JPH0874506A - Anti-corrosion coating member and manufacture thereof - Google Patents
Anti-corrosion coating member and manufacture thereofInfo
- Publication number
- JPH0874506A JPH0874506A JP21618094A JP21618094A JPH0874506A JP H0874506 A JPH0874506 A JP H0874506A JP 21618094 A JP21618094 A JP 21618094A JP 21618094 A JP21618094 A JP 21618094A JP H0874506 A JPH0874506 A JP H0874506A
- Authority
- JP
- Japan
- Prior art keywords
- corrosion
- dispersed
- ceramic
- layer
- resistant coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は高温の酸化または腐食性
雰囲気中で使用される耐蝕コーティング部材およびその
製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a corrosion resistant coating member used in a high temperature oxidizing or corrosive atmosphere and a method for producing the same.
【０００２】[0002]
【従来の技術】発電用ガスタービンにおいては、運転ガ
ス温度の高温化が発電効率の向上のために有効である。
この高温化にともない、動翼、靜翼、燃焼機などの高温
部品にあっては、部品材料の温度を下げるための冷却特
性の向上、材料の耐熱性の向上の二つの観点から耐久性
の向上が検討されている。2. Description of the Related Art In a gas turbine for power generation, raising the operating gas temperature is effective for improving power generation efficiency.
With this rise in temperature, high-temperature parts such as rotor blades, blades, and combustors have improved durability from the two perspectives of improving the cooling characteristics to reduce the temperature of the parts materials and improving the heat resistance of the materials. Improvements are being considered.
【０００３】冷却性向上のについては、冷却用空気流量
の増大が有効である。ところが、単に冷却空気の流量を
増大するだけでは、燃焼ガスの温度低下につながり、結
果的に発電効率が低下する。すなわち、冷却空気流量の
増大は発電効率の向上策とは相反することとなる。そこ
で、冷却用空気流量を増大させずに冷却性能を向上させ
る方法として、フィルム冷却やインピンジ冷却に代表さ
れる材料／冷却ガスの接触面積を増大させる冷却方式が
試みられている。ところが、これ等の冷却方式は基本的
には部品の構造が複雑となる欠点がある。一方、高温化
のために部材の耐熱性の向上のための材料開発が進めら
れている。高温部品材料として、Ｎｉ、ＣｏまたはＦｅ
基の超合金が開発されているが、高温強度と耐酸化性、
耐蝕性の両立が困難であり、高温強度が基材、耐蝕、耐
酸化性をコーティング被膜に負担させる機能分担が現状
の考え方として確立され、超合金表面には耐蝕、耐酸化
性に優れたＭＣｒＡｌＹ（Ｍ：Ｎｉ、ＣｏまたはＦｅ基
の何れか一つの元素または複数の元素の組合せよりな
る）被膜を形成する方法が実施されている。To improve the cooling performance, it is effective to increase the flow rate of cooling air. However, simply increasing the flow rate of the cooling air leads to a decrease in the temperature of the combustion gas, resulting in a decrease in power generation efficiency. That is, an increase in the cooling air flow rate is contrary to a measure for improving power generation efficiency. Therefore, as a method of improving the cooling performance without increasing the flow rate of the cooling air, a cooling method of increasing the contact area of the material / cooling gas represented by film cooling or impingement cooling has been attempted. However, these cooling methods basically have a drawback that the structure of parts is complicated. On the other hand, the development of materials for improving the heat resistance of members due to higher temperatures is underway. Ni, Co or Fe as high temperature component materials
Although base superalloys have been developed, high temperature strength and oxidation resistance,
MCrAlY is excellent in corrosion resistance and oxidation resistance on the surface of superalloys, because it is difficult to achieve both corrosion resistance at the same time. A method of forming a coating (M: Ni, Co, Fe, any one element or combination of elements) is practiced.
【０００４】しかしながら、ガスタービンの運転ガス温
度の高温化に伴い、ＭＣｒＡｌＹ合金にはさらに高温で
の耐蝕性、耐酸化性が望まれている。一般に、ＭＣｒＡ
ｌＹ合金の耐蝕性、耐酸化性を向上させるためには、Ｍ
ＣｒＡｌＹ合金中のＣｒ、Ａｌ濃度を高めたり、Ａｌ2
Ｏ3 、ＴｈＯ2 、Ｙ2 Ｏ3 などのセラミックスを分散さ
せる（特開昭６３−９５８２８号）ことが有効である
が、この場合被膜の靭性がとぼしくなり、クラックを生
じやすくなる欠点があった。However, as the operating gas temperature of the gas turbine becomes higher, the MCrAlY alloy is desired to have corrosion resistance and oxidation resistance at higher temperatures. Generally, MCrA
In order to improve the corrosion resistance and oxidation resistance of the 1Y alloy, M
Cr in CrAlY alloy and increasing the Al concentration, Al 2
It is effective to disperse ceramics such as O 3 , ThO 2 and Y 2 O 3 (JP-A-63-95828), but in this case, the toughness of the coating becomes poor and cracks are likely to occur. .
【０００５】[0005]
【発明が解決しようとする課題】以上のように、ガスタ
ービンのような高温や酸化、腐食性雰囲気下で使用され
る部材においては、耐蝕コーティングを施すことは不可
欠である。しかしながら、運転ガス温度の高温下にとも
ない、より優れた耐酸化性、耐蝕性が耐蝕コーティング
被膜に求められる。セラミック粒子の分散は、コーティ
ング被膜の耐酸化性、耐蝕性にが向上すること（特開昭
６３−９５８２８号）は、公知であるが、被膜自体の靭
性の低下により、発生した亀裂のコーティング部材の疲
労強度、クリープ強度の低下に大きな影響をおよぼすこ
とにより、逆に耐酸化性、耐蝕製に好ましくない影響を
およぼす。As described above, it is indispensable to apply a corrosion resistant coating to a member such as a gas turbine which is used under a high temperature, an oxidizing or corrosive atmosphere. However, as the operating gas temperature becomes higher, the corrosion-resistant coating film is required to have better oxidation resistance and corrosion resistance. It is known that the dispersion of the ceramic particles improves the oxidation resistance and corrosion resistance of the coating film (Japanese Patent Laid-Open No. 63-95828), but the coating member has cracks caused by the decrease in the toughness of the coating film itself. It exerts a great influence on the deterioration of fatigue strength and creep strength of the steel, but adversely affects the oxidation resistance and corrosion resistance.
【０００６】本発明は上記の事情に基づきなされたもの
で、セラミック粒子を分散させて耐酸化性、耐蝕性を向
上させ、しかもセラミック粒子の分散による耐酸化性、
耐蝕性被膜の強度の低下を防止した耐蝕性コーティング
部材およびその製造法を提供する。The present invention has been made in view of the above circumstances, in which ceramic particles are dispersed to improve oxidation resistance and corrosion resistance, and further, the oxidation resistance due to the dispersion of ceramic particles,
(EN) Provided are a corrosion-resistant coating member in which the strength of a corrosion-resistant coating is prevented from decreasing, and a method for producing the same.
【０００７】[0007]
【課題を解決するための手段】本発明の耐蝕性コーティ
ング部材は、Ｎｉ、ＣｏまたはＦｅ基の高温強度に優れ
た超合金の基材上に、耐蝕、耐酸化性に優れたＮｉ、Ｃ
ｏまたはＦｅ基の金属層を設け、さらに耐蝕、耐酸化性
に優れたＮｉ、ＣｏまたはＦｅ基の金属マトリックス中
にセラミック質の分散した層を設けてなることを特徴と
する。The corrosion-resistant coating member of the present invention comprises a Ni, Co or Fe-based superalloy base material having excellent high-temperature strength and excellent corrosion resistance and oxidation resistance.
It is characterized in that an o or Fe-based metal layer is provided, and further a ceramic-dispersed layer is provided in a Ni, Co or Fe-based metal matrix having excellent corrosion resistance and oxidation resistance.
【０００８】[0008]
【作用】上記構成の本発明の耐蝕性コーティング部材に
おいては、耐蝕コーティング部材によれば、Ｎｉ、Ｃ
ｏ、Ｆｅの少なくとも一つの中に、Ｃｒ、Ａｌ、Ｙを含
むＭＣｒＡｌＹにセラミック粒子が微細分散した表面層
をも用いることにより、耐酸化性、耐蝕性が向上され
る。In the corrosion-resistant coating member of the present invention having the above structure, the corrosion-resistant coating member is made of Ni, C
Oxidation resistance and corrosion resistance are improved by using a surface layer in which ceramic particles are finely dispersed in MCrAlY containing Cr, Al, and Y in at least one of o and Fe.
【０００９】[0009]
【実施例】図１は、本発明の耐蝕コーティング部材の一
実施例の断面図である。この図において、Ｎｉ、Ｃｏ、
またはＦｅをベースとした高温強度に優れた超合金から
なる金属基材１には、Ｍｉ、ＣｏまたはＦｅ基のの靭性
に優れた耐蝕合金からなる中間層２が設けられている。
さらに、Ｎｉ、Ｃｏ、またはＦｅ基の超合金マトリック
ス４中にセラミック５を微細に分散させた表面層３が設
けてある。前記のセラミック分散質としては、Ａｌ2 Ｏ
3 、Ｙ2 Ｏ3 、ＴｈＯ2 など、硬質でしかも化学的に安
定な酸化物系セラミックが含まれ、それ等は一種以上用
いられている。また、セラミック分散質の大きさは、
１．０μｍ以下であり、その表面層の強化と耐酸化性、
耐蝕性を満たすに十分に小さいものとしてある。1 is a sectional view of an embodiment of the corrosion-resistant coating member of the present invention. In this figure, Ni, Co,
Alternatively, an intermediate layer 2 made of a corrosion-resistant alloy based on Mi, Co or Fe and having excellent toughness is provided on a metal base 1 made of Fe and based on a superalloy having excellent high-temperature strength.
Furthermore, a surface layer 3 in which a ceramic 5 is finely dispersed in a Ni-, Co-, or Fe-based superalloy matrix 4 is provided. As the ceramic dispersoid, Al 2 O
Hard and chemically stable oxide-based ceramics such as 3 , Y 2 O 3 and ThO 2 are included, and one or more of them are used. The size of the ceramic dispersoid is
1.0 μm or less, strengthening the surface layer and oxidation resistance,
It is small enough to satisfy the corrosion resistance.
【００１０】図２は、上記の耐蝕コーティング部材の製
造法の一例の工程図である。第１の工程６は溶射用の原
料粉末の作成工程を示す。Ｎｉ、Ｃｏ、Ｆｅの少なくと
も一種の中に、Ｃｒ、Ａｌ、Ｙを含む金属質のＭＣｒＡ
ｌＹ粉末とセラミック質のＹ2 Ｏ3 、Ａｌ2 Ｏ3 、Ｔｈ
Ｏ2 粉末を、アトライクや高速ボールミルよりメカニカ
ルアロイングすることにより、機械エネルギによる粉末
の混合複合化を行い、ＭＣｒＡｌＹ粉末中にセラミック
の粉末が分散した粉末を作成する。FIG. 2 is a process chart of an example of a method for manufacturing the above-mentioned corrosion resistant coating member. The first step 6 is a step of preparing a raw material powder for thermal spraying. Metallic MCrA containing Cr, Al and Y in at least one of Ni, Co and Fe
1Y powder and ceramic Y 2 O 3 , Al 2 O 3 , Th
By mechanically alloying the O 2 powder with an attrike or a high-speed ball mill, the powder is mixed and composited by mechanical energy to prepare a powder in which the ceramic powder is dispersed in the MCrAlY powder.
【００１１】第２の工程７から第６の工程１１までは、
Ｎｉ、Ｃｏ、Ｆｅの少なくとも一種の中に、Ｃｒ、Ａ
ｌ、Ｙを含む高温強度に優れた超合金基材上に、上記の
ＭＣｒＡｌＹ粉末中にセラミック粒子が分散された粉末
を形成させる工程である。まず、第２の工程７では、Ｎ
ｉ、Ｃｏ、Ｆｅの少なくとも一種の中には、Ｃｒ、Ａ
ｌ、Ｙを含む高温強度に優れた超合金基材の洗浄脱脂
と、その後のＡｌ2 Ｏ3 グリッドを用いたブラスィング
の前処理を行う。From the second step 7 to the sixth step 11,
At least one of Ni, Co and Fe contains Cr, A
This is a step of forming a powder in which ceramic particles are dispersed in the above-mentioned MCrAlY powder on a superalloy base material containing l, Y and excellent in high temperature strength. First, in the second step 7, N
Among at least one of i, Co and Fe, Cr, A
Cleaning and degreasing of a superalloy substrate containing l, Y and having excellent high-temperature strength, and subsequent pretreatment of blasting using an Al 2 O 3 grid.
【００１２】第３の工程８では、前記前処理を施した超
合金基材をチャンバー中にセットする。チャンバーの真
空とガス置換とを繰り返し、その酸素濃度を１０-2ＭＰ
ａ以下とし、雰囲気圧力を１０-4P ａとする。In the third step 8, the pretreated superalloy substrate is set in a chamber. The chamber vacuum and gas replacement are repeated to adjust the oxygen concentration to 10 -2 MP.
The pressure is not more than a and the atmospheric pressure is 10 −4 Pa .
【００１３】第４の工程９は、超合金基材表面のクリー
ニング処理を行う工程である。超合金基材を負極とした
トランスファードアークにり、超合金基材表面の酸化物
を分解する。The fourth step 9 is a step of cleaning the surface of the superalloy substrate. Oxides on the surface of the superalloy substrate are decomposed by a transferred arc using the superalloy substrate as a negative electrode.
【００１４】第５の工程１０は、超合金基材の予熱工程
である。プラズマジェットにより、超合金基材を８００
℃まで加熱する。The fifth step 10 is a preheating step for the superalloy substrate. 800 super alloy base material by plasma jet
Heat to ℃.
【００１５】第６の工程１１は、超合金基材の表面に靭
性に優れたＭＣｒＡｌＹ合金被膜、例えばＣｏＭＣｒＡ
ｌＹＴなどを減圧プラズマ溶射により形成する。The sixth step 11 is the MCrAlY alloy coating having excellent toughness such as CoMCrA on the surface of the superalloy substrate.
1YT or the like is formed by low pressure plasma spraying.
【００１６】第７の工程１２は、メカニカルアロイング
により作成したＭＣｒＡｌＹ粉末中にセラミック粒子が
分散した粉末の溶射工程である。この粉末を減圧プラズ
マ溶射法により、超合金基材表面にぶっつけて凝固させ
て被膜を形成する。The seventh step 12 is a thermal spraying step of powder in which ceramic particles are dispersed in MCrAlY powder prepared by mechanical alloying. This powder is applied to the surface of the superalloy substrate by the low pressure plasma spraying method and solidified to form a coating film.
【００１７】最後に第８の工程１３は、Ａｒなどの不活
性ガス雰囲気中でコーティング部材を、１１００℃、４
ｈの熱処理を施す。これにより、減圧プラズマ溶射法に
より超合金基材が受けたダメージを回復させるととも
に、超合金基材との溶射被膜間の元素拡散による密着性
の向上と、溶射被膜の焼結による緻密化などの特性改善
を図ることができる。Finally, in the eighth step 13, the coating member is placed at 1100 ° C. for 4 hours in an atmosphere of an inert gas such as Ar.
Heat treatment of h is performed. As a result, the damage received by the superalloy base material by the low pressure plasma spraying method is recovered, the adhesion between the superalloy base material and the sprayed coating is improved by the diffusion of elements, and the sprayed coating is densified by sintering. It is possible to improve the characteristics.
【００１８】上記実施例の作用について図３〜図６を参
照して説明する。The operation of the above embodiment will be described with reference to FIGS.
【００１９】まず、Ｎｉ、Ｃｏ、Ｆｅの少なくとも一種
の中に、Ｃｒ、Ａｌ、Ｙを含む金属質のＭＣｒＡｌＹ粉
末とＹ2 Ｏ3 、Ａｌ2 Ｏ3 、ＴｈＯ2 などのセラミック
粉末を、アトライタによりメカニカルアロイングするこ
とにより、ＭＣｒＡｌＹ粉末中にセラミック粉末が超微
細分散したメカニカルアロイ粉末が作成できる。図３
は、横軸に機械エネルギＥとして回転数Ｒ×時間ｔを、
縦軸にはＹ2 Ｏ3 粉末粒径をとって示す。横軸の機械エ
ネルギが大きくなるほど、Ｙ2 Ｏ3 Ｙ2 Ｏ3 粒径ｒが小
さくできることが明らかである。初期粒径ｒが数十μｍ
のＹ2 Ｏ3 粉末も、回転数５００ｒｐｍで１０ｈのメカ
ニカルアロイ処理を行えば、Ｙ2 Ｏ3 粉末粒径ｒを１μ
ｍ未満とすることができる。また、メカニカルアロイ粉
末の特徴としては、一つのＭＣｒＡｌＹマトリックスの
中に微細なＹ2 Ｏ3 粉末が分散した形で存在する。Firstly, Ni, Co, in at least one of Fe, Cr, Al, MCrAlY powder metallic including Y and Y 2 O 3, Al 2 O 3, a ceramic powder such as ThO 2, the attritor By mechanical alloying, a mechanical alloy powder in which ceramic powder is ultrafinely dispersed in MCrAlY powder can be prepared. FIG.
Is the rotational energy R × time t as mechanical energy E on the horizontal axis,
The vertical axis indicates the Y 2 O 3 powder particle size. It is clear that the larger the mechanical energy on the horizontal axis, the smaller the Y 2 O 3 Y 2 O 3 particle size r. Initial particle size r is several tens of μm
The Y 2 O 3 powder of No. 1 also has a Y 2 O 3 powder particle size r of 1 μ if it is mechanically alloyed for 10 hours at a rotation speed of 500 rpm.
It can be less than m. A characteristic of the mechanical alloy powder is that a fine Y 2 O 3 powder is dispersed in one MCrAlY matrix.
【００２０】図４に大気中の温度が１０００℃、１０ｈ
の雰囲気注に各種コーティング材を保持した場合の酸化
増量比を示す（Ｙ2 Ｏ3 分散、ＣｏＮｉＣｒＡｌＹ耐蝕
コーティングの場合を１とする）。ＣｏＮｉＣｒＡｌＹ
単体の耐蝕コーティングを施した部材と比較して、Ｙ2
Ｏ3 粒子を分散したＣｏＮｉＣｒＡｌＹ耐蝕コーティン
グ部材の酸化増量比は著しく少ないことが分かる。これ
はＹ2 Ｏ3 の分散が耐酸化性の向上に大きく寄与してい
ることを示す。その理由は、ＣｏＮｉＣｒＡｌＹ表面に
形成され耐酸化性を保持するＡｌ2 Ｏ3 被膜の保持に有
効であると考えられるが、詳細については今後の検討課
題である。本発明における表面層にＹ2Ｏ3 分散ＣｏＮ
ｉＣｒＡｌＹ、中間層にＣｏＮｉＣｒＡｌＹを用いた耐
蝕コーティング部材は、Ｙ2 Ｏ3 粒子分散ＣｏＮｉＣｒ
ＡｌＹ単体のコーティング部材と耐酸化性については、
顕著な差は認められない。FIG. 4 shows that the temperature in the atmosphere is 1000 ° C. for 10 hours.
Shows the oxidation weight increase ratio when various coating materials are held in the atmosphere injection (Y 2 O 3 dispersion, CoNiCrAlY anticorrosion coating is 1). CoNiCrAlY
Compared to a single element with a corrosion resistant coating, Y 2
It can be seen that the oxidation weight increase ratio of the CoNiCrAlY anti-corrosion coating member in which O 3 particles are dispersed is extremely small. This indicates that the dispersion of Y 2 O 3 greatly contributes to the improvement of the oxidation resistance. The reason is considered to be effective for retaining the Al 2 O 3 coating formed on the surface of CoNiCrAlY and retaining the oxidation resistance, but the details are for further study. In the surface layer of the present invention, Y 2 O 3 -dispersed CoN is used.
The corrosion resistant coating member using iCrAlY and CoNiCrAlY for the intermediate layer is Y 2 O 3 particle dispersed CoNiCr.
For the coating material and oxidation resistance of AlY alone,
There is no noticeable difference.
【００２１】図５は、１０００℃、０．５ｈ大気中雰囲
気での熱サイクル試験における被試験体の酸化増量比
（等温酸化試験図４）におけるＹ2 Ｏ3 粒子分散（Ｃｏ
ＮｉＣｒＡｌＹ耐蝕コーティングの場合を１とする）を
示す。ＣｏＮｉＣｒＡｌＹ単体の耐蝕コーティング部材
の場合には、酸化試験中に生じた表面のＡｌ2 Ｏ3 被膜
が熱サイクル試験中に損傷を受け、酸化の加速をする傾
向がある。一方、Ｙ2 Ｏ3 粒子分散ＣｏＮｉＣｒＡｌＹ
についても、熱サイクル中に被膜に亀裂が生じそのため
等温酸化試験の場合には問題がないが、熱サイクル試験
の場合には急激な酸化増量が増える傾向を示した。一
方、本発明におけるＹ2 Ｏ3 分散とＣｏＮｉＣｒＡｌＹ
との２層より形成された退職コーティング部材において
は、表面層のＹ2 Ｏ3 分散ＣｏＮｉＣｒＡｌＹ層に明瞭
な亀裂等の損傷が認められず、熱サイクル試験の場合に
おいても等温酸化の場合に比して酸化増量の明瞭な差異
は認められず、酸化特性に優れたコーティングであると
言い得る。FIG. 5 shows the Y 2 O 3 particle dispersion (Co) in the oxidation weight gain ratio (isothermal oxidation test FIG. 4) of the test object in the thermal cycle test in the atmosphere of 1000 ° C. for 0.5 h.
The case of the NiCrAlY corrosion resistant coating is 1). In the case of a corrosion resistant coated member of CoNiCrAlY alone, the surface Al 2 O 3 coating formed during the oxidation test is damaged during the thermal cycle test, and the oxidation tends to be accelerated. On the other hand, Y 2 O 3 particle-dispersed CoNiCrAlY
Regarding, also, there was no problem in the isothermal oxidation test because cracks were formed in the coating film during the thermal cycle, but in the case of the thermal cycle test, there was a tendency that the rapid increase in the amount of oxidation increased. On the other hand, in the present invention, Y 2 O 3 dispersion and CoNiCrAlY
In the retired coating member formed by two layers, the Y 2 O 3 -dispersed CoNiCrAlY layer of the surface layer showed no obvious damage such as cracks, and even in the thermal cycle test, compared with the case of isothermal oxidation. Therefore, it can be said that the coating has excellent oxidative properties, since no clear difference in oxidative increase is observed.
【００２２】図６には、従来のＹ2 Ｏ3 分散ＣｏＮｉＣ
ｒＡｌＹ単層からなる耐蝕コーティングの場合と、本発
明であるＹ2 Ｏ3 分散ＣｏＮｉＣｒＡｌＹ／ＣｏＮｉＣ
ｒＡｌＹ２層からなる耐蝕コーティング部材の場合と
の、コーティング後の後処理時点での（図２）残留応力
の板厚方向分布（板表面に平行な方向の分布）について
の有限要素法による解析結果を示す。Ｙ2 Ｏ3 ＣｏＮｉ
ＣｒＡｌＹの熱膨張係数は調合金基材のＩＮ７３８ＬＣ
よりも大きいため、後処理の拡散熱処理を施すことで被
膜には図６に示すように引張残留応力が生じる。これ
は、熱サイクル試験中の冷却時点において常に生じる高
い引張残留応力により、被膜表面に亀裂が生じる原因の
一つと考えられる。一方、本発明におけるＹ2 Ｏ3 分散
ＣｏＮｉＣｒＡｌＹとＣｏＮｉＣｒＡｌＹとの２層コー
ティングでは、Ｙ2 Ｏ3 分散ＣｏＮｉＣｒＡｌＹの熱膨
張係数がＣｏＮｉＣｒＡｌＹよりも小さいため、残留応
力が低減される傾向にあることが分かる。FIG. 6 shows a conventional Y 2 O 3 -dispersed CoNiC.
In the case of a corrosion-resistant coating composed of a single rAlY layer, and in the present invention, Y 2 O 3 -dispersed CoNiCrAlY / CoNiC
The analysis results by the finite element method for the distribution of residual stress in the plate thickness direction (distribution in the direction parallel to the plate surface) at the time of post-treatment after coating (Fig. 2) in the case of a corrosion resistant coating member composed of two layers of rAlY Show. Y 2 O 3 CoNi
The thermal expansion coefficient of CrAlY is IN738LC, which is a toned alloy base material.
Therefore, the post-treatment diffusion heat treatment causes tensile residual stress in the film as shown in FIG. It is considered that this is one of the causes of cracking on the surface of the coating film due to the high tensile residual stress that always occurs at the time of cooling during the heat cycle test. On the other hand, in the two-layer coating of Y 2 O 3 -dispersed CoNiCrAlY and CoNiCrAlY according to the present invention, the residual stress tends to be reduced because the thermal expansion coefficient of Y 2 O 3 -dispersed CoNiCrAlY is smaller than that of CoNiCrAlY.
【００２３】また、比較的靭性の低いＹ2 Ｏ3 分散Ｃｏ
ＮｉＣｒＡｌＹ層に熱サイクル過程で亀裂が生じても、
本発明においては靭性に優れたＣｏＮｉＣｒＡｌＹ層が
あるために、亀裂がＹ2 Ｏ3 分散ＣｏＮｉＣｒＡｌＹ層
とＣｏＮｉＣｒＡｌＹ層との間で停止することにより、
亀裂の発生による耐酸化性や耐蝕性の低下は最小限に食
い止められる。Further, Y 2 O 3 -dispersed Co having a relatively low toughness is used.
Even if the NiCrAlY layer is cracked during the thermal cycle,
In the present invention, due to the CoNiCrAlY layer having excellent toughness, the cracks stop between the Y 2 O 3 -dispersed CoNiCrAlY layer and the CoNiCrAlY layer.
The deterioration of oxidation resistance and corrosion resistance due to the generation of cracks can be minimized.
【００２４】一方、コーティング被膜の残留応力や熱応
力の低減については、Ｙ2 Ｏ3 分散ＣｏＮｉＣｒＡｌＹ
層とＣｏＮｉＣｒＡｌＹ層との間を組織を連続的に変化
させることにより、さらに有効とんる。すなわち、熱膨
張係数の急激な変化をなくすことができるからである。On the other hand, for reducing the residual stress and thermal stress of the coating film, Y 2 O 3 -dispersed CoNiCrAlY is used.
Further improvement is achieved by continuously changing the structure between the layer and the CoNiCrAlY layer. That is, it is possible to eliminate a rapid change in the coefficient of thermal expansion.
【００２５】図７は、超合金基材表面に耐蝕、耐酸化性
に優れたＭＣｒＡｌＹ合金をコーティングし、ＭＣｒＡ
ｌＹ合金中のセラミック粒子を徐々に最小表面に向けて
増加させた耐蝕コーティング部材を示す。これは、プラ
ズマ溶射の過程において、溶射用の粉末としてセラミッ
ク含有量の少ない粉末から徐々に多い粉末に変えること
によって得られる。FIG. 7 shows a superalloy substrate surface coated with MCrAlY alloy having excellent corrosion resistance and oxidation resistance.
Figure 3 shows a corrosion resistant coated member with gradually increasing ceramic particles in the 1Y alloy towards a minimum surface. This is obtained in the course of plasma spraying by changing the powder for ceramic spraying from a powder with a low ceramic content to a powder with a progressively higher ceramic content.
【００２６】本発明の耐蝕コーティング部材によれば、
Ｎｉ、Ｃｏ、Ｆｅの少なくとも一つの中に、Ｃｒ、Ａ
ｌ、Ｙを含むＭＣｒＡｌＹにセラミック粒子が微細分散
した表面層をも用いることにより、耐酸化性、耐蝕性が
向上される。According to the corrosion resistant coating member of the present invention,
Cr, A in at least one of Ni, Co, Fe
By using a surface layer in which ceramic particles are finely dispersed in MCrAlY containing 1 and Y, oxidation resistance and corrosion resistance are improved.
【００２７】基材と表面層との中間層に、セラミック粒
子を分散しない靭性に優れた層を用いることで、熱サイ
クル性も含めて耐酸性、耐蝕性がさらに向上される。By using a layer having excellent toughness in which ceramic particles are not dispersed as an intermediate layer between the base material and the surface layer, acid resistance and corrosion resistance including thermal cycleability are further improved.
【００２８】基材と表面層との中間に設ける中間層に、
セラミック粒子を分散しない靭性に優れた層を用いるこ
とで、表面層の熱応力緩和がなされ、表面層屁の亀裂発
生を低減させ、亀裂発生に起因する強度ならびに耐酸化
性、耐蝕性を向上させることができる。In the intermediate layer provided between the substrate and the surface layer,
By using a layer with excellent toughness that does not disperse ceramic particles, the thermal stress of the surface layer is relieved, the occurrence of cracks in the surface layer is reduced, and the strength, oxidation resistance, and corrosion resistance due to the occurrence of cracks are improved. be able to.
【００２９】セラミックを分散した表面層からセラミッ
ク粒子を分散しない中間層を、セラミック粒子が助助に
減少するようにして耐蝕コーティング被膜を形成するこ
とにより、層間の界面の熱応力の低減がさらに顕著とな
り、対処コーティング部材の耐久性が向上される。By forming the anticorrosion coating film from the surface layer in which the ceramic particles are dispersed to the intermediate layer in which the ceramic particles are not dispersed so that the ceramic particles are reduced, the thermal stress at the interface between the layers is further remarkably reduced. Therefore, the durability of the countermeasure coating member is improved.
【００３０】[0030]
【発明の効果】上記から明らかなように、Ｎｉ、Ｃｏま
たはＦｅ基の高温強度に優れた超合金基材と、Ｎｉ、Ｃ
ｏまたはＦｅ基等の耐蝕合金の中に、セラミック粒子を
分散したコーティング被膜と、中間層としてＮｉ、Ｃ
ｏ、またはＦｅ基の耐蝕合金を用いることにより、ガス
タービン用高温部品のような高温酸化、腐食性雰囲気中
で用いる部品において耐久性に優れた耐蝕コーティング
部材とすることができる。また、ＮｉＣｏまたはＦｅ基
の耐蝕合金からセラミック粒子を分散させた耐蝕合金表
面層まで、セラミック粒子を徐々に増やすことにより、
耐久性が向上した耐蝕コーティング部材とすることがで
きる。As is apparent from the above, a Ni, Co or Fe-based superalloy base material excellent in high temperature strength, and Ni, C
A coating film in which ceramic particles are dispersed in a corrosion resistant alloy such as o or Fe base, and Ni, C as an intermediate layer
By using an o- or Fe-based corrosion-resistant alloy, it is possible to obtain a corrosion-resistant coated member having excellent durability in a component used in a high temperature oxidizing or corrosive atmosphere such as a high temperature component for a gas turbine. Further, by gradually increasing the ceramic particles from the NiCo or Fe-based corrosion resistant alloy to the corrosion resistant alloy surface layer in which the ceramic particles are dispersed,
A corrosion resistant coating member having improved durability can be obtained.
【図１】本発明の耐蝕コーティング部材の一実施例の断
面図。FIG. 1 is a sectional view of an embodiment of a corrosion-resistant coating member of the present invention.
【図２】上記の耐蝕コーティング部材の製造法の一例の
工程図。FIG. 2 is a process drawing of an example of a method for manufacturing the above corrosion-resistant coating member.
【図３】本発明のセラミック粒子分散コーティング用耐
蝕合金の製造条件を示す線図。FIG. 3 is a diagram showing the production conditions of the corrosion resistant alloy for ceramic particle dispersion coating of the present invention.
【図４】等温酸化試験を実施した時の各コーティング部
材評価試験結果を示す線図。FIG. 4 is a diagram showing the results of each coating member evaluation test when an isothermal oxidation test was performed.
【図５】熱サイクル試験を実施した場合の各コーティン
グ部材の評価試験結果を示す線図。FIG. 5 is a diagram showing an evaluation test result of each coating member when a heat cycle test is performed.
【図６】従来の一層コーティングと本発明の二層コーテ
ィングとを比較して示す線図。FIG. 6 is a diagram showing a conventional single layer coating and a double layer coating of the present invention in comparison.
【図７】本発明の他の実施例の断面図。FIG. 7 is a sectional view of another embodiment of the present invention.
１………超合金基材 ２………中間層 ３………表面耐蝕層 ４………耐蝕金属マトリックス ５………分散セラミック粒子 1 --- Superalloy substrate 2 --- Intermediate layer 3 --- Surface corrosion-resistant layer 4 --- Corrosion-resistant metal matrix 5 --- Dispersed ceramic particles
───────────────────────────────────────────────────── フロントページの続き (72)発明者 齋藤 正弘 神奈川県横浜市鶴見区末広町２の４ 株式 会社東芝京浜事業所内 (72)発明者 石渡 裕 神奈川県横浜市鶴見区末広町２の４ 株式 会社東芝京浜事業所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masahiro Saito, Inventor Masahiro Saito, 4 shares 2-4, Suehiro-cho, Tsurumi-ku, Yokohama-shi, Kanagawa (72) Inventor, Yutaka Ishiwata 4 shares, 2 Suehiro-cho, Tsurumi-ku, Yokohama, Kanagawa Company Toshiba Keihin Office
Claims (7)
れた超合金の基材上に、耐蝕、耐酸化性に優れたＮｉ、
ＣｏまたはＦｅ基の金属層を設け、さらに耐蝕、耐酸化
性に優れたＮｉ、ＣｏまたはＦｅ基の金属マトリックス
中にセラミック質の分散した層を設けてなることを特徴
とする二層からなる耐蝕コーティング部材。1. A Ni, Co or Fe-based superalloy substrate having excellent high-temperature strength, on which Ni, which has excellent corrosion resistance and oxidation resistance,
Corrosion resistance consisting of two layers, characterized in that a metal layer based on Co or Fe is provided, and further a layer in which a ceramic material is dispersed in a metal matrix based on Ni, Co or Fe which is excellent in corrosion resistance and oxidation resistance is provided. Coating material.
ＡｒまたはＨ2 の条件下で、減圧プラズマ溶射法により
被膜を形成したことを特徴とする請求項１記載の耐熱コ
ーティング部材。2. The heat resistant coating member according to claim 1, wherein a coating film is formed by a low pressure plasma spraying method under an atmosphere of Ar or H 2 under an atmosphere pressure of 200 Torr or less.
Ｙ2 Ｏ3 、ＴｈＯ2等硬質で化学的に安定な酸化物セラ
ミックを少なくとも一種用いたことを特徴とする請求項
１記載の耐蝕コーティング部材。3. The dispersed ceramic material is Al 2 O 3 ,
The corrosion-resistant coating member according to claim 1, wherein at least one hard and chemically stable oxide ceramic such as Y 2 O 3 or ThO 2 is used.
として、平均粒径が１．０μｍ以下の粒子を用いたこと
を特徴とする請求項１記載の耐蝕コーティング部材。4. The corrosion-resistant coating member according to claim 1, wherein particles having an average particle diameter of 1.0 μm or less are used as the dispersed ceramic material of the corrosion-resistant and oxidation-resistant coating.
はＦｅ基の被膜を形成する材料を、高エネルギボールミ
ルを用いて機械的に混合、複合化して作成したことを特
徴とする請求項１記載の耐蝕コーティング部材。5. The material according to claim 1, which is prepared by mechanically mixing and compounding a material for forming a Ni-, Co-, or Fe-based coating film having a ceramic material dispersed therein by using a high energy ball mill. Corrosion resistant coating material.
脹係数が、Ｎｉ、ＣｏまたはＦｅ基の金属層または超合
金基材よりも小さなことを特徴とする請求項１記載の耐
蝕コーティング部材。6. The corrosion-resistant coating member according to claim 1, wherein the coefficient of linear expansion of the outermost surface ceramic dispersion layer is smaller than that of the Ni-, Co- or Fe-based metal layer or the superalloy substrate.
れた超合金基材上に、耐蝕、耐酸化性に優れたＮｉ、Ｃ
ｏまたはＦｅ基の金属層を設け、さらに耐蝕性に優れた
Ｎｉ、ＣｏまたはＦｅ基の金属マトリックス中にセラミ
ック質が分散した層について、セラミック質の量比が徐
々に増加するように積層したことを特徴とする請求項１
記載の耐蝕コーティング部材の製造法。7. A Ni, C or Fe-based superalloy base material having excellent high-temperature strength, and Ni, C having excellent corrosion resistance and oxidation resistance.
An o or Fe-based metal layer is provided, and a layer in which the ceramic is dispersed in a Ni, Co or Fe-based metal matrix having excellent corrosion resistance is laminated so that the amount ratio of the ceramic is gradually increased. Claim 1 characterized by the above-mentioned.
A method for producing the corrosion-resistant coated member as described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21618094A JPH0874506A (en) | 1994-09-09 | 1994-09-09 | Anti-corrosion coating member and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21618094A JPH0874506A (en) | 1994-09-09 | 1994-09-09 | Anti-corrosion coating member and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0874506A true JPH0874506A (en) | 1996-03-19 |
Family
ID=16684548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21618094A Withdrawn JPH0874506A (en) | 1994-09-09 | 1994-09-09 | Anti-corrosion coating member and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0874506A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004501275A (en) * | 2000-03-27 | 2004-01-15 | サルツァー・メトコ（ユーエス）・インコーポレーテッド | Superalloy HVOF powder with improved high temperature oxidation, corrosion and creep resistance |
| CN103878346A (en) * | 2014-03-12 | 2014-06-25 | 昆明理工大学 | Preparing method of ceramic particle multi-scale enhanced metallic matrix composite materials |
| WO2015129083A1 (en) * | 2014-02-27 | 2015-09-03 | 三菱日立パワーシステムズ株式会社 | Wet bottom furnace |
-
1994
- 1994-09-09 JP JP21618094A patent/JPH0874506A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004501275A (en) * | 2000-03-27 | 2004-01-15 | サルツァー・メトコ（ユーエス）・インコーポレーテッド | Superalloy HVOF powder with improved high temperature oxidation, corrosion and creep resistance |
| WO2015129083A1 (en) * | 2014-02-27 | 2015-09-03 | 三菱日立パワーシステムズ株式会社 | Wet bottom furnace |
| CN103878346A (en) * | 2014-03-12 | 2014-06-25 | 昆明理工大学 | Preparing method of ceramic particle multi-scale enhanced metallic matrix composite materials |
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