JPH0978257A - Thermal insulation coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a ceramic thermal insulation layer having excellent strength and characteristics for heat resistance cycles and excellent adhesion property to a metal base body or a metal bonding layer. SOLUTION: This material coated with a heat-insulation film is produced by forming a metal bonding layer 2 on a metal base body 1 and forming a ceramic heat-insulating layer 3 thereon. In this material, an intermediate layer 4 essentially comprising at least one compd. selected from active metals and oxides of active metals and containing <=1wt.% rare earth oxide is formed between the metal bonding layer 2 and the ceramic heat-insulation layer 3, or, the ceramic heat-insulation layer is formed to have a structure comprising an inner layer by thermal spraying method and an outer layer by EB-PVD method, or, the ceramic heat-insulation layer consists of a stabilized zirconia layer having the orientation in at least one plane direction selected from (100) and (001) planes to the surface of the metal bonding layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material, such as a constituent material of a moving / static vane of a gas turbine, which is required to have high temperature and high stress for a long time high temperature strength, heat shielding property, oxidation resistance and corrosion resistance. And a method for producing the same.

[0002]

2. Description of the Related Art As the operating temperature of equipment increases with the aim of increasing the efficiency of high-temperature equipment such as gas turbines for power generation and engines, materials used for equipment components include:
Even higher levels of properties, such as high temperature strength, high temperature corrosion and oxidation resistance, are required. Therefore, high-strength Ni-based and Co-based
A technology has been developed to apply a corrosion-resistant and oxidation-resistant metal coating made of M-Cr-Al-Y (M = Ni, Co, etc.) alloys to the surface of base superalloys, such as gas turbines for power generation and jet engines for aircraft. In the field of, it is already widely recognized as an indispensable technology.

However, in the trend of higher temperatures,
Metal coating alone is already insufficient as a material property, so a thermal barrier coating technology that cools the inside by applying a ceramic coating with low thermal conductivity to the surface of the metal coating layer was developed as a next-generation technology, It is being put to practical use as a stationary blade for jet engines for aircraft. As a type of ceramic material, Y ₂ O ₃ stabilization is considered due to its characteristics such as high temperature strength, thermal conductivity, and thermal expansion coefficient.
ZrO ₂ is the most widely applied. In addition, M-Cr-Al-Y (M =
The metal coating layer made of an alloy such as Ni, Co, etc. also functions as a bonding layer that alleviates a difference in thermal expansion between the metal base material and the ceramic layer.

Various coating techniques have been applied to the above-mentioned metal coating and thermal barrier coating (ceramics coating). Among them, the plasma spraying method allows a wide selection of coating materials and has a high film-forming rate. It is widely used for coating M-Cr-Al-Y alloys and ceramic materials in high-temperature equipment based on its advantages such as rapid and thick film formation. But,
The ceramic layer formed by the plasma spraying method may be inferior in peeling resistance under thermal cycling, particularly peeling easily from the inside of the ceramic layer, that is, strength and heat cycle resistance, due to the structure peculiar to the thermal spraying layer and numerous internal defects. It has been pointed out.

On the other hand, the electron beam PVD method (EB-PVD
The ceramic layer formed by the physical / chemical vapor deposition method represented by the method (2) has a lower film formation rate and a higher cost than the thermal spraying method, but grows in the direction perpendicular to the interface peculiar to the EB-PVD method. It has a columnar structure, and it is known that this structure acts extremely effectively on the thermal cycle resistance. However, regarding the adhesiveness between the metal bonding layer and the ceramics layer, the current EB-PVD method has no choice but to rely on the chemical bonding force, so that peeling easily occurs at the interface between the metal bonding layer and the ceramics layer. have.

Further, in an actual use environment of a gas turbine or the like, there is a problem of wear and damage of members due to collision of coarse particles and the like. Particularly, a ceramic layer formed by the plasma spraying method has a large unevenness on the surface and the inside of the layer. Since the ZrO ₂ particles have a low bonding force with each other, there is a problem that the damage at the time of collision is large and the ceramic layer surface is easily worn or damaged.

[0007]

As described above, as a method of forming a ceramics layer that functions as a heat shield layer,
Both the plasma spraying method and the EB-PVD method are regarded as promising, but each has its advantages and disadvantages, and simultaneously satisfies all performances such as strength of ceramic layer, heat cycle characteristics, and adhesion between metal / ceramics interface. The current situation is that a ceramics thermal barrier layer has not been obtained.

The present invention has been made in order to solve such a problem, and is a ceramics heat shield layer having excellent heat resistance cycle characteristics and strength and excellent adhesion to a metal base material and a metal bonding layer. The purpose of the present invention is to provide a thermal barrier coating material that can withstand long-term use in a high temperature atmosphere.

Another object of the present invention is to provide a thermal barrier coating material having improved wear resistance, resistance to damage due to collision of flying objects (FOD resistance) and the like.

[0010]

A first thermal barrier coating material according to the present invention is, as described in claim 1, a metal base material, and a metal bonding layer formed by coating on the metal base material. In a thermal barrier coating material comprising a ceramic thermal barrier layer formed on the metal bonding layer, at least an active metal and an oxide of an active metal are provided between the metal bonding layer and the ceramic thermal barrier layer. It is characterized in that an intermediate layer containing one kind as a main component and having a rare earth oxide content of 1% by weight or less is provided.

Further, the first method for producing a thermal barrier coating material comprises the steps of forming the metal bonding layer on the metal base material by coating, and forming an active metal layer on the metal bonding layer. And a step of coating the ceramics heat shield layer directly on the active metal layer or on the active metal layer that has been subjected to an oxidation treatment.

The second thermal barrier coating material according to the present invention comprises, as described in claim 2, a metal base material, a metal bonding layer formed by coating on the metal base material, and the metal bonding layer. In a thermal barrier coating material having a ceramics thermal barrier layer formed as a coating, the ceramics thermal barrier layer is composed of an inner layer formed by a thermal spraying method and a surface layer formed by an electron beam PVD method (hereinafter referred to as EB-PVD method). It is characterized by

The third thermal barrier coating material is, as described in claim 3, a ceramic comprising a metal substrate and stabilized zirconia coated on the metal substrate directly or through a metal bonding layer. In the thermal barrier coating material including a thermal barrier layer, the ceramic thermal barrier layer has a stabilized zirconia layer, and the diffraction intensity ratio of the stabilized zirconia layer surface by X-ray diffraction {I (200) + I (002 )} / {I (200) + I (002) + I (111)}
It is characterized by satisfying the range of 0.9 to 1.0. This third thermal barrier coating material, as described in claim 4,
The ceramics heat shield layer further comprises a stabilized zirconia layer having an orientation in the (111) plane direction with respect to the surface of the metal base material or the surface of the metal bonding layer.

In the first thermal barrier coating material, Ti, Zr,
An intermediate layer containing, as a main component, at least one selected from active metals such as Hf and oxides of these active metals is provided between the metal bonding layer and the ceramics heat shield layer. Ti, Z
Active metals such as r and Hf have a strong affinity with oxygen and nitrogen and easily reduce oxides and the like which are constituent materials of the ceramics heat shield layer. Adhesion can be improved. Further, when the active metal layer is pre-oxidized, the wettability of the outermost surface of the ceramics heat shield layer is improved, so that the adhesion between the metal bonding layer and the ceramics heat shield layer can be similarly enhanced.

In the second thermal barrier coating material, the ceramic thermal barrier layer and the inner layer formed by the thermal spraying method and EB-PV are used.
It is composed of the surface layer formed by the D method, and the metal bonding layer and the ceramics heat shield layer can be more closely adhered to the inner layer formed by the thermal spraying method, which provides good mechanical bonding. In addition, since the surface layer formed by the EB-PVD method is formed on the inner layer formed by the thermal spraying method, the composition of both layers is extremely close even in the case of the EB-PVD method that depends on the chemical bonding force for adhesion. In addition, a higher bonding strength can be obtained as compared with the case where it is directly formed on the metal bonding layer. Since the ceramic surface layer formed by the EB-PVD method has a high effect of relaxing thermal stress due to the growth of a specific columnar structure, it is possible to improve the thermal cycle resistance of the ceramic heat shield layer. Further, the ceramic layer formed by the EB-PVD method has less defects as compared with the plasma spraying method, and thus has a high hardness, and the abrasion resistance and FOD resistance of the surface can be improved at the same time.

In the third thermal barrier coating material, the diffraction intensity ratio of the stabilized zirconia layer surface by X-ray diffraction is {I (200) + I
(002)} / {I (200) + I (002) + I (111)} satisfies the range of 0.9 to 1.0. Here, the stabilized zirconia layer,
(100) and for metal substrate surface and metal bonding layer surface
It has orientation in at least one plane direction selected from (001), but since diffraction peaks of the (100) plane and the (001) plane cannot be obtained by X-ray diffraction, the (200) plane is used in the present invention. ,
It is defined using the diffraction peak of the (002) plane. Both the (200) plane and the (002) plane shown below mean the above.

The crack propagation in the in-layer parallel direction, which causes cracking and peeling of the stabilized zirconia layer, is caused by the existence of the (111) plane which is the cleavage plane that is most easily peeled.
In the stabilized zirconia layer, which is oriented in the (100) or (001) plane, which has the largest face angle with the plane, and the (111) plane is almost not oriented in the in-layer parallel direction, the (111) plane is cracked. Since the angle is high with respect to the propagation direction, it becomes difficult for the crack to propagate in the horizontal direction, and as a result, it is possible to suppress damage due to cracking or peeling of the stabilized zirconia layer.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Modes for carrying out the present invention will be described below.

FIG. 1 is a diagram showing an embodiment of the first thermal barrier coating material of the present invention. In the figure, 1 is a metal base material, and the metal base material 1 is Fe, Ni and Co.
A heat-resistant alloy containing at least one element selected from the following as a main component is used, and various known heat-resistant alloys can be appropriately selected and used according to the intended use. In practice, IN
738, IN939, Mar-M247, RENE80 and other Ni-based superalloys, and FSX
It is effective to use a Co-based superalloy such as 414 or Mar-M509.

On the surface of the above-mentioned metal base material 1, M-Cr-Al- which has excellent corrosion resistance and oxidation resistance and a thermal expansion coefficient intermediate between that of the metal base material 1 and the ceramics heat shield layer 3 described later. Y
A metal bonding layer 2 made of an alloy (M = Co, Ni) or the like is formed by coating. The metal bonding layer 2 made of the M-Cr-Al-Y alloy ensures the corrosion resistance and the oxidation resistance of the metal substrate 1 as described above, and at the same time, the thermal expansion coefficient between the metal substrate 1 and the ceramics heat shield layer 3. The purpose is to reduce the thermal stress due to the difference in
~ 20 wt% Al, 10-35 wt% Cr, 0.1-5 wt%
At least 1 including Y and the balance Ni and Co
An alloy with a composition consisting essentially of the M element is used.
Depending on the application, M-Cr-Al-Y alloy with Ti, Nb, Hf,
It is also possible to add a trace amount of at least one additive element selected from Zr, Ta and W in a range of 5% by weight or less.

The metal bonding layer 2 is formed by plasma spraying method, HVO.
It can be formed by a film forming method such as the F method, the PVD method, or the CVD method, but the plasma spraying method is most effective in practice. Particularly, among the plasma spraying methods, a low pressure plasma spraying method (VPS method) in which a spraying process is performed in a reduced pressure atmosphere is preferable, whereby oxidation of the metal bonding layer 2 during film formation is suppressed, and excellent oxidation resistance is imparted. can do. Further, when the plasma spraying method is used, it is preferable that the surface thereof is smoothed by mechanical polishing or the like and a subsequent film forming step is performed, as described later in detail.

The thickness of the metal bonding layer 2 can be selected from the range of about 10 to 500 μm according to the application. For example, about 50 to 300 μm in the gas turbine blade portion, the oxidation life or the metal base material 1 and the ceramic heat shield layer 3 is reduced. It is suitable from the viewpoint of stress relaxation effect.

Between the above-mentioned metal bonding layer 2 and the outermost ceramic heat shield layer 3, at least one selected from active metals such as Ti, Zr and Hf and oxides of these active metals is a main component. The intermediate layer 4 is provided. That is,
Active metals such as Ti, Zr, and Hf have a strong affinity with oxygen and nitrogen, and easily reduce oxides such as stabilized ZrO _{2 that} is a constituent material of the ceramics heat shield layer 3 which will be described later. By forming an active metal layer as the layer 4, adhesion between the metal bonding layer 2 and the ceramics heat shield layer 3 can be enhanced. In addition, T formed on the metal bonding layer 2
When the active metal layer of i, Zr, Hf or the like is pre-oxidized by heat treatment or the like to form the intermediate layer 4 containing these oxides as the main components, the wettability with respect to the ceramics heat shield layer 3 on the outermost surface is Because of the improvement, the adhesiveness between the metal bonding layer 2 and the ceramics heat shield layer 3 can be similarly enhanced.

Here, even when the main component of the intermediate layer 4 is an oxide, the oxide of this active metal reduces the thermal oxide or the reduction oxide (the constituent material of the ceramics heat shield layer 3) as described above. And the like), which is different from the oxide layer formed by using the oxide as a film-forming raw material. Therefore, like the stabilized zirconia layer used as the ceramics heat shield layer 3, it does not substantially contain a stabilizer such as a rare earth oxide, and more specifically, an activity with a rare earth oxide content of 1% by weight or less. It has a metal oxide as a constituent.

That is, in the first thermal barrier coating material, as shown in FIG. 2, first, an active metal layer 4'having a rare earth oxide content of 1% by weight or less is formed on the metal bonding layer 2 ( FIG. 2A). Thereby, good adhesion with the metal bonding layer 2 can be obtained. Next, the ceramics heat shield layer 3 is formed on the active metal layer 4 ', and an interface metal reaction (reduction reaction) with the ceramics heat shield layer 3 causes, for example, an active metal oxide (reduction oxide) as a main component. To form an intermediate layer 4 (main component may be a single active metal), or to shield the ceramics on the intermediate layer 4 whose main component is a thermal oxide generated by thermal oxidation of the active metal layer 4 '. By forming the heat layer 3 (FIG. 2B), the ceramic heat shield layer 3 is formed.
Good adhesion with is obtained. On the other hand, when the oxide layer is formed on the metal bonding layer 2 from the beginning, sufficient adhesion between the oxide layer and the metal bonding layer 2 cannot be obtained.

When a Zr oxide is used as the intermediate layer 4, the structure thereof is not particularly limited, but monoclinic zirconia and the like can be mentioned. T constituting the middle layer 4
Oxides such as i, Zr and Hf include Ti and Z in which oxygen is in a metallic state.
It may be a solid solution in r or Hf.

The method for forming the active metal layer 4'is not particularly limited, but it is preferable to apply a physical / chemical vapor deposition method such as an EB-PVD method or a sputtering method.
This is because, according to the EB-PVD method or the like, a film can be directly formed on a smooth surface, and peeling due to stress near the interface due to surface roughness can be effectively suppressed.

The active metal layer formed as the above-mentioned intermediate layer 4 may be one containing at least one selected from Ti, Zr and Hf as a main component, and an alloy containing at least one of the above active metal elements. It is also possible to use. Although the active metal layer may be formed as a single layer, it may be present as an alloying element in the vicinity of the surface of the metal bonding layer 2 so that the ceramic heat shield layer 3 may be formed during the formation of the ceramic heat shield layer 3 or in the subsequent heat treatment process. You may make it react with 3.

The thickness of the intermediate layer 4 is not particularly limited, but almost all is used for the reaction with the ceramics heat shield layer 3 during the formation of the ceramics heat shield layer 3 and in the subsequent heat treatment process. It is preferable. When the active metal layer 4'is previously oxidized to form the intermediate layer 4 containing an oxide as a main component, its thickness is preferably 10 μm or less. When the thickness of the intermediate layer 4 containing an oxide as a main component exceeds 10 μm, the peeling property becomes high.

As the constituent material of the ceramics heat shield layer 3, ZrO ₂ , Si ₃ N ₄ , SiC, Al ₂ O ₃ , TiN, AlN,
Although various ceramic materials such as sialon can be used, ZrO ₂ is suitable as the ceramic heat shield layer 3 because of its low thermal conductivity and large thermal expansion coefficient. As the stabilizing agent for controlling a phase change ZrO _2, Y ₂ O _3, CaO, although MgO or the like is used, and most preferably is Y ₂ O ₃ Among these, in particular Y ₂ O ₃ 8
Partially stabilized zirconia containing about wt% shows extremely excellent characteristics. The total thickness of the ceramics heat shield layer 3 can be appropriately selected from the range of about 50 to 3000 μm according to the application, for example, about 100 to 300 μm for the gas turbine blade and about 500 to 2000 μm for the inner surface of the combustor. preferable.

The method for forming the ceramics heat shield layer 3 is not particularly limited, but it is preferable to use a physical / chemical vapor deposition method typified by an EB-PVD method or a sputtering method. This is because, for example, according to the EB-PVD method, a peculiar columnar structure that grows in the direction perpendicular to the interface can be obtained, and the ceramic heat shield layer 3 having excellent heat cycle characteristics, that is, the propagation of cracks in the surface direction. This is because the ceramics heat shield layer 3 that can be suppressed is obtained. Further, according to the EB-PVD method or the like, the ceramics heat shield layer 3 having less defects and higher hardness than the plasma spraying method is used.
Therefore, the wear resistance and FOD resistance of the ceramic heat shield layer 3 can be improved at the same time.

Furthermore, according to the EB-PVD method or the like, since it is possible to easily form a film on a smooth surface, the peeling of the ceramics heat shield layer 3 due to the stress due to the uneven shape of the interface is suppressed. be able to. That is, when the ceramics thermal barrier layer is formed on the ordinary metal bonding layer by the plasma spraying method, these adhesions are based on the so-called anchor effect utilizing the surface roughness of the metal bonding layer, and therefore When stress due to the surface shape is generated in the ceramic layer near the interface and exposed to the operating environment of a gas turbine or the like, the ceramic layer is liable to peel off based on the stress. On the other hand, by using the EB-PVD method or the like, which can easily form a film on a smooth surface, it becomes possible to suppress the peeling of the ceramic layer. However, in the present invention, since the chemical bonding force of the intermediate layer 4 is positively utilized, the ceramic heat shield layer can be formed on the smooth surface by the plasma spraying method.

Next, an embodiment of the second thermal barrier coating material of the present invention will be described. FIG. 3 is a view showing an embodiment of the second thermal barrier coating material, and 1 is a metal base material made of the same heat-resistant alloy as in the above-described first embodiment. Similar to the first embodiment, the metal bonding layer 2 made of M-Cr-Al-Y alloy or the like is formed by coating. Formed on the metal bonding layer 2 is a ceramics heat shield layer 3 that shields external heat, enhances the cooling effect inside the member, improves the service temperature, and extends the life of the member.

The ceramic heat shield layer 3 comprises a ceramic inner layer 5 formed by a thermal spraying method and a ceramic surface layer 6 formed by an EB-PVD method. The ceramics inner layer 5 formed by the thermal spraying method is a layer formed to enhance the bondability with the metal bonding layer 2 made of an M-Cr-Al-Y alloy or the like, and is good by engaging with the irregularities on the surface of the metal bonding layer 2. A good mechanical connection can be obtained. As a thermal spraying method applied to the formation of the ceramic inner layer 5, the plasma thermal spraying method is most effective in practice.

On the ceramic inner layer 5, EB-
When the ceramic surface layer 6 is formed by the PVD method, even if the EB-PVD method, which depends on the chemical bonding force for the adhesiveness, the composition of both layers is very close, and therefore the metal bonding layer 2
A higher binding force can be obtained as compared with the case of forming directly on top. Ceramic surface layer 6 by EB-PVD method
Has a high effect of alleviating thermal stress due to the growth of a peculiar columnar structure, and can improve the peeling resistance of the ceramics heat shield layer 3. Further, the ceramic surface layer 6 has less defects as compared with the plasma spraying method, and thus has high hardness, and it is possible to simultaneously improve the wear resistance and FOD resistance of the surface. Combining the ceramic inner layer 5 by the thermal spraying method and the ceramic surface layer 6 by the EB-PVD method is
-It is also effective as a solution to the problem of high cost by the PVD method.

The thickness ratio between the ceramic inner layer 5 and the ceramic surface layer 6 can be appropriately selected from 1:99 to 99: 1. Further, depending on the application, as shown in FIG.
-The ceramic surface layer 6 formed by the PVD method only fills the surface irregularities of the ceramic inner layer 5 formed by the thermal spraying method, or the ceramic inner layer 5 formed by the thermal spraying method fills the unevenness of the metal bonding layer 2 as shown in FIG. Various forms such as one having a thickness can be adopted.

However, in practice, it is preferable to select the following thickness ratio. That is, for example, in a region where heat cycle resistance is extremely required, the ratio of the ceramic surface layer 6 by the EB-PVD method is high, and the inner layer 5: surface layer 6 is preferably in the range of about 1: 9 to 4: 6. In addition, it is preferable to control the inner layer 5: surface layer 6 in the range of about 4: 1 to 99: 1 in a region where improvement in erosion resistance and FOD resistance and low cost are required.

Further, in the ceramic heat shield layer 3 in which the ceramics inner layer 5 formed by the thermal spraying method and the ceramics surface layer 6 formed by the EB-PVD method are combined, the convex portion at the interface between the metal bonding layer 2 and the ceramics inner layer 5 formed by the thermal spraying method. And the height difference between the recesses (as an average value) is set in the range of 5 to 200 μm, and the ceramic inner layer 5 and EB-PV by the thermal spraying method are used.
It is preferable that the height difference (as an average value) between the convex portion and the concave portion at the interface with the ceramic surface layer 6 by the D method is in the range of 0.01 to 10 μm.

It is known that the roughness of the interface between the metal bonding layer 2 and the ceramics inner layer 5 has a significant effect on the adhesion strength of both layers. The larger the roughness of the interface, the higher the adhesion strength. is there. Scanning electron microscope (SE
When magnified 500 to 1000 times with M) and the difference in height between the convex and concave portions is in the range of 5 to 200 μm on average at 5 places, the thermal barrier coating material has an excellent heat resistance cycle. Shows sex. Practically, the interface roughness in the range of 7 to 20 μm is more preferable because the plasma spraying facilitates the construction.

The surface roughness of the sprayed layer is 65 μm at R _max .
Extent, R _max 40 [mu Subsequent sandblasting
It is possible to directly form the ceramic surface layer 6 by the EB-PVD method on this surface regardless of the presence or absence of the sandblast treatment.
It has been clarified that the roughness of the base has a great influence on the properties of the ceramic surface layer 6 by the D method, and if the surface roughness is made 0.01 to 10 μm by performing a smoothing treatment such as polishing, A good columnar structure can be obtained. If the roughness of the interface between the ceramic inner layer 5 and the ceramic surface layer 6 is larger than the above range, the growth direction of each structure is disturbed, and thus the columnar structure may not be able to grow sufficiently. In addition, if it is made smoother than the above-mentioned roughness range, polishing processing becomes difficult, which is not preferable in practical use.

In order to increase the bond strength between the ceramics inner layer 5 formed by the thermal spraying method and the ceramics surface layer 6 formed by the EB-PVD method, Ca is added to the thermal spraying powder or the target of the EB-PVD method to form an interface. It is also possible to further form an oxide layer in which Ca and Zr coexist. Further, as the constituent material of the ceramic inner layer 5 and the ceramic surface layer 6, the same material as the ceramic material exemplified in the above-mentioned first embodiment can be used,
Partially stabilized zirconia containing about 8% by weight of ZrO _2, particularly Y ₂ O ₃ , exhibits extremely excellent characteristics.

Next, an embodiment of the third thermal barrier coating material of the present invention will be described. FIG. 6 is a view showing an embodiment of the third heat-shielding coating material, and 1 is a metal base material made of a heat-resistant alloy similar to that of the first embodiment described above. Similar to the first embodiment, the metal bonding layer 2 made of M-Cr-Al-Y alloy or the like is formed by coating. The metal bonding layer 2 does not necessarily have to be formed. In the following description, it is assumed that the metal bonding layer 2 is provided, but when the metal bonding layer 2 is not formed, the surface of the metal base 1 serves as a reference.

A ceramics heat shield layer (hereinafter, referred to as a zirconia heat shield layer) 7 made of stabilized zirconia is formed on the metal bonding layer 2. The thickness of the zirconia heat shield layer 7 is preferably about 50 to 500 μm. Stabilized zirconia, Y ₂ O _3, the mechanical strength and high toughness can be expected
Stabilized zirconia is preferred. When used for a long time in a high-temperature atmosphere of 1523K or higher or in an environment that is chemically corrosive, add rare earth elements such as Nd and Sm, which have an ionic radius larger than Y, or stabilize them with them. In some cases, it is preferable to use zirconia that has been made to be a material, and it is possible to suppress the decrease in strength of the zirconia heat shield layer 7 due to them.

The zirconia thermal barrier layer 7 described above has a stabilizing zirconia layer 8 having an orientation in at least one plane direction selected from (100) and (001) with respect to the surface of the metal bonding layer 2. There is. The stabilized zirconia layer 8 is
Either (100) or (001) may be oriented in one direction, or the two directions may be mixed. Desirably, because the crack propagation path can be deflected,
It is better to be random in the dimensional direction, and also with respect to the orientation, randomly orienting (100) and (001) gives better thermal stress relaxation, and a member with excellent heat stress resistance is obtained. To be Both of the above-mentioned orientation surfaces have good conformity, and the surfaces that are easily peeled off are not laminated in parallel with the metal bonding layer 2.

The orientation described here means that the diffraction peak intensity ratio of each surface measured by the X-ray diffraction method is the JCPDS card.
This means that it is more than double that of (17-923). Further, the X-ray diffraction intensity ratios are all based on the diffraction result when X-rays are applied to the zirconia heat shield layer 7 in the vertical direction.

The orientation of the stabilized zirconia layer 8 is (100) or
The reason for defining in (001) is that in the stabilized zirconia layer 8 having these orientations, the (111) plane corresponding to the cleavage plane of the stabilized zirconia is laminated parallel to the surface of the metal bonding layer 2. Because there is no. Originally, cracking or peeling of the stabilized zirconia layer occurs due to the crack propagating in the stabilized zirconia layer parallel to the metal bonding layer 2.
That is, it is said that the (111) plane, which is the cleavage plane that is the most easily cleaved, in which the crack progresses easily, is gathered parallel to the surface of the metal bonding layer 2 in the stabilized zirconia layer. The cracking and peeling of the stabilized zirconia layer easily occur.

On the other hand, in the stabilized zirconia layer 8 oriented to the (100) plane or the (001) plane having the largest face angle with the (111) plane, the (111) plane, which is liable to peel, is a metal. Since the angle is high with respect to the surface of the bonding layer 2 and the (111) planes do not assemble parallel to the surface of the metal bonding layer 2, cracks do not easily propagate in the horizontal direction, and as a result, stabilized zirconia It is possible to suppress damage due to cracking or peeling of the layer 8.

From the above, in order to obtain the obtained zirconia heat shield layer 7 which is excellent in heat stress / peeling resistance, it is desired that the orientation of the stabilized zirconia layer 8 does not substantially include the (111) plane. Specifically, the diffraction intensity ratio {I (200) + I (002)} / {I (200) + I (002) + I (111)} in the X-ray diffraction result is 0.9.
It is necessary to satisfy the range of ~ 1.0, and it is desirable to be as close as possible to 1. That is, the cleavage plane
The (111) plane does not exist in the direction parallel to the surface of the metal bonding layer 2. If the X-ray diffraction intensity ratio is less than 0.9, the cracks propagate in the horizontal direction due to the (111) plane existing in parallel with the surface of the metal bonding layer 2. As a result, it is impossible to obtain the zirconia coating layer 7 having excellent durability against cracking and peeling. This structure in which peeling or cracking does not easily occur does not impair the heat resistance and oxidation resistance of the metal part.

In the stabilized zirconia layer 8, it is desirable that crystal planes other than the (100) plane and the (001) plane do not exist parallel to the surface of the metal bonding layer 2. Specifically, in the X-ray diffraction result of the stabilized zirconia layer 8, the diffraction intensity ratio {I
(200) + I (002)} / {I (200) + I (002) + I (HKL)} (however, (HK
(L) represents at least one crystal plane selected from (311), (113), (220) and (202)) is preferably in the range of 0.8 to 1, and is even closer to 1 as much as possible. More desirable.

The above-mentioned X-ray diffraction intensity ratio is based on the value measured from the surface of the coated zirconia heat shield layer 7, and the metal base material 1 or the metal bonding layer 2 having a large thermal stress.
It is desirable to satisfy the above-mentioned diffraction intensity ratio exhibiting the orientation at a position about 1 to 20 μm above.

Further, in the above-mentioned embodiment, the orientation of the zirconia coating layer 7 made of tetragonal zirconia having excellent thermal fatigue properties is specified. However, for members that require chemical stability rather than thermal fatigue properties, May be mixed with cubic zirconia, or may be composed of only cubic crystals. Therefore, when it is composed of cubic zirconia, I
Consider (200) = I (200) + I (002). Furthermore, the amount of monoclinic zirconia calculated using the diffraction intensity obtained by the X-ray diffraction method is desirably so small that it cannot be detected by the X-ray diffraction method. Can be prevented, and the strength reduction of the zirconia heat shield layer 7 can be suppressed.

By the way, in a practical use environment of a gas turbine or an aircraft engine using the above-mentioned thermal barrier coating material, there is a problem that fine dust or coarse particles collide with the zirconia thermal barrier layer 7 to cause damage. . In particular, the zirconia coating layer produced by the atmospheric spraying method has large irregularities on the surface, and the damage when the flying object collides is large. Further, if it is used for a long time, the wear due to friction with a small flying object becomes a serious problem.

On the other hand, the zirconia heat shield layer having a columnar structure formed by the EB-PVD method or the like has excellent characteristics as compared with the zirconia heat shield layer formed by the thermal spraying method because of its large hardness. When used as an actual machine for a long time in a high temperature atmosphere, a crack may propagate inside the coating due to collision and wear of flying objects, and a part of the zirconia heat shield layer may be peeled off. Such consumption of the zirconia heat shield layer lowers the heat shield effect and must be suppressed.

In order to prevent the peeling of the zirconia thermal barrier layer due to the collision and abrasion of flying objects as described above, the thermal barrier coating material according to the third embodiment described above is further oriented in the (111) plane direction. It is effective to add a stabilized zirconia layer having The thermal barrier coating material having such a structure will be described with reference to FIG. 7.

In the thermal barrier coating material shown in FIG. 7, a stabilized zirconia layer having orientation in at least one direction of the (100) plane and the (001) plane on the metal bonding layer 2, that is, similar to the above-mentioned embodiment. Zirconia layer with various orientations (hereinafter referred to as (100) / (001) plane oriented zirconia layer)
8 is first formed as a coating, on which a (100) / (001) oriented zirconia layer 8 and a stabilized zirconia layer having an orientation in the (111) plane direction (hereinafter referred to as (111) plane oriented zirconia layer). Is provided), and a zirconia multilayer heat-insulating layer 7 is constituted by these. In the zirconia multilayer laminated film 10,
The thickness of one layer of the (111) plane-oriented zirconia layer 9 is 0.5 to
The range is preferably 5 μm.

The reason why the (111) plane-oriented zirconia layer 9 is used for the multilayer film 10 on the surface side is that the zirconia heat shield layer 7 is used.
Of cracks that spread from the surface to the inside of the layer due to the collision and wear of flying objects that cause damage (cracking and peeling) of the
This is for stopping at the orientation plane having the (111) orientation. Specifically, the propagation path of the crack propagating into the zirconia thermal barrier layer 7 is changed by the (111) -oriented zirconia layer 9 by 90 degrees to suppress the propagation of the crack spreading inside the layer. . The (111) -oriented zirconia layer 9 may be peeled off in order to suppress crack propagation. (111)
The reason for defining the film thickness of the plane-oriented zirconia layer 9 is that if the thickness is less than 0.5 μm, the effect of suppressing crack propagation cannot be sufficiently obtained, and if it exceeds 5 μm, the strength of the zirconia multilayer laminated film 10 decreases. As a result, it may not be possible to endure long-term operation in which a heat cycle occurs.

The thickness of the multilayer laminated film 10 portion in the zirconia heat shield layer 7 may be 20 μm or less in a portion where relatively high wear resistance is not required although it varies depending on the use environment. Considering the adhesion strength of the multilayer laminated film 10, the area exposed to 20 to 200 μm
It is preferable to set the degree. The film thickness ratio of the (111) -oriented zirconia layer 9 to the (100) / (001) -oriented zirconia layer 8 is preferably 0.01 to 1.0. The number of layers is not particularly limited, but the more the zirconia layer 9 having the (111) plane orientation is included, the better the peeling due to wear can be suppressed.

Further, a zirconia layer 9 having a (111) plane orientation and
For the site where the interface strength with the (100) / (001) plane-oriented zirconia layer 8 is required, it is preferable to add a compound layer containing Ca with a thickness of about 0.5 to 10 μm between these layers.
Thereby, the interface strength can be maintained. The reason for using the Ca compound is to cause a solid-phase reaction with the stabilized zirconia constituting each layer 8 and 9 at around 1273K to bond the interface. This Ca-stabilized zirconia may be formed at the same time as the heat shield layer 7 is formed, or a compound containing Ca such as Ca (OH) ₂ may be applied to form a (111) -oriented zirconia layer 9 and heat treatment (1123 ˜1473 K) to form Ca-stabilized zirconia. Further, it is preferably Ca-stabilized zirconia, but may be a compound of Ca and Zr such as CaZrO ₃ or a compound including other rare earth elements. Furthermore, when a Ca compound or Ca-stabilized zirconia is formed at the same time when the heat shield layer 7 is formed, it is preferable to apply PVD or the CVD method because the film thickness can be easily controlled.

Next, the method for producing the thermal barrier coating material according to the above-described third and fourth embodiments, particularly, the (100) / (001) plane-oriented zirconia layer 8 and the (111) plane-oriented zirconia layer 9 are formed. The forming method will be described.

The zirconia heat shield layer 7 is formed by coating on the metal base material 1 or on the metal bonding layer 2 formed thereon. At this time, it is preferable that the surface of the metal base material 1 or the metal bonding layer 2 be subjected to mirror-polishing treatment, which improves the formability of the zirconia layers 8 and 9 having excellent orientation.

The zirconia layers 8 and 9 having orientation are made of P
It is formed by the VD method or the CVD method. When the PVD method is used, since zirconia is a high melting point material, vapor deposition with an electron beam improves the film forming efficiency and also has excellent film characteristics.
That is, it is particularly preferable to apply the EB-PVD method. The orientation of the zirconia layer can be controlled by the temperature of the metal part (substrate temperature), the oxygen partial pressure, the input energy of the electron beam, and the like.

For example, when the metal portion to be coated is heated to 973 K or more, the (100) / (001) plane oriented zirconia layer 8 is obtained. Further, in the case of less than 973K, the orientation plane of the zirconia layer is the (111) direction. When the zirconia layer 8 having the (100) / (001) plane orientation is formed, it is preferable to heat the metal portion to a high temperature of 1023 K or higher in order to improve the film formation rate and the orientation. In addition, the intermediate layer 4 described in the first embodiment is provided on the metal base material 1 or the metal bonding layer 2.
Alternatively, by forming the inner layer 5 by the thermal spraying method described in the second embodiment, the adhesion between the metal bonding layer 2 and the zirconia heat shield layer 3 can be improved, and the thermal stress resistance is further excellent. A thermal barrier coating material is obtained.

Further, the presence of a compound containing at least one kind of noble metal element such as Pt, Au, Pd, and Ag on the surface of the metal base material 1 or the metal bonding layer 2 allows the zirconia heat shield layer 7 to be closely contacted. Since it is possible to form a compound bonded to the zirconia, a better thermal fatigue property can be obtained, and a zirconia heat shield layer 7 that is strong against cracking and peeling can be obtained. Further, when it is difficult to heat the metal part for a long time, it is preferable to use an ion plating method together or cool only the ceramic part by condensing and heating the metal part. Furthermore, by heating only the part where the stress concentration is large,
The zirconia layer 8 having (100) / (001) plane orientation may be partially formed.

The oxygen partial pressure during the formation of the zirconia thermal barrier layer is
1.0 × 10 ³ Pa or less is desirable, and in order to control the oxide during deposition in obtaining the zirconia heat shield layer 7 that is resistant to cracking / peeling, it is 1.0 × 10 ^-1 Pa or less. Is desirable. The oxygen partial pressure during film formation also affects the orientation. For example, when forming the zirconia layer 8 having the (100) / (001) plane orientation, the oxygen partial pressure is 1.0 × 10 ² Pa or less. It is preferable.

The (111) plane-oriented zirconia layer 9 and (100) / (0
When the (01) plane-oriented zirconia layers 8 are alternately laminated, for example, the substrate temperature of the coating portion is controlled. In particular,
After forming the zirconia layer 8 with (100) / (001) orientation, form the zirconia layer 9 with (111) orientation with the coating temperature of 923K or less, and then with the coating temperature of 1023K or more. Then, a zirconia layer 8 having a (100) / (001) plane orientation is formed. The film thickness ratio is controlled by the film formation time, and the multilayer structure is controlled by controlling the temperature cycle.

When Ca-stabilized zirconia or the like is inserted between the (100) / (001) -oriented zirconia layer 8 and the (111) -oriented zirconia layer 9, (100) / (001 ) After forming the plane-oriented zirconia layer 8, Ca-stabilized zirconia is added.
After coating about 0.5 to 10 μm, a (111) oriented zirconia layer 9 is formed.

[0067]

Next, specific examples of the present invention will be described.

First, concrete examples of the first thermal barrier coating material will be described.

Example 1 A surface of a blade-shaped IN738 alloy was blasted, and a NiCoCrAlY alloy layer (N with a thickness of 100 μm was formed by a low pressure plasma spraying method.
i-23% Co-17% Cr-12% Al-0.5% Y (wt%)) was deposited as a metal bonding layer. Next, after the surface of the NiCoCrAlY alloy layer was mirror-polished, the sample was transferred to a chamber for EB-PVD, and a metal Zr layer was formed to a thickness of 1 μm. After that, the 8 wt% Y ₂ O ₃ -ZrO ₂ layer was formed at room temperature using oxygen gas as an assist gas.
A film of 00 μm was formed as a heat shield layer.

Observation of the cross-sectional structure of the thus-obtained thermal barrier coating member after film formation revealed that a metal Zr layer was formed at the interface between the ceramic thermal barrier layer made of stabilized zirconia and the metal bonding layer made of NiCoCrAlY alloy. A ZrO ₂ layer formed by the oxidation of Al was observed. This ZrO ₂ layer is substantially free of rare earth oxides.

Further, as a comparative example with the present invention, a thermal barrier coating member was formed by coating only two layers of a NiCoCrAlY alloy layer and a stabilized zirconia layer without interposing a metal Zr layer under the same conditions as in the above-mentioned examples. Was produced. When the thermal barrier coating member of this comparative example and the thermal barrier coating member of Example 1 were subjected to a repeated thermal fatigue test at room temperature and 1173K-3600 seconds at the same time, the thermal barrier coating member of the example showed 1000 times or more. In contrast, the thermal barrier coating member of the comparative example peeled off the thermal barrier layer after 30 times.

Example 2 A surface of a blade-shaped IN738 alloy was blasted, and a NiCoCrAlY alloy layer (N with a thickness of 100 μm was formed by a low pressure plasma spraying method.
i-23% Co-17% Cr-12% Al-0.5% Y (wt%)) was deposited as a metal bonding layer. Then, after mirror-polishing the surface of the NiCoCrAlY alloy layer, the sample is transferred to a chamber for EB-PVD,
A metal Zr layer was formed to a thickness of 1 μm. After forming the metal Zr layer, it was oxidized to form a ZrO ₂ layer. After that, an 8 wt% Y ₂ O ₃ —ZrO ₂ layer was formed to a thickness of 200 μm at a sample temperature of 773 K while using oxygen gas as an assist gas to form a heat shield layer.

Observation of the cross-sectional structure of the thus-obtained thermal barrier coating member after film formation revealed that a metallic Zr layer was formed at the interface between the ceramic thermal barrier layer made of stabilized zirconia and the metallic bonding layer made of NiCoCrAlY alloy. Pre-oxidized ZrO
_Two layers were observed. This ZrO ₂ layer is substantially free of rare earth oxides.

Further, as a comparative example with the present invention, a thermal barrier coating member was formed by coating only two layers of a NiCoCrAlY alloy layer and a stabilized zirconia layer without interposing a metal Zr layer under the same conditions as in the above-mentioned examples. Was produced. When the thermal barrier coating member of this comparative example and the thermal barrier coating member of Example 2 were simultaneously subjected to a repeated thermal fatigue test at room temperature and 1173K for 3600 seconds, the thermal barrier coating member of the example was 1000 times or more. In contrast, the thermal barrier coating member of the comparative example peeled off the thermal barrier layer after 30 times.

Example 3 A surface of a blade-shaped CMSX-2 alloy was blasted, and a NiCoCrAlY alloy layer (N having a thickness of 100 μm was formed by a low pressure plasma spraying method.
i-23% Co-17% Cr-12% Al-0.5% Y (wt%)) was deposited as a metal bonding layer. Next, after the surface of the NiCoCrAlY alloy layer was mirror-polished, the sample was transferred to a chamber for EB-PVD, and a metal Ti layer was formed to a thickness of 0.7 μm. After that, an 8 wt% Y ₂ O ₃ —ZrO ₂ layer was formed to a thickness of 200 μm at a sample temperature of 773 K while using oxygen gas as an assist gas to form a heat shield layer.

Observation of the cross-sectional structure of the thus-obtained thermal barrier coating member after film formation revealed that a metallic Ti layer was formed at the interface between the ceramic thermal barrier layer made of stabilized zirconia and the metallic bonding layer made of NiCoCrAlY alloy. A TiO ₂ layer formed by the oxidation of TiO ₂ was observed. This TiO ₂ layer is substantially free of rare earth oxides.

In addition, as a comparative example with the present invention, a thermal barrier coating member was formed by coating only two layers of a NiCoCrAlY alloy layer and a stabilized zirconia layer without interposing a metal Ti layer under the same conditions as in the above-mentioned examples. Was produced. The thermal barrier coating member of this comparative example and the thermal barrier coating member of Example 3 were simultaneously subjected to repeated thermal fatigue tests at room temperature and 1173K for 3600 seconds. In contrast, the thermal barrier coating member of the comparative example peeled off the thermal barrier layer 100 times.

Example 4 The surface of a blade-shaped CMSX-2 alloy was blasted, and a NiCoCrAlY alloy layer (N
i-23% Co-17% Cr-12% Al-0.5% Y (wt%)) was deposited as a metal bonding layer. Then, after the surface of the NiCoCrAlY alloy layer was mirror-polished, the sample was transferred to a chamber for EB-PVD, and a metal Hf layer was formed to a thickness of 0.5 μm. After that, an 8 wt% Y ₂ O ₃ —ZrO ₂ layer was formed to a thickness of 200 μm at a sample temperature of 773 K while using oxygen gas as an assist gas to form a heat shield layer.

Observation of the cross-sectional structure of the thus obtained thermal barrier coating member after film formation revealed that a metallic Hf layer was formed at the interface between the ceramic thermal barrier layer made of stabilized zirconia and the metallic bonding layer made of NiCoCrAlY alloy. The HfO ₂ layer formed by the oxidation of the HfO ₂ was observed. This HfO ₂ layer is substantially free of rare earth oxides.

Further, as a comparative example with the present invention, a thermal barrier coating member formed by coating only two layers of a NiCoCrAlY alloy layer and a stabilized zirconia layer without interposing a metal Hf layer under the same conditions as in the above-mentioned examples. Was produced. When the thermal barrier coating member of this comparative example and the thermal barrier coating member of Example 2 were simultaneously subjected to a repeated thermal fatigue test at room temperature and 1173K for 3600 seconds, the thermal barrier coating member of the example was 1000 times or more. In contrast, the thermal barrier coating member of the comparative example peeled off the thermal barrier layer 100 times.

Next, concrete examples of the second thermal barrier coating material will be described.

Example 5 A Ni-base superalloy IN738LC was prepared as a base material, and this alloy base material was processed into a size of 20 × 20 × 3 mm. Ni-23% on its surface
A Co-17% Cr-12% Al-0.5% Y alloy layer was formed by low pressure plasma spraying. After that, as a ceramic inner layer, 8 wt% Y ₂ O ₃ -ZrO was formed by an atmospheric plasma spraying method (APS method).
₂ is formed to a thickness of 20 μm, the surface is polished to # 1000, and then a ceramic surface layer of the same composition is formed on EB-P.
A film having a thickness of 180 μm was formed by the VD method.

On the other hand, as a comparative example with the present invention, after forming the metal bonding layer (NiCoCrAlY alloy layer) in the same process, a ceramic having the same composition as in Example 5 was formed by the APS method.
200 μm formed sample (Comparative Example 5-1) and EB-
A sample (Comparative Example 5-2) having a thickness of 200 μm formed by the PVD method was prepared.

The above-mentioned Example 5 and Comparative Examples 5-1 and 5-2
Each of the thermal barrier coating members according to the above was subjected to the following tests. First, room temperature x 30min-1273K x 30min for each of these samples
The thermal cycle test was carried out to measure the number of cycles until macroscopic peeling of the ceramic layer occurred. as a result,
In Comparative Example 5-1, peeling occurred 1300 times and in Comparative Example 5-2 2100 times, whereas in Example 5, peeling did not occur even after 5000 times.

Next, each sample was measured at 1073K with a particle size of about 500 μm.
The erosion state of the surface was observed by exposing to an air atmosphere containing Al ₂ O ₃ particles at a flow rate of about 100 L / min. As a result, in Comparative Example 5-1, the ceramic layer was chipped in the shape of flakes with the passage of time, whereas in Example 5 having the ceramic surface layer formed by the EB-PVD method, the surface texture was not significantly changed. Not observed.

Example 6 A Ni-base superalloy IN738 was used as a base alloy, and this was used as 20 × 20.
Processed to a size of × 3 mm. Apply M-Cr-Al-Y alloy on the surface under the conditions of thermal spraying so that the surface roughness becomes 15 μm.
The coating was formed by the PS method. Further, after spraying 8 wt% Y ₂ O ₃ -ZrO ₂ to a thickness of about 20 μm by the APS method,
The surface is polished to # 1000 and the roughness (difference in height between concave and convex parts /
The average value) was 0.7 μm, and then a ceramic surface layer having the same composition was formed by the EB-PVD method so as to have a thickness of about 180 μm.

As a comparative example, the composition and layer constitution of the substrate and each layer were the same as in Example 6, and the thermal spraying conditions were such that the roughness of the M-Cr-Al-Y alloy layer / sprayed ceramics layer interface was 3 μm. A sample having an alloy layer formed thereon in Comparative Example 6-1 and a sample having a ceramic layer formed by the EB-PVD method without polishing the sprayed ceramics layer (Comparative Example 6-2) were prepared.

These samples were tested at room temperature × 30 min-1273K × 30 mi.
It was subjected to a heat cycle test of n to evaluate the peel resistance. As a result, peeling of the ceramic layer occurred 1800 times in Comparative Example 6-1 and 1300 times in Comparative Example 6-2. On the other hand, in Example 6, peeling was not observed even after exceeding 5000 times.

Next, concrete examples of the third thermal barrier coating material (third and fourth embodiments) will be described.

Example 7 A metal bonding layer composed of a Ni-Co-Cr-Al-Y alloy was formed on a metal base material containing Ni as a main component by a plasma spraying method, and a Y element concentration was further formed thereon. Of the stabilized zirconia coating layer with the change of 1.0 to 22 mol% at the substrate temperature of 1
It was formed by the EB-PVD method at 073K. Thermal fatigue test of each obtained sample (1273K × 1 hour hold −423K × 1 hour hold)
Was served. Table 1 shows the results. The zirconia coating layer composed of tetragonal zirconia and cubic zirconia has excellent thermal fatigue properties, and good results were obtained when the Y concentration was in the range of 2.0 to 20.0 mol%.

[0091]

[Table 1] Example 8 A metal bonding layer made of a Ni-Co-Cr-Al-Y alloy was formed on a metal base material containing Ni as a main component by a plasma spraying method, and a Y element concentration of 8.5 mol% was further formed thereon. A stabilized zirconia layer,
EB-PV by changing the substrate temperature in the range of 673 to 1273K
It was formed by the D method. During the formation of the stabilized zirconia layer, the angle between the target and the substrate was changed in addition to the substrate temperature. The thermal fatigue test (1
273K x 1 hour hold-423K x 1 hour hold). The results are shown in Table 2. Sample Nos. 24 to 34 in Table 2 are listed as comparative examples with the present invention. Further, the orientation degrees A and B in Table 2 are values calculated from the X-ray diffraction intensity ratio of each sample based on the following formula.

Orientation degree A = {I (200) + I (002)} / {I (200) + I (002) + I (111)} Orientation degree B = {I (200) + I (002)} / {I (200) + I (002) + I (311)}

[Table 2] As is clear from Table 2, when the substrate temperature is on the low temperature side, or when the substrate temperature is on the high temperature side and the angle between the target and the substrate is shallow, the (111) plane or (311) plane orientation is obtained. It can be seen that the zirconia layer of (100) / (001) plane orientation is obtained when the zirconia layer is formed on the other hand and the substrate temperature is set to the high temperature side and the angle between the target and the substrate is increased. Then, it was confirmed that the sample having the zirconia layer with the (100) / (001) plane orientation has a better thermal fatigue life than the sample having the zirconia layer having a large amount of the (111) plane or the (311) plane orientation. Was done.

Example 9 Ni-Co-Cr- was formed on a metal substrate (IN738LC) containing Ni as a main component.
A metal bonding layer made of Al-Y alloy is formed by plasma spraying method, and stabilized zirconia with Y element concentration of 8.5mol% is used on it, and the substrate temperature is 1073K by EB-PVD method. / (001) -oriented zirconia layer with a thickness of 150 μm
Formed. Then, a zirconia layer having a (111) plane orientation having a thickness of 5 μm and a zirconia layer having a (100) / (001) plane orientation having a thickness of 10 μm were sequentially laminated thereon to form a zirconia multilayer laminated film.

On the other hand, as a reference example, a sample in which a zirconia layer was formed to a thickness of 250 μm while maintaining the substrate temperature at 1073 K was prepared.

SiC powder was applied to the zirconia heat shield layer of each sample according to these Examples and Comparative Examples by the sandblast method.
After spraying for 1 minute, thermal fatigue test (1273K x 1 hour hold −42
3K × 1 hour) and this operation was repeated until the zirconia layer was peeled off. The life of each sample was 1000 times or more in the thermal fatigue test.

In the sample according to Example 9, wear damage was suppressed by the (111) plane oriented zirconia layer, cracks and the like did not extend to the deep portion of the zirconia heat shield layer, and the zirconia test was repeated 1000 times or more. The heat shield layer did not peel off.
On the other hand, in the reference example, the zirconia heat shield layer peeled off within the oxide formed at the interface of the metal bonding layer within 200 times. From the above, it was clarified that the thermal fatigue properties of the zirconia thermal barrier layer having a zirconia multilayer coating structure having different orientations are not deteriorated by abrasion damage.

[0097]

As described above, since the thermal barrier coating material of the present invention has the ceramic thermal barrier layer excellent in adhesion and film characteristics, it has excellent peeling resistance, heat cycle resistance, and
FOD resistance and the like can be obtained, and life and service temperature can be remarkably improved. Therefore, even in an environment in which thermal stress and oxidation, and further stress acts on the material, such as the environment in which the gas turbine blade is used, excellent thermal insulation, oxidation resistance, and high temperature strength can be maintained for a long time. It is possible to provide a thermal barrier coating material that can be maintained over the entire length.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an embodiment of a first thermal barrier coating material of the present invention.

FIG. 2 is a cross-sectional view showing a main part manufacturing process of the thermal barrier coating material shown in FIG.

FIG. 3 is a cross-sectional view showing an embodiment of a second thermal barrier coating material of the present invention.

FIG. 4 is a cross-sectional view showing a modified example of the thermal barrier coating material shown in FIG.

5 is a cross-sectional view showing another modified example of the thermal barrier coating material shown in FIG.

FIG. 6 is a cross-sectional view showing an embodiment of a third thermal barrier coating material of the present invention.

FIG. 7 is a sectional view showing another embodiment of the third thermal barrier coating material of the present invention.

[Explanation of symbols]

 1 ... Metal substrate 2 ... Metal bonding layer 3 ... Ceramics heat shield layer 4 ... Intermediate layer 5 ... Ceramics inner layer by thermal spraying method 6 ... Ceramics surface layer by EB-PVD method 7 ... Stabilized zirconia shielding layer Thermal layer 8 …… (100) / (001) plane-stabilized zirconia layer 9 …… (111) plane-stabilized zirconia layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiroshi Tateishi, No. 1 Komukai Toshiba-cho, Sachi-ku, Kawasaki City, Kanagawa Prefecture, Corporate Research & Development Center, Toshiba (72) Inventor Masako Nakahashi, Komukai-Toshiba, Kawasaki-shi, Kanagawa Prefecture Town No. 1 Incorporated company Toshiba Research and Development Center (72) Inventor Kazuhide Matsumoto No. 1 Toshiba-cho, Fuchu-shi, Tokyo Inside Toshiba Fuchu factory

Claims (5)

[Claims] 1. A thermal barrier coating material comprising a metal base material, a metal bonding layer coated on the metal base material, and a ceramics thermal barrier layer coated on the metal bonding layer, wherein: An intermediate layer containing at least one selected from an active metal and an oxide of an active metal as a main component and a rare earth oxide content of 1% by weight or less is provided between the metal bonding layer and the ceramics heat shield layer. A thermal barrier coating material characterized in that 2. A thermal barrier coating material comprising: a metal base material; a metal bonding layer coated on the metal base material; and a ceramics thermal barrier layer coated on the metal bonding layer. The thermal barrier coating material is characterized in that the ceramic thermal barrier layer comprises an inner layer formed by a thermal spraying method and a surface layer formed by an electron beam PVD method. 3. A thermal barrier coating material comprising a metal substrate and a ceramic thermal barrier layer made of stabilized zirconia coated on the metal substrate directly or via a metal bonding layer, wherein The thermal layer has a stabilized zirconia layer,
The diffraction intensity ratio {I (200) + I (002)} / {I (200) + I (002) + I (111)} of X-ray diffraction on the surface of the stabilized zirconia layer is 0.9 to 1.
A thermal barrier coating material characterized by satisfying a range of 0. 4. The thermal barrier coating material according to claim 3, wherein the ceramic thermal barrier layer further has an orientation in the (111) plane direction with respect to the surface of the metal substrate or the surface of the metal bonding layer. A thermal barrier coating material having a zirconia layer. 5. The method for producing a thermal barrier coating material according to claim 1, wherein the step of coating the metal bonding layer on the metal base material and the step of forming an active metal layer on the metal bonding layer. A method of manufacturing a thermal barrier coating material, comprising: a step; and a step of coating the ceramic thermal barrier layer directly on the active metal layer or on the active metal layer subjected to an oxidation treatment. .