となり、このマトリックス中に合金粉末粒子１４が分散した組織を呈する。単独でコールドスプレーした場合には付着性が悪い合金粉末粒子１４も、本発明の方法においては、純金属粉末粒子１３によるマトリックスが結合材として機能するため付着性が向上する。このようにして得られた皮膜１２は、この状態では未だ、純金属１３と合金１４の混合皮膜であるので、これを熱処理によって均質化，合金化する。
FIG. 3 shows a schematic cross-sectional view of the heat-resistant alloy film formed according to the method of the present invention before the heat treatment by the cold spray method. A
この結果、図４に示すように、基体１１上に目的の耐熱合金組成を有する皮膜１５を形成することができる。この熱処理は、純金属１３と合金１４間の固相拡散が十分に進行し、均質化，合金化が達成される条件で行う。望ましくは、真空中、１０００℃以上の温度で１ｈ以上、熱処理を行うことが好ましい。また、基体耐熱合金の溶体化熱処理，時効熱処理と合わせて行うことも可能である。
As a result, as shown in FIG. 4, a
以下、本発明の実施例を説明する。 Examples of the present invention will be described below.
原料粉末として、平均粒径１５μｍの、純ニッケル粉末と合金粉末（４２％Ｃｒ−２２％Ｃｏ−９％Ｔｉ−９％Ａｌ−７％Ｗ−４.５％Ｍｏ−４.５％Ｔａ−２.３％Ｎｂ−０.３％Ｃ−０.１％Ｚｒ−０.０３％Ｂ、重量％）を準備した。これらの粉末を、重量比で純ニッケル粉末７に対し、合金粉末３の割合で配合し、Ｖミキサーを用いて十分混合した。この混合粉末を、コールドスプレー装置を用い、ニッケル耐熱合金ＩＮ７３８（１６％Ｃｒ−８.５％Ｃｏ−３.４％Ｔｉ−３.４％Ａｌ−２.６％Ｗ−１.７％Ｍｏ−１.７％Ｔａ−０.９％Ｎｂ−０.１％Ｃ−０.０５％Ｚｒ−０.０１％Ｂ−残部Ｎｉ、重量％）製の基体上に成膜した。成膜条件は、作動ガスに窒素ガスを用い、ガス圧力が２ＭＰａ、ガス温度が５
００℃、粉末供給量が１０ｇ／min、成膜距離が２０mmを用いた。堆積層の厚さが約１mm
まで成膜を実施した。
As raw material powder, pure nickel powder and alloy powder (42% Cr-22% Co-9% Ti-9% Al-7% W-4.5% Mo-4.5% Ta-2 with an average particle size of 15 μm) 0.3% Nb-0.3% C-0.1% Zr-0.03% B, wt%). These powders were blended in a ratio by weight of the alloy powder 3 with respect to the pure nickel powder 7 in a weight ratio and sufficiently mixed using a V mixer. This mixed powder was mixed with a nickel heat resistant alloy IN738 (16% Cr-8.5% Co-3.4% Ti-3.4% Al-2.6% W-1.7% Mo- The film was formed on a substrate made of 1.7% Ta-0.9% Nb-0.1% C-0.05% Zr-0.01% B-balance Ni, wt%). The film formation conditions were as follows: nitrogen gas was used as the working gas, the gas pressure was 2 MPa, and the gas temperature was 5
A temperature of 00 ° C., a powder supply amount of 10 g / min, and a film formation distance of 20 mm were used. The thickness of the deposited layer is about 1mm
Film formation was carried out.
コールドスプレーにて堆積層を形成した後、試験片を真空中で、１１２０℃×２ｈの熱処理を実施した。熱処理後、堆積層は強固に基体と密着し、緻密な堆積層が得られた。堆積層の成分を分析したところ、ほぼニッケル基耐熱合金ＩＮ７３８と同等の組成が得られた。また、大気中１０００℃にて１０００ｈの酸化試験を実施したところ、基体とほぼ同等の耐酸化性を示した。このように、作動ガスに窒素ガスを用いたコールドスプレー法で、実質的にニッケル基耐熱合金ＩＮ７３８に相当する堆積層が得られた。 After forming the deposited layer by cold spraying, the test piece was heat-treated at 1120 ° C. for 2 hours in vacuum. After the heat treatment, the deposited layer was firmly adhered to the substrate, and a dense deposited layer was obtained. When the components of the deposited layer were analyzed, a composition almost equivalent to that of the nickel-base heat-resistant alloy IN738 was obtained. Further, when an oxidation test for 1000 hours was performed at 1000 ° C. in the atmosphere, the oxidation resistance was almost the same as that of the substrate. As described above, a deposited layer substantially corresponding to the nickel-based heat-resistant alloy IN738 was obtained by the cold spray method using nitrogen gas as the working gas.
原料粉末として、平均粒径１５μｍの、純コバルト粉末と合金粉末（５３％Ｎｉ−３５％Ｃｒ−１３％Ａｌ−０.８％Ｙ、重量％）を準備した。これらの粉末を、重量比で純コバルト粉末４に対し、合金粉末６の割合で配合し、Ｖミキサーを用いて十分混合した。この混合粉末を、コールドスプレー装置を用い、ニッケル耐熱合金ＩＮ７３８（１６％Ｃｒ−８.５％Ｃｏ−３.４％Ｔｉ−３.４％Ａｌ−２.６％Ｗ−１.７％Ｍｏ−１.７％Ｔａ−０.９％Ｎｂ−０.１％Ｃ−０.０５％Ｚｒ−０.０１％Ｂ−残部Ｎｉ、重量％）製の基体上に成膜した。成膜条件は、作動ガスに窒素ガスを用い、ガス圧力が２ＭＰａ、ガス温度が３
００℃、粉末供給量が１０ｇ／min、成膜距離が２０mmを用いた。堆積層の厚さが０.３mm
まで成膜を実施した。
Pure cobalt powder and alloy powder (53% Ni-35% Cr-13% Al-0.8% Y, wt%) having an average particle size of 15 μm were prepared as raw material powders. These powders were blended at a weight ratio of the alloy powder 6 with respect to the
A temperature of 00 ° C., a powder supply amount of 10 g / min, and a film formation distance of 20 mm were used. The thickness of the deposited layer is 0.3mm
Film formation was carried out.
コールドスプレーにて堆積層を形成した後、試験片を真空中で、１１２０℃×２ｈの熱処理を実施した。熱処理後、堆積層は強固に基体と密着し、緻密な堆積層が得られた。また、堆積層の成分を分析したところ、ほぼＣｏＮｉＣｒＡｌＹ合金（３２％Ｎｉ−２１％Ｃｒ−８％Ａｌ−０.５％Ｙ―残部Ｃｏ、重量％）の組成が得られた。また、大気中１０００℃にて１０００ｈの酸化試験を実施したところ、ＨＶＯＦ溶射法にて成膜した試験片とほぼ同等の耐酸化性を示した。このように、作動ガスに窒素ガスを用いたコールドスプレー法で、実質的にＣｏＮｉＣｒＡｌＹ合金に相当する堆積層が得られた。 After forming the deposited layer by cold spraying, the test piece was heat-treated at 1120 ° C. for 2 hours in vacuum. After the heat treatment, the deposited layer was firmly adhered to the substrate, and a dense deposited layer was obtained. Further, when the components of the deposited layer were analyzed, a composition of a CoNiCrAlY alloy (32% Ni-21% Cr-8% Al-0.5% Y—balance Co, wt%) was obtained. Further, when an oxidation test was performed for 1000 hours at 1000 ° C. in the atmosphere, the oxidation resistance was almost equal to that of a test piece formed by HVOF spraying. Thus, a deposited layer substantially corresponding to the CoNiCrAlY alloy was obtained by the cold spray method using nitrogen gas as the working gas.
原料粉末として、平均粒径１５μｍの合金粉末（４２％Ｃｒ−２２％Ｃｏ−９％Ｔｉ−９％Ａｌ−７％Ｗ−４.５％Ｍｏ−４.５％Ｔａ−２.３％Ｎｂ−０.３％Ｃ−０.１％Ｚｒ−０.０３％Ｂ、重量％）に、ニッケル被覆層を厚さ約５μｍ形成した複合粉末を準備し
た。コールドスプレー装置を用いて、この複合粉末をニッケル耐熱合金ＩＮ７３８（１６％Ｃｒ−８.５％Ｃｏ−３.４％Ｔｉ−３.４％Ａｌ−２.６％Ｗ−１.７％Ｍｏ−１.７％Ｔａ−０.９％Ｎｂ−０.１％Ｃ−０.０５％Ｚｒ−０.０１％Ｂ−残部Ｎｉ、重量％）製の基
体上に成膜した。成膜条件は、作動ガスに窒素ガスを用い、ガス圧力が２.５ＭＰａ、ガス温度が４００℃、粉末供給量が１０ｇ／min、成膜距離が２０mmを用いた。皮膜の厚さが約１mmまで成膜を実施した。
Alloy powder having an average particle size of 15 μm (42% Cr-22% Co-9% Ti-9% Al-7% W-4.5% Mo-4.5% Ta-2.3% Nb- 0.3% C-0.1% Zr-0.03% B, wt%) was prepared as a composite powder having a nickel coating layer with a thickness of about 5 μm. Using a cold spray apparatus, this composite powder was mixed with nickel heat-resistant alloy IN738 (16% Cr-8.5% Co-3.4% Ti-3.4% Al-2.6% W-1.7% Mo- The film was formed on a substrate made of 1.7% Ta-0.9% Nb-0.1% C-0.05% Zr-0.01% B-balance Ni, wt%). The film formation conditions were as follows. Nitrogen gas was used as the working gas, the gas pressure was 2.5 MPa, the gas temperature was 400 ° C., the powder supply amount was 10 g / min, and the film formation distance was 20 mm. Film formation was carried out until the film thickness was about 1 mm.
コールドスプレーにて皮膜を形成した後、試験片を真空中で、１１２０℃×２ｈの熱処理を実施した。熱処理後、皮膜は強固に基体と密着し、緻密な皮膜が得られた。皮膜の成分を分析したところ、ほぼニッケル基耐熱合金ＩＮ７３８と同等の組成が得られた。また、大気中１０００℃にて１０００ｈの酸化試験を実施したところ、基体とほぼ同等の耐酸化性を示した。このように、作動ガスに窒素ガスを用いたコールドスプレー法で、実質的にニッケル基耐熱合金ＩＮ７３８に相当する皮膜が得られた。 After forming a film by cold spraying, the test piece was heat-treated at 1120 ° C. for 2 hours in vacuum. After the heat treatment, the film firmly adhered to the substrate, and a dense film was obtained. When the components of the film were analyzed, a composition almost equivalent to that of the nickel-base heat-resistant alloy IN738 was obtained. Further, when an oxidation test for 1000 hours was performed at 1000 ° C. in the atmosphere, the oxidation resistance was almost the same as that of the substrate. Thus, a film substantially corresponding to the nickel-based heat-resistant alloy IN738 was obtained by the cold spray method using nitrogen gas as the working gas.
原料粉末として、平均粒径１５μｍの合金粉末（５３％Ｎｉ−３５％Ｃｒ−１３％Ａｌ−０.８％Ｙ、重量％）の表面に平均粒径３μｍのコバルト粉末を、重量比でコバルト粉末４に対し、合金粉末６の割合で、造粒して付着させた複合粉末を準備した。この複合粉末を、コールドスプレー装置を用い、ニッケル耐熱合金ＩＮ７３８（１６％Ｃｒ−８.５％Ｃｏ−３.４％Ｔｉ−３.４％Ａｌ−２.６％Ｗ−１.７％Ｍｏ−１.７％Ｔａ−０.９％Ｎｂ−０.１％Ｃ−０.０５％Ｚｒ−０.０１％Ｂ−残部Ｎｉ、重量％）製の基体上に成膜し
た。成膜条件は、作動ガスに窒素ガスを用い、ガス圧力が３ＭＰａ、ガス温度が４００℃、粉末供給量が１０ｇ／min、成膜距離が２０mmを用いた。皮膜の厚さが０.３mmまで成膜
を実施した。
As a raw material powder, an alloy powder (53% Ni-35% Cr-13% Al-0.8% Y, wt%) having an average particle diameter of 15 μm is coated with a cobalt powder having an average particle diameter of 3 μm on the surface and cobalt powder in a weight ratio. 4, a composite powder was prepared by granulating and adhering at a ratio of alloy powder 6. Using a cold spray apparatus, this composite powder was heated to a nickel heat resistant alloy IN738 (16% Cr-8.5% Co-3.4% Ti-3.4% Al-2.6% W-1.7% Mo- The film was formed on a substrate made of 1.7% Ta-0.9% Nb-0.1% C-0.05% Zr-0.01% B-balance Ni, wt%). As the film forming conditions, nitrogen gas was used as the working gas, the gas pressure was 3 MPa, the gas temperature was 400 ° C., the powder supply amount was 10 g / min, and the film forming distance was 20 mm. Film formation was performed until the film thickness was 0.3 mm.
コールドスプレーにて皮膜を形成した後、試験片を真空中で、１１２０℃×２ｈの熱処理を実施した。熱処理後、皮膜は強固に基体と密着し、緻密な皮膜が得られた。また、皮膜の成分を分析したところ、ほぼＣｏＮｉＣｒＡｌＹ合金（３２％Ｎｉ−２１％Ｃｒ−８％Ａｌ−０.５％Ｙ―残部Ｃｏ、重量％）の組成が得られた。また、大気中１０００℃にて１０００ｈの酸化試験を実施したところ、ＨＶＯＦ溶射法にて成膜した試験片とほぼ同等の耐酸化性を示した。このように、作動ガスに窒素ガスを用いたコールドスプレー法で、実質的にＣｏＮｉＣｒＡｌＹ合金に相当する皮膜が得られた。 After forming a film by cold spraying, the test piece was heat-treated at 1120 ° C. for 2 hours in vacuum. After the heat treatment, the film firmly adhered to the substrate, and a dense film was obtained. Further, when the components of the film were analyzed, a composition of a CoNiCrAlY alloy (32% Ni-21% Cr-8% Al-0.5% Y—balance Co, wt%) was obtained. Further, when an oxidation test was performed for 1000 hours at 1000 ° C. in the atmosphere, the oxidation resistance was almost equal to that of a test piece formed by HVOF spraying. Thus, a film substantially corresponding to the CoNiCrAlY alloy was obtained by the cold spray method using nitrogen gas as the working gas.
本発明は、ガスタービン耐熱部材へのＭＣｒＡｌＸ合金のコーティング、あるいは、ニッケル基，コバルト基耐熱合金の肉盛補修に応用可能である。また、これら合金系に限らず、熱処理による合金化が可能な合金系にも適用可能で、ガスタービン以外にも、蒸気タービン，ボイラ，自動車エンジン等の耐熱部材に利用可能である。 The present invention can be applied to MCrAlX alloy coating on a gas turbine heat-resistant member or build-up repair of nickel-based and cobalt-based heat resistant alloys. Further, the present invention can be applied not only to these alloy systems but also to alloy systems that can be alloyed by heat treatment, and can be used for heat-resistant members such as steam turbines, boilers, and automobile engines in addition to gas turbines.
また、本発明は、コールドスプレー法を用いるため、施工時の入熱が従来の溶射法，溶接法に比べ極めて小さく、作業性，信頼性に優れる。また、粉末の付着効率が高いため、経済性にも優れる。 In addition, since the present invention uses a cold spray method, heat input during construction is extremely small compared to conventional thermal spraying and welding methods, and is excellent in workability and reliability. Moreover, since the adhesion efficiency of powder is high, it is excellent also in economical efficiency.
１ 合金粒子
２ 純金属被覆層
３ 純金属粒子
１１ 基体
１２ 混合皮膜
１３ 純金属
１４ 合金
１５ 耐熱合金皮膜
DESCRIPTION OF
Claims (11)
（ａ）前記耐熱合金を構成する元素の内から選択された組成を有し、かつ、その総和が前記耐熱合金の組成となるよう選択された、複数種類の金属粉末を選択する工程と、
（ｂ）前記複数種類の金属粉末が溶融しない温度に保たれた超音速ガス流を形成し、この超音速ガス流中に前記複数種類の金属粉末を投入し、前記複数種類の金属粉末を基体に超音速で衝突させて、金属基体上に、前記複数種類の金属粉末からなる混合皮膜を形成する工程と、
（ｃ）前記複数種類の金属粉末からなる混合皮膜を形成した金属基体に熱処理を施し、混合皮膜を均質化，合金化して、前記耐熱合金の皮膜を得ると共に、金属基体と耐熱合金の皮膜との間で拡散を生じさせて、両者の密着を強固にする工程と、
を有し、
前記複数種類の金属粉末は、金属単体と合金を含み、
前記金属単体はニッケル、または、コバルトであることを特徴とする耐熱合金皮膜の形成方法。 A method of forming a nickel- or cobalt-based heat-resistant alloy film on a surface of a metal substrate,
(A) selecting a plurality of types of metal powders having a composition selected from the elements constituting the heat-resistant alloy, and the sum of which is selected to be the composition of the heat-resistant alloy;
(B) forming a supersonic gas flow maintained at a temperature at which the plurality of types of metal powders are not melted, charging the plurality of types of metal powders into the supersonic gas flow, and applying the plurality of types of metal powders to a substrate; Forming a mixed film composed of the plurality of types of metal powders on the metal substrate,
(C) A heat treatment is performed on the metal substrate on which the mixed film composed of the plurality of types of metal powders is formed, and the mixed film is homogenized and alloyed to obtain the heat-resistant alloy film, and the metal substrate and the heat-resistant alloy film Producing a diffusion between the two, strengthening the adhesion between the two,
I have a,
The plurality of types of metal powders include a simple metal and an alloy,
The method for forming a heat-resistant alloy film, wherein the metal simple substance is nickel or cobalt .
少なくともニッケル，コバルト，クロム，アルミニウムのいずれかを含む合金の表面に、ニッケルまたはコバルトの粒子が付着した、またはニッケルまたはコバルトの被覆層を形成したことを特徴とする耐熱合金皮膜形成用金属粉末。 Forming a supersonic gas flow maintained at a temperature at which a plurality of types of metal powder including a simple metal and an alloy are not melted, and injecting the plurality of types of metal powder into the supersonic gas flow, the plurality of types of metal powder In a metal powder for forming a heat-resistant alloy film used in a film forming method in which a substrate is made to collide with a substrate at supersonic speed and deposited on the substrate surface,
A metal powder for forming a heat-resistant alloy film, characterized in that nickel or cobalt particles adhere to the surface of an alloy containing at least one of nickel, cobalt, chromium, and aluminum , or a coating layer of nickel or cobalt is formed .
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