JP2948066B2 - Thermal stress relaxation type ceramic coated heat resistant member and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant member provided with a coating layer, and more particularly to a heat-relaxed ceramic-coated heat-resistant member and a method of manufacturing the same.

[0002]

2. Description of the Related Art The operating temperature of heat-resistant components, such as gas turbines for power generation, has been increasing for the purpose of improving efficiency. Is strongly desired. Against this background, heat-resistant alloys having high strength at high temperatures and excellent reliability have been developed, but their heat-resistant temperatures are limited. As a method of reducing the metal temperature of the substrate of a component used under high temperature conditions, ceramics having a low thermal conductivity (for example, Z
rO ₂ ) thermal barrier coating (Thermal
Barrier Coating: Abbreviated as TBC). TBC can reduce the base metal temperature of a part by 50 to 100 ° C.

[0003] However, T used under severe heat load conditions
BC tends to cause damage such as peeling of a coating layer such as a ceramic layer. In particular, heat load conditions are extremely severe in gas turbines with high operating temperatures for the purpose of improving efficiency,
Damage is more likely to occur.

Therefore, there are known examples of heat-resistant parts having various types of thermal stress-relieving ceramic coatings (for example, US Pat.
4,503,130, 4,095,003, 4,321,311). In these techniques, a ceramic coating layer having a structure in which a porous ceramic layer and a dense ceramic layer are laminated, or a coating layer made of columnar crystal ceramics has been proposed.

However, in the case of a ceramic coating layer having a multilayer structure, the residual strain in the multilayer ceramic coating layer is reduced by controlling the temperature of the base material during film formation and forming the porous ceramic layer by spraying a mixture of ceramic powder and polyester. This is a control, and damage occurs in the ceramic coating layer under extremely severe thermal load conditions. On the other hand, the durability of the coating layer made of columnar crystal ceramics is improved due to the thermal stress relaxation action, but the coating layer is separated from the boundary between the ceramic coating layer and the lower layer under extremely severe heat load conditions. .

As described above, in the heat-resistant component provided with the conventional thermal stress-relieving type ceramic coating layer, the ceramic coating layer is damaged under severe thermal load conditions where the operating temperature is high, and the heat shielding effect, which is the original purpose, is not obtained. It will not fully demonstrate.

[0007]

In the above-mentioned known technology, a ceramic coating layer having a thermal stress relieving function has been proposed. In addition, it was found that they did not always show sufficient heat resistance.

[0008] As a result of examining the thermal stress relaxation function, it was found that the ZrO ₂ -based ceramic coating layer having a small thermal expansion provided on the surface of the heat-resistant alloy base material having a large thermal expansion has a high thermal stress under severe thermal load conditions where the operating temperature is high. Analysis reveals tensile stress in the ceramic layer. This tensile stress shows a distribution which is maximum in the ceramic coating layer near the boundary between the ceramic coating layer and the lower layer (for example, the alloy coating layer). When the maximum stress value exceeds the strength of the ceramic coating layer, the ceramic layer is broken.

[0009] The ceramic coating layer has a variety of structures, unlike sintered ceramics. Such a difference in the structure causes a large difference in the fracture mode of the ceramic layer. In other words, in a porous layered structure having a weak bonding force between particles, the ceramic coating layer is worn and lost due to the phenomenon of particles falling off. Such a structure can be produced, for example, by spraying a known technique of a mixture of ZrO ₂ ceramic particles and polyester powder.

Next, in a layered structure having relatively strong bonding force between particles and having internal defects such as voids, the coating layer is broken in the longitudinal direction and cracks occur. This is because, in this structure, the strength of the ceramic coating layer is as small as several kg / mm ² , so that the ceramic coating layer is broken. Also, in such a particle stacking structure, there are many stacking faults of the particles in the lateral direction of the coating layer,
In a stress state in which a shearing force is generated (for example, when there is a temperature distribution and local heating is performed), cracks occur due to destruction in the lateral direction, and the coating layer is separated. Such a laminated structure can be produced by spraying ZrO ₂ -based particles.

Next, since the strength of the coating layer having a dense structure with almost no internal defects becomes equal to or higher than that of the sintered material, the coating layer having the strength equal to or higher than the tensile stress is formed vertically in the coating layer. No cracks occur due to directional or lateral fracture. Rather, since the adhesion between the ceramic coating layer and the coating layer thereunder (for example, an alloy coating layer) is smaller, peeling from the boundary is caused by shear stress. The coating layer having such a structure can be prepared by evaporating a ZrO ₂ -based material by an electron beam and setting the substrate (corresponding to a part) temperature in this case to 500 ° C. or less. On the other hand, when the dense ceramic is composed of a dense ceramic and the dense ceramic has a columnar structure, the strength of the ceramic coating layer is small at the boundaries (grain boundaries) of the respective columnar structures. Therefore, tensile stress causes fractures in the longitudinal direction of the coating layer along those grain boundaries, resulting in a very large number of microcracks. It is known that such a structure can be produced by evaporating a ZrO ₂ material with an electron beam and setting the substrate temperature in that case to 500 ° C. or more, preferably 700 ° C. or more.

As described above, the ZrO ₂ -based ceramic coating layer for TBC exhibits a specific fracture mode depending on its structure. When these various types of fracture are compared, a columnar type structure is most advantageous as the ceramic coating layer for TBC. In this case, thermal stress generated in the ceramic coating layer due to micro cracks in the ceramic coating layer is reduced, so that wear and peeling are less likely to occur,
It is expected that the heat shielding effect of TBC can be maintained for a long time. Such a fact can be found in the ASME meeting document ('91 -GT-
40).

[0013] However, a TB for a gas turbine having a very high operating temperature or a heat-resistant part of an aircraft engine
As a result of examining the columnar ceramic coating layer described above as C, the present inventors have clarified that the columnar ceramic coating layer does not always have sufficient heat resistance. That is, the TBC provided with the columnar-structured ceramic coating layer under the heating condition of a heat flux of ² to 4 MW / m ² , which is a severe condition of the heat load condition, has a thickness equal to the thickness provided below the ZrO ₂ -based columnar-structured ceramic layer. It was separated from the Al ₂ O ₃ layer near the boundary between the μm Al ₂ O ₃ layer and the alloy coating layer thereunder. Such a destructive phenomenon is consistent with the damage form of the above-mentioned published material ('91 -GT-40). Under the high heat flux heating conditions of the present inventors, the number of repeated heating and cooling up to separation was several tens of times. As described above, under extremely severe heating conditions, the columnar-structured ceramic coating layer expected to have a thermal stress relaxing action was not always sufficient.

The results of a study by the present inventors on such a result contrary to expectations will be described below. In the columnar structure ceramic coating layer, a single heating caused longitudinal microcracks to occur uniformly along each grain boundary of the columnar structure. Therefore, when used as a TBC for heat-resistant components, it is essential to provide a dense Al ₂ O ₃ layer as a barrier layer for environmental protection in order to prevent high-temperature corrosion and oxidation through such micro cracks. Since Al ₂ O ₃ and ZrO ₂ have a slight solid solubility limit, they mutually diffuse in a high-temperature heating state, and ZrO ₂
The ceramic-based coating layer and the Al ₂ O ₃ layer are in close contact with each other. However, there is no solid solubility limit between Al ₂ O ₃ and the alloy layer thereunder, and their adhesion is weak.

Therefore, the thick-film columnar-structure coating layer made of ZrO ₂ -based ceramics and the very thin environmental barrier layer made of Al ₂ O ₃ can be regarded as integrated when considering thermal stress. In the case of such a coating layer, despite the presence of microcracks at the boundary of the columnar structure and the thermal stress relaxation type ceramic coating layer, when the thermal load is large, the damage may be considered as follows. The thermal stress generated by the thermal load is the driving force for the destruction of the ceramic coating layer, but it is the destruction phenomenon that governs the damage.
A major factor is the mechanism of destruction due to thermal stress. Therefore, it is important to consider where the fracture origin is when considering the fracture mechanism. In the columnar structure type ZrO ₂ -based ceramic coating layer, the microcracks along the boundary of the columnar structure reach the boundary between the ZrO ₂ -based coating layer and the Al ₂ O ₃ layer.

As a result of the thermal stress analysis of the coating layer having such a structure, the thermal stress has a maximum tensile stress near the boundary between the ZrO ₂ -based coating layer and the Al ₂ O ₃ layer. Further, the maximum value increases as the thermal load condition becomes severe. on the other hand,
Considering the fracture mechanism, the coating layer having such a structure has a tip of a microcrack, that is, an end of each columnar body of the segmented ZrO ₂ -based coating layer at the boundary with the Al ₂ O ₃ layer. Is the starting point of destruction. The thermal stress around the fracture starting point is the largest. as a result,
It is considered that when the thermal load is severe, the thermal stress at the fracture starting point exceeds the material strength, and a fracture phenomenon occurs, leading to damage. In spite of the fact that the coating layer having this structure has the effect of relaxing thermal stress due to microcracks, it is presumed that there was a problem in the material configuration around the fracture starting point as a cause of damage under severe conditions of thermal load. That is, there is an Al ₂ O ₃ layer that is vulnerable to thermal shock below the fracture origin,
If the Al ₂ O ₃ layer is the number μm and thin cracks the Al ₂ O ₃ layer has occurred, it can be mentioned that there is a boundary between the intensity weakest the Al ₂ O ₃ layer and the alloy coating layer.

The ZrO ₂ -based coating layer is formed by adding Y ₂ O ₃ , Mg to ZrO _2.
The ceramics are excellent in thermal shock resistance by adding a stabilizer such as O and CaO for preventing phase transformation. However, in the case of Al ₂ O ₃ , the thermal shock resistance is very poor due to α⇔γ phase transformation. Therefore, the Al ₂ O ₃ layer is a material that is easily broken when the thermal load is turned on / off. Although the effectiveness of the coating layer having this structure is recognized in terms of relaxation of thermal stress, the fact that the Al ₂ O ₃ layer is present at the starting point of the fracture and its A
that there is a boundary with the alloy coating layer immediately below the l ₂ O ₃ layer,
This is a reason why sufficient durability is not shown under severe conditions with a large heat load. The Al ₂ O ₃ layer is a barrier layer essential for obtaining corrosion resistance as described above, and omitting the Al ₂ O ₃ layer is impossible with a columnar texture type ZrO ₂ ceramic coating layer. .

From the results of the study by the present inventors as described above,
The inventors have paid attention to a fracture starting point that controls the fracture of the coating layer using the thermal stress as a driving force, and have arrived at the present invention. In other words, it is very effective to cause microcracks along the columnar structure boundary in the columnar structure type ZrO ₂ -based ceramics coating layer in order to alleviate the thermal stress and reduce the maximum tensile stress. However, when considering the fracture mechanism, the material at the tip of the microcrack and the material configuration around it become very important.

As a method for forming a columnar structure type ZrO ₂ -based ceramic coating layer having microcracks, there is a method in which a ZrO ₂ -based ceramic material is electron-beam evaporated while the temperature of the substrate is maintained at 538 to 816 ° C. It has been revealed (US AT 4095003). Similarly, at 538 ° C. or lower, a ZrO ₂ ceramic coating layer having a dense structure can be obtained. Therefore, first, a ZrO ₂ -based material is vapor-deposited at a substrate preheating temperature of 538 ° C. or less on the alloy coating layer having an Al ₂ O ₃ layer having a thickness of several μm on the outermost surface. Is preheated to 538 to 816 ° C., and the ZrO ₂ -based material is evaporated to form a ZrO ₂ -based coating layer having a different composition including a dense structure and a columnar structure.
However, in this case, after the lower ZrO ₂ coating layer composed of a dense structure is formed, the substrate temperature is increased to increase the Zr of the upper columnar structure.
When the rO ₂ coating layer is formed, the lower ZrO ₂ coating layer composed of a dense structure generates thermal stress (tensile) due to heating during the preheating of the base material at a high temperature, and the lower ZrO ₂ coating layer has a vertical crack. Will occur. Then, an upper ZrO ₂ coating layer composed of a columnar structure is formed thereon.

Therefore, the Zr having a two-layer structure in such a state is
In the case of a TBC having an O ₂ -based coating layer, a Zr having a columnar structure is formed during heating as a post-treatment or when used as a turbine component.
Although vertical cracks occur along the columnar boundaries of the O ₂ coating layer, there are also vertical cracks in the dense ZrO ₂ -based coating layer under the O ₂ coating layer, and the two-layer ZrO ₂ -based coating layer of the present invention has Not enough. That is, Al ₂ having a thickness of several μm
A crack tip is formed near the boundary between the O ₃ layer and the alloy coating layer below the O ₃ layer, and the starting point of fracture due to thermal stress is in a portion where damage (peeling, etc.) of the ZrO ₂ -based coating layer is likely to occur.

An object of the present invention is to provide a heat-relaxing ceramic-coated heat-resistant member having sufficient durability under severe conditions of high operating temperature and high thermal load, a method of manufacturing the same, and An object of the present invention is to provide a ceramic-coated gas turbine moving blade and a stationary blade.

[0022]

In order to achieve the above object, the present invention provides a heat-resistant member having a heat-resistant coating layer provided on a surface of a heat-resistant alloy base material containing Ni and Co as a main component. Is provided on the base material, a metal layer made of an alloy having better high-temperature corrosion resistance and oxidation resistance than the base material, and an Al ₂ O ₃ ceramic thin film layer and a dense structure sequentially formed thereon. ZrO ₂ ceramic coating layer and Z of columnar structure
An rO ₂ -based ceramic coating layer is provided, and a ceramic-coated heat-resistant member in which cracks occur in the thickness direction along the boundary of the columnar structure only in the ZrO ₂ -based ceramic layer having the columnar structure. In the ceramic-coated heat-resistant member, a mixed layer of a metal and a ZrO ₂ -based ceramic having better high-temperature corrosion resistance and oxidation resistance than the substrate is provided between the substrate and the metal layer, or a metal layer is formed from the metal on the substrate side. It is preferable to provide a mixed layer in which the mixing ratio is continuously changed on the ZrO ₂ -based ceramic on the side, and it is preferable to further provide a metal layer between the base material and the mixed layer.

[0023] The metal layer is mainly composed of Co and / or Ni, Cr, Al, well that an alloy containing one or more selected from Y, the ZrO ₂ based ceramics, a ZrO ₂ As a main component, it is preferable to include at least one selected from Y ₂ O ₃ , MgO, and CaO.

The dense ZrO ₂ -based ceramic layer comprises:
The thickness is in the range of 10 to 60 μm and (Z of columnar structure
The value of (thickness of rO ₂ -based ceramic layer) / (thickness of dense ZrO ₂ -based ceramic layer) satisfies the relationship of 1.5 to 15 and more dense ZrO ₂ -based and columnar ZrO _2.
It is preferable that the total sum of the base ceramic layers is in a range of 400 μm or less, and the cracks formed in the ZrO ₂ -based ceramic coating layer having the columnar structure have an opening width of 5 to 20 μm and a columnar structure. It is preferable that the size of each of the pillars constituting the above is within the range of 20 to 200 μm.

The present invention also relates to a method for manufacturing a heat-resistant member comprising a heat-resistant coating layer provided on the surface of a heat-resistant alloy base material containing Ni and Co as a main component. A step of forming a metal layer made of an alloy having excellent corrosion resistance and oxidation resistance by plasma spraying, a step of sequentially forming an Al ₂ O ₃ -based ceramic thin film layer thereon,
After performing a step of forming an O ₂ -based ceramics layer by an electron beam evaporation method and a step of forming a ZrO ₂ -based ceramics layer by a method of simultaneously performing electron beam evaporation and ion beam irradiation, a columnar structure is formed by heating. A crack is formed in the ZrO ₂ -based ceramic layer in the thickness direction along the boundary of the columnar structure.

In the above-mentioned manufacturing method, the ion beam preferably has an acceleration voltage in the range of 1 to 50 kV, and the main element constituting the ion beam is preferably oxygen.

In order to achieve the above and other objects, the present invention provides a gas turbine rotor blade and stationary blade component made of a heat-resistant alloy containing Ni and Co as a main component, and the entire surface of a portion exposed to combustion gas. Alternatively, a metal layer made of an alloy having better high-temperature corrosion resistance and oxidation resistance than the heat-resistant alloy is provided on a part thereof, and an Al ₂ O ₃ -based ceramic thin film layer is sequentially formed thereon.
Providing a ZrO ₂ -based ceramics coating layer having a dense structure, and a ZrO ₂ -based ceramics layer having a columnar structure, and
A ceramic-coated gas turbine rotor blade and a stationary blade in which cracks occur in the thickness direction along the boundary of the columnar structure only in the columnar structure ZrO ₂ -based ceramic layer.

In the above description, a part of the gas turbine rotor blade and the stationary blade exposed to the combustion gas is a leading edge of the blade, and another part exposed to the combustion gas is a heat-resistant alloy. A metal layer made of an alloy having better high temperature corrosion resistance and oxidation resistance can be provided, and a ZrO ₂ ceramic layer can be provided on the metal layer. , Polycrystalline material, unidirectional solidified material,
Alternatively, a single crystal material is preferable.

Further, according to the present invention, in a heat-resistant member having a heat-resistant coating layer provided on the surface of a heat-resistant alloy base material containing Ni and Co as a main component, the outermost ZrO ₂ -based ceramic coating layer is formed of a ZrO ₂ ceramic column. Columnar structure (called secondary columnar structure) consisting of an aggregate of structures (called primary columnar structure)
Has obtained a heat-relaxation-type heat-resistant covering member having a hybrid columnar structure composed of one or more columnar structures (referred to as a tertiary columnar structure). ZrO ₂ -based ceramics mainly contain ZrO ₂ , CdO, MgO,
Those containing at least one selected from Y ₂ O ₃ are preferable.

The primary columnar structure is a fine structure having a width of 1 to 10 μm, and these are aggregated into a columnar body having a width of 20 to 200 μm to form a secondary columnar structure. A tertiary columnar structure in which one or a plurality of aggregates are separated by minute voids (microcracks: width 5 to 20 μm). Tertiary column width is 20-600 μm
It is. Each columnar structure has a direction substantially parallel to the thickness direction of the coating layer. In the ceramic coating layer having such a structure, thermal stress caused by a difference in thermal expansion between the ceramic coating layer and the substrate, which is generated in a direction perpendicular to the thickness direction of the coating layer, is remarkably reduced. The reason for this is that the primary to tertiary roles of the columnar structures are such that the growth direction of many crystals is almost aligned in one direction in the first order, so that the strength in the growth direction is high and the direction perpendicular to the growth direction is high. Then the strength is small. It has a so-called fiber reinforced structure,
When an external force due to thermal stress or the like is applied, minute damage is caused in a direction of weak strength, and as a result, an effect of relaxing the external force (thermal stress) is generated. The secondary columnar structure is an aggregate of the primary columnar structure, and such an aggregate is aligned in the growth direction and in one direction of the tissue, and the bonding force at the boundary of each secondary columnar structure has a strength in the growth direction. Smaller than. Therefore, when an external force (thermal stress) is applied, a minute gap (microcrack) is generated at the boundary between the secondary columnar structures having a small bonding force, and the effect of reducing the external force is exerted. The tertiary columnar structure is an aggregate of one or a plurality of secondary columnar structures, and there are minute voids (microcracks) at the boundaries thereof. Further, the thermal stress is reduced (the thermal stress is reduced) by the dimensional effect due to the minute division of the coating layer into the size of the tertiary columnar structure. As mentioned above,
In the heat-resistant member provided with the ceramic coating layer of the present invention, even when used for a heat-resistant component having a high operating temperature and a high heat load condition,
Due to the thermal stress relaxation effect in which the primary, secondary and tertiary columnar structures are hybridized, it can be used even under conditions where various known ceramic coating layers are damaged. FIG. 1 is a schematic cross-sectional view of a heat shield coating provided with such a hybrid columnar structure ceramic coating layer of the present invention. There is no particular restriction on the layer structure of the lower portion of the ceramic coating layer, the Al ₂ O ₃ layer at the bottom of the ceramic coating layer of the present invention as shown in FIG. 1, the lower portion of the Al ₂ O ₃ layer MCrAlY (M Is either Co or Ni,
Or a combination) layer. Al ₂ O
_{The three} layers and the MCrAlY layer have an effect of preventing external oxidation and high-temperature corrosion through microcracks.

The important points in obtaining the coating layer of the present invention as shown in FIG. 14 are that the film is formed while applying energy to the ceramic layer during film formation as described below, To strengthen the adhesion between the layer and its lower layer. Without such means,
The ceramic coating layer of the present invention cannot be obtained. First, as a general method for applying energy to a ceramic layer during film formation, there is thermal energy by heating a substrate. The ZrO ₂ based ceramic was melted by an electron beam or the like, a physical deposition method to form a film by adhering vaporized particles of ZrO ₂ based ceramic on the substrate surface (Physic
In al Vapor Deposition (PVD), there is a method in which, in addition to the energy of the evaporated particles, the temperature of the adhered substrate is increased so that the particles adhered to the substrate are crystal-grown and the growth method is controlled. In this case, when the temperature of the base material is low, the crystal growth of the formed ceramic layer after adhesion of the evaporating particles is difficult to progress, so that the structure is composed of fine crystal grains. As a result of conducting the same study by the present inventors, an electron diffraction experiment using a transmission electron microscope of the ceramic coating layer did not show a specific diffraction point indicating crystal growth, and a substantially ring-shaped diffraction line was obtained. It was found that the crystal grains were fine. That is, a columnar structure cannot be obtained. On the other hand, 700
When the film was formed at a substrate temperature condition of not less than ° C., a ceramic coating layer having a columnar structure of several μm was obtained due to crystal growth after the attachment of the evaporated particles. However, in this case, the ceramic coating layer had only a columnar structure having a substantially uniform size (several μm). Further, the substrate temperature is increased (1000
C) When the film was formed, the size of the columnar structure was only slightly larger than that at 700C. Further, in the film formation at 1000 ° C., cracks were generated in which the surface of the ceramic coating layer was divided into a size of several millimeters during cooling after the film formation, and peeling of the ceramic coating layer was observed in some parts. As described above, heating the substrate used as an energy imparting method for forming a ZrO ₂ ceramic by PVD only provides a columnar ceramic structure of several μm. In the heat treatment after the film formation, the width of the cracks is large (0.1 to 0.5 mm) and divided by cracks because the ceramic coating layer has a uniform structure composed of columns having a width of several μm. The size also increases.

On the other hand, the present inventors have paid attention to a method of obtaining a first to third hybrid columnar structure ceramic coating layer because the method for applying energy to the ceramic coating layer during film formation is an ion-imprinting method. Beam energy. The ion beam energy determines the ion beam implantation depth depending on the acceleration voltage. The acceleration voltage noted by the present inventors is 1 to 50 kV, and an injection effect of several hundreds of square meters can be expected with such an acceleration voltage. Further, by simultaneously performing evaporation and ion beam irradiation, when forming a film at an evaporation rate of several tens of Å / sec, the energy of the ion beam can be given from the surface of the film to a depth of several hundred Å below. . Most of the energy of the implanted ion beam is changed to thermal energy, so that the ion beam is heated to a depth of several hundred square meters from the film formation surface. It should be noted that the important point here is that the thermal energy of the implanted ion beam is easily concentrated only in the vicinity of the film formation surface because the ZrO ₂ -based ceramics targeted by the present inventors have low thermal conductivity. . Therefore, ZrO ₂
In PVD in which vapor deposition and ion beam irradiation are performed simultaneously in film formation of a system ceramic, large thermal energy can be applied to the vicinity of the film formation surface.

Next, the ion beam also has a unique action in improving the adhesion between the ceramic coating layer and the lower layer. That is, the mixed layer of the lower layer and the formed ceramic layer is formed at the boundary by the sputtering action using the ion beam. The formation of the mixed layer using an ion beam enhances the adhesion. It is desirable that the main element constituting the ion beam is oxygen. As a reason,
It is possible to obtain a stoichiometric ceramic which does not prevent oxygen deficiency during the deposition of the ZrO ₂ -based ceramic.

Using a process having such characteristics,
Further, by roughening the roughness of the underlayer of the ceramic coating layer (surface roughness Rmax. 50 to 80 μm), the hybrid columnar ceramic coating layer of the present invention is obtained as follows. In the PVD method using only evaporation, a uniform structure composed of columnar structures on the order of several μm can be obtained by increasing the temperature of the substrate (600 to 800 ° C.).
However, it is difficult to obtain a columnar structure (secondary columnar shape) on the order of 20 to 200 μm composed of an aggregate of columnar structures (primary columnar shape) on the order of several μm. The reason is that when the surface roughness of the lower layer of the ceramic coating layer is reduced in order to obtain a secondary columnar shape, the ceramic coating layer is easily peeled off. Further, even when the structure is not peeled, the structure is almost columnar with a size of several μm, and a columnar shape (primary columnar shape) of 20 μm to 200 μm (secondary columnar shape), which is an aggregate of a columnar shape (primary columnar shape) of several μm, is hardly formed. Further, when the substrate temperature is 100
Even when the temperature is further increased to 0 ° C., a clear secondary columnar shape is unlikely to occur, and as described above, the ceramic coating layer peels off during cooling after film formation.

As described above, the secondary columnar structure constituting the hybridized columnar structure of the present invention is a P-type column formed only by the conventional vapor deposition.
In VD, it was regarded as a defect of the coating layer, and rather, care was taken not to form such a structure. And a columnar shape of the order of several μm (the present inventors call it a primary columnar shape).
A highly reliable thermal shielding coating was obtained only by forming a uniform ceramic coating layer consisting of only the thermal stress relaxing action (US Pat. No. 4321310). This is because the applied energy at the time of film formation and the adhesion to the lower layer are all small. The present inventors could not form by the conventional film forming method. Alternatively, even if an attempt is made to form a coating layer, on the contrary, it becomes a defect, but by combining ion beam and vapor deposition, and by roughening the lower layer, several μm, which cannot be formed conventionally, can be obtained. A method for obtaining a hybrid columnar structure ceramic coating layer having a primary columnar shape and a secondary columnar shape of 20 to 200 μm as an aggregate thereof and having excellent thermal stress relaxation characteristics has been found.

Further, the member having the obtained hybridized columnar-structured ceramic coating layer is subjected to a uniform heating treatment, so that the thermal stress caused by the difference in thermal expansion between the base material and the ceramic coating layer causes the boundary between the secondary columnar boundaries to be formed. A microcrack is formed in part, and a tertiary columnar structure composed of one or a plurality of secondary columnar aggregates can be obtained. Even in this case, in the method of the present inventors, since the strength between the secondary columnar structures is lower than that between the primary columnar structures, fracture due to thermal stress occurs along a part of the boundary of the secondary columnar structure. I do. The width of the microcracks between the tertiary columnar structures thus formed is 5
ミ ク ロ 20 μm, and the microcracks also have an effect of relaxing thermal stress. The tertiary pillars divided by microcracks are composed of one or a plurality of secondary pillars, each having a size of 20 to 600 μm. In the method of the present invention, the heating temperature is set at 850 to 1200 in order to generate microcracks due to thermal stress.
C is desirable. By uniform heating in such a temperature range, a tertiary columnar structure can be obtained by thermal stress due to a difference in thermal expansion between the base material and the ceramic coating layer. The heating temperature is desirably set to the heat treatment temperature of the superalloy used as the base material.

On the other hand, the present inventors uniformly heat-treated a member having a ceramic coating layer composed of a primary columnar structure and formed by PVD only for vapor deposition. As a result, cracks were observed due to the destruction of the ceramics coating layer due to thermal stress. Is several hundred μm to several mm
And the width of the microcracks is 0.1 to 0.1.
It was as large as 5 μm. Although the ceramic coating layer divided into such large units is expected to relieve some thermal stress, its effect is smaller than that of the hybrid columnar ceramic coating layer of the present invention.

The elements constituting the ion beam used in the present invention are not particularly limited.
_The stoichiometric composition of oxygen-deficient ceramics
Oxygen is desirable in obtaining the ZrO _2. It should be noted that there is no particular problem even if an ion beam such as N ₂ or Ar is used.

According to the method of the present invention as described above, a hybrid columnar ceramic coating layer of the present invention comprising primary to tertiary columnar structures is obtained. Further, since the member provided with the coating layer of the present invention has excellent thermal stress relaxation characteristics, when used as a heat shielding coating for a high-temperature component of a gas turbine having a high combustion gas temperature, the gas turbine is repeatedly started and stopped or has a long duration. Even when used for a long time, damage such as peeling of the ceramic coating layer hardly occurs, and the effect of reducing the temperature of the base material, which is the purpose of the thermal shielding coating, can be maintained.

According to the present invention, there is provided a platform having a wing portion, a flat portion connected to the wing portion, a shank portion connected to the platform, fins formed on both sides of the shank portion, and fins formed on both sides of the shank portion. In a moving blade for gas turbine having a continuous dovetil, a heat-resistant coating layer is provided on the blade surface, and the configuration of the heat-resistant coating layer is superior to the base material in high-temperature corrosion resistance and oxidation resistance. A metal layer made of an alloy is provided, and Al ₂ O ₃
-Based ceramics thin film layer, ZrO composed of dense granular structure
₂ ceramic coating layer and the ZrO ₂ based ceramic coating layer of the columnar texture is provided, and the columnar texture ZrO ₂
It is characterized in that cracks occur in the thickness direction along the boundaries of the columnar structure only in the system ceramic layer.

Further, a heat-resistant coating layer is provided on the wing surface, and the ZrO ₂ -based ceramic layer constituting the heat-resistant coating layer is composed of a large number of columnar structures (primary columnar structures) of ZrO ₂ -based ceramics. One or more of the columnar structures (secondary columnar structures) is formed of an aggregated columnar structure (tertiary columnar structure), and the tertiary columnar structure is divided by fine cracks.

According to the present invention, there is provided a gas turbine in which fuel gas compressed by a compressor impinges on a moving blade provided on a disk through a stationary blade to rotate the moving blade. The moving blade and the stationary blade have three or more stages. At least the first stage of the rotor blade has a wing portion, a platform having a flat portion connected to the wing portion, a shank connected to the platform, fins including protrusions provided on both sides of the shank, and connected to the shank. A dovetail, and the heat-resistant coating layer described above is provided on at least one of the blade surfaces of the moving blade and the stationary blade.

According to the present invention, there is provided a gas turbine in which combustion gas compressed by a compressor is caused to collide with a moving blade implanted on a disk through a stationary blade to rotate the moving blade.
The combustion gas temperature is 1500 ° C. or higher, the blades have three or more stages, the combustion gas temperature at the first stage inlet of the blades is 1300 ° C. or more, and the first stage of the blades has a total length of 20 ° C.
0 mm or more, the first stage of the moving blade is a wing, a platform having a flat portion connected to the wing, a shank portion connected to the platform, a fin comprising projections provided on both sides of the shank portion, The heat-resistant coating layer described above is provided on at least one blade surface of a moving blade and a stationary blade for a gas turbine having a dovetil connected to a shank portion.

The present invention provides a gas turbine driven by combustion gas flowing at high speed, an exhaust heat recovery boiler for obtaining steam from combustion exhaust gas of the gas turbine, a steam turbine driven by the steam, the gas turbine and the steam turbine. And a generator driven by the gas turbine, wherein the gas turbine has three or more moving blades, the temperature of the first stage of the moving blade of the combustion gas is 1300 ° C. or more, and the temperature of the combustion exhaust gas at the turbine outlet is Is 560 ° C. or higher, and 53
The steam turbine is a high-low pressure integrated type, the steam temperature to the first stage of the steam turbine blade is 530 ° C. or more, and the power generation capacity of the gas turbine is 50,000 KW or more. The power generation capacity of the steam turbine is 30,000 kW or more, the total thermal efficiency is 45% or more, the first stage of the moving blade has a total length of 200 mm or more, and the first stage of the moving blade is connected to the wing and the wing. A platform having a flat portion, a shank portion connected to the platform, fins formed of protrusions provided on both sides of the shank portion, and a dovetail connected to the shank portion; and at least one of the moving blade and the stationary blade Characterized by having the above-mentioned heat-resistant coating layer on the wing surface.

[0045]

According to the present invention, ceramics having various structures (Zr
For O ₂ system) coating layer performs a high-temperature heat load test simulating the operating temperature is higher severe thermal load conditions, ZrO ₂ based ceramic coating layer is a thermal stress relaxation type ceramic coating layer having a variety of purposes and effects A heat-resistant part having a two-layer structure of a columnar structure and a dense structure was found. With such a two-layered ZrO ₂ -based ceramic coating layer, when the thickness is the same, the thermal stress generated in the ZrO ₂ -based ceramic layer is larger than that of a columnar structure-type single layer having microcracks. However, by increasing the strength around the starting point of the destruction caused by the thermal stress as the driving force, the destruction can be made difficult to occur, and the ceramic coating layer can be prevented from being damaged.

[0046] That is, by the structure in which a ZrO ₂ based coating layer of dense tissue in the lower part of the columnar texture type ZrO ₂ based ceramic coating layer having a micro-crack in the present invention, a portion to be a starting point of fracture Inside the ZrO ₂ -based coating layer. Such a coating layer having the structure of the present invention is a ZrO ₂ -based ceramic having a thermal shock resistance superior to Al ₂ O ₃ at a fracture origin due to thermal stress, and has a high strength because of its dense structure. Further, unlike the case of a thin Al ₂ O ₃ layer having a thickness of several μm, the boundary with the alloy coating layer having weak adhesion is not provided around the tip of the micro crack. Therefore, in the coating layer of the present invention, it is possible for the ZrO ₂ -based coating layer to withstand a larger heat load as compared with a single layer having a columnar structure having microcracks.

Further, a method of forming the ZrO ₂ -based ceramic coating layer having a two-layer structure of the present invention is also important. That is, as a method of controlling the structure of the coating layer during the formation of the ZrO ₂ -based coating layer, attention was paid to a method of applying energy to the portion at the same time as the film formation instead of the substrate temperature. As a result of various studies on the compatibility with the deposition process as an energy source, it was found that an ion beam was most suitable.
The deposition of the ZrO ₂ -based material itself is a method of irradiating a base material with an ion beam using electron beam deposition, which is a known method. The ion beam is a high-density energy source, and the energy is applied only to the outermost surface of the irradiated material. Therefore, by simultaneously performing ion beam irradiation and vapor deposition, even if the film is formed at a low substrate temperature, if the energy of the ion beam is sufficiently large, the coating layer formed has a columnar structure.

This is attributable to the fact that the energy due to the irradiation of the ion beam has the same effect as the residual heat of the substrate in the case of only the vapor deposition. Furthermore, in the present method, a mixing layer in which the components of the respective coating layers are mixed can be formed between the ZrO ₂ coating layer and the lower coating layer by the injection effect of the ion beam irradiation, and an extremely excellent adhesion can be obtained. Can be Therefore, as a production method of the present invention, first, ion beam irradiation and deposition of a ZrO ₂ -based material are simultaneously performed on the alloy coating layer having an Al ₂ O ₃ layer of several μm on the outermost surface. To form Thereafter, the energy of the ion beam is reduced, or the energy is reduced to zero and Z
An rO ₂ -based material is deposited to form a dense ZrO ₂ -based coating layer at a low substrate temperature.

Thereafter, by increasing the energy of the ion beam and using it together with the deposition of a ZrO ₂ -based material,
Energy is applied only to the vicinity of the lower portion of the coating layer being formed, and a ZrO ₂ -based coating layer having a columnar structure is formed while the temperature of the base material itself is 500 ° C. or less. According to such a production method of the present invention, since the substrate temperature is low even when forming a dense ZrO ₂ -based coating layer and any coating layer having a columnar structure,
In particular, cracks do not occur in the dense ZrO ₂ -based coating layer serving as the lower layer. By subjecting the TBC having a coating layer having a two-layer structure having a different structure on the outermost surface to heat treatment as a post-treatment, cracks in the longitudinal direction can be generated only in the upper coating layer along the boundary of the columnar structure. it can.

The T produced by the production method of the present invention as described above.
In the case of BC, the ZrO ₂ -based coating layer has a function of relieving the thermal stress, has a high reliability of the material around the starting point of the destruction caused by the thermal stress, and is hardly peeled off by the destruction.
In the above-described manufacturing method of the present invention, it is preferable to use oxygen ions as the ion beam. The reason is that in the case of deposition of a ZrO ₂ -based material, an oxygen ion beam is desirable in order to obtain ZrO _2, which tends to be ZrO _{2 -x} and close to the stoichiometric value. It should be noted that there is no particular problem even if an ion beam such as N ₂ or Ar is used. Further, the reason why the ion beam is used is that, in controlling the structure of the ZrO ₂ -based coating layer, the speed of energy response due to the irradiation of the ion beam is raised. That is, as soon as the ion beam is turned on, its energy is reflected in the film formation state,
If it is FF or small, its energy will immediately disappear. Such a high response speed is very difficult to achieve by heating a large-sized product such as a wing in a vacuum.

[0051]

The present invention will be described below in more detail with reference to examples.

Example 1 As an example of the present invention, a TBC having a _two -layered ZrO ₂ -based coating layer on the outermost surface was prepared as follows.
The heat resistance was examined. Ni-base superalloy (Rene'-80: Ni-14% Cr-4% Mo-
4% W-3% Al-5% Ti-9.5% Co)
An MCrAlY alloy (Co-32% Ni-21)
% Cr-8% Al-0.5% Y 2) powder was used to form a bonding layer by plasma spraying in a reduced pressure atmosphere. The condition is A
The alloy powder is injected into a plasma jet (50 kW) formed by using an r-7% H ₂ mixed gas and sprayed, and the atmospheric pressure during the spraying is about 50 Torr. In addition, as a pretreatment, degreasing and cleaning of the test piece base material and Al
Blasting with ₂ O ₃ grit is performed. The thickness of the formed bonding layer is 100 μm.

Thereafter, a two-layered ZrO ₂ -based coating layer of the present invention was formed on the surface of the test piece substrate provided with the bonding layer using a film forming apparatus having an evaporation source and an ion beam source. ZrO ₂ -6% Y ₂ O ₃ was used as the material of the evaporation source, and oxygen ions were used as the ion beam. As the film formation method,
First, an oxygen ion beam (acceleration voltage 10
keV), sputter cleaning of the bonding layer surface with oxygen ions and surface oxidation of the bonding layer surface with oxygen ion implantation were performed. In this case, the pressure of the film forming chamber is 10 ⁻⁵ Torr, and the substrate temperature is about 50 ° C. As a result, the surface of the bonding layer is cleaned, and
Al ₂ O ₃ was formed.

Thereafter, ZrO ₂ -6% Y ₂ O ₃ was vapor-deposited while irradiating with oxygen ions. The output of the evaporation source was 10 kW, and was measured with
Vapor deposition was performed while ion irradiation was performed to a thickness of. In this case, the pressure of the film forming chamber is 5 × 10 ⁻⁵ Torr.
And the substrate temperature is about 50 ° C. As a result, a mixed layer of Al ₂ O _{3 on} the surface of the bonding layer and ZrO ₂ -6% Y ₂ O _{3 as} a deposition material was formed. The thickness of this layer was analyzed to be about 0.1 μm, and about 0.4 μm
ZrO ₂ -6% Y ₂ O ₃ coating layer was formed.

Thereafter, the irradiation of oxygen ions is stopped, and Zr
Of O ₂ -6% Y ₂ O ₃ deposited only was performed.

In this case, the pressure of the film forming chamber is 5 × 1
0 ^-5 Torr and the substrate temperature is about 100 ° C. As a result, a dense coating layer made of ZrO ₂ -6% Y ₂ O ₃ was formed, and its thickness was controlled to 20 μm by a film thickness monitor. Thereafter, the deposition of ZrO ₂ -6% Y ₂ O ₃ is continued,
Further, irradiation with an oxygen ion beam (acceleration voltage: 10 keV) was performed, and vapor deposition and irradiation were performed simultaneously. In this case, the pressure of the film forming chamber is 7 × 10 ⁻⁵ Torr, and the substrate temperature is about 150 ° C. In this state, film formation was continued to form a coating layer of about 130 μm on the dense ZrO ₂ -6% Y ₂ O ₃ coating layer. In this case, the ZrO ₂ -6% Y ₂ O ₃ coating layer has a columnar structure, and the size of each column constituting the columnar structure is 20 to 200 μm.

The reason why the columnar structure is formed as described above is ion irradiation. The columnar structure is formed by epitaxial growth even in the high melting point material ZrO ₂ -6% Y ₂ O ₃ due to the energy of the irradiated ion beam. can get. The TBC having the coating layer formed by each of the above-described film forming processes is subjected to a heat treatment as a next step to give a thermal stress, thereby generating a micro crack in the ceramic coating layer for the purpose of relaxing thermal stress. I let it. The heat treatment is heating in the air at 1000 ° C. for 1 hour.

As a result, a crack having a width of 5 to 20 μm is generated along the boundary of the columnar structure of the ZrO ₂ -6% Y ₂ O ₃ coating layer on the outermost surface side composed of the columnar structure, and the columnar structure is divided into individual columns. It was done. The microcracks did not occur in the dense ZrO ₂ -6% Y ₂ O ₃ coating layer under the columnar structure, but stopped at the boundary between the columnar structure and the dense structure. The state of such micro cracks is
This is because, in the ceramic coating layer having the two-layer structure of the present invention, the strengths of the coating layers of the respective structures are significantly different.

The thus-prepared ZrO having a two-layer structure
FIG. 1 is a schematic cross-sectional view of a TBC having a _2- system coating layer on the outermost surface.
Shown in The surface was observed by SEM. In the TBC manufactured according to the present invention, the ZrO ₂ -based ceramic coating layer has a two-layer structure, and the outermost surface layer has a columnar structure of 20 to 20.
There is an open crack having a width of 5 to 20 μm at the boundary of the columnar structure of 0 μm, and the ZrO ₂ -based coating layer as a lower layer thereof has a dense structure without cracks or the like. In addition, this precise Z
Below the rO ₂ -based coating layer is an Al ₂ O ₃ layer, below it is a CoNiCrAlY alloy coating layer, and below the alloy coating layer is a Ni-based heat-resistant alloy.

FIGS. 2 to 5 show a ZrO ₂ -6% Y ₂ O ₃ ceramic coating layer having a two-layer structure produced by the production method of the present invention.
It is a cross section of a TBC of the present invention. The T of the present invention of FIG.
In BC, after pretreatment of a Ni-base heat-resistant alloy (Rene '80), C was sprayed under reduced pressure atmosphere under the same conditions as above.
o-32% Ni-21% Cr-8% Al-0.5% Y and mixed powder of ZrO ₂ -6% Y ₂ O ₃ (mixed ratio: 1/1) was sprayed, the coating layer of 100μm thickness Thereafter, Co-32% is sprayed under reduced pressure atmosphere under the same conditions as above.
Ni-21% Cr-8% Al-0.5% Y 2
A coating layer having a thickness of 0 μm was formed. Thereafter, in the same manner and under the same conditions as above, an Al ₂ O ₃ layer and a dense Z
An rO ₂ -6% Y ₂ O ₃ coating layer is formed to a thickness of 20 μm, and a ZrO ₂ -6% Y ₂ O ₃ coating layer having a columnar structure is formed thereon to a thickness of 130 μm. Was performed. As a result, ZrO ₂ -6% Y of the columnar structure on the outermost surface
_{The 2} O ₃ coating layer had a columnar structure having a size of 20 to ₂₀₀ μm, and an opening crack of 5 to 20 μm was formed at the columnar boundary.

In the TBC of the present invention shown in FIG. 3, in the method of manufacturing the TBC shown in FIG. 3, when forming the coating layer on the Ni-base heat-resistant alloy, first, Co-32% Ni-21% Cr-8% Al-
Spray only 0.5% Y alloy powder and then ZrO ₂ -6
% Y ₂ O ₃ powder was gradually increased, and finally the mixing ratio between the alloy and the ceramic was set to 1/1. Thereafter, the TBC of the present invention was produced in the same manner as in the present invention shown in FIG. In the TBC of the present invention shown in FIG. 4, Co-32% Ni-21% C
r-8% Al-0.5% Y alloy powder is sprayed, 50μm
After forming a coating layer having a thickness, each coating layer was formed thereon similarly to the TBC of FIG. The T of the present invention shown in FIG.
In BC, Co-32% Ni-21% Cr-8% A is sprayed on the surface of the Ni-base heat-resistant alloy in the same reduced pressure atmosphere as above.
After spraying l-0.5% Y alloy powder to form a coating layer having a thickness of 50 μm, each coating layer was formed thereon in the same manner as the TBC of FIG.

Each of the TBCs of the present invention shown in FIGS.
It has a ZrO ₂ -based ceramic coating layer with a columnar structure on its outermost surface. The columnar structure has a size of 20 to ₂₀₀ μm, and an opening crack of 5 to 20 μm has occurred at the columnar boundary. The ZrO ₂ -based coating layer thereunder has a dense structure with no cracks. The T of the present invention shown in FIGS.
Table 1 shows the test pieces provided with BC. Test pieces Nos. 1 to 9 are the TBCs of the present invention shown in FIG. 1 in which the thickness of the ZrO ₂ -based coating layer of the columnar structure and the dense structure is variously changed. Test pieces Nos. 10 to 16 show the TBC of the present invention shown in FIGS.

For comparison, the following TBC was also prepared. FIG. 6 shows a TBC comprising a bonding layer and a ZrO ₂ -based ceramic coating layer having a columnar structure, and having an Al ₂ O ₃ layer of about 2 μm at the boundary. The TBC is formed by spraying Co-32% Ni-2 on the surface of the Ni-base heat-resistant alloy by spraying in a reduced pressure atmosphere.
1% Cr-8% Al-0.5% Y
A bonding layer of μm is formed, and then ZrO ₂ −
6% Y ₂ O ₃ was deposited to form a coating layer of 150 μm. The deposition conditions are as follows: the pressure of the deposition chamber is 5
At 10 × 10 ⁻⁵ Torr, a 10 kW E.C. B deposited. In this case, the obtained columnar structure has a columnar shape with a size of 50 to 200 μm. After the deposition and deposition, a heat treatment in the air at 1000 ° C. for 1 hour causes an opening crack of 1 to 5 μm at the columnar boundary. The crack penetrated the ceramic coating layer and reached the boundary with the bonding layer. Further, a 2 μm thick Al ₂ O ₃ layer is formed on the surface of the bonding layer at the boundary between the ceramic coating layer and the bonding layer.
A layer had been formed.

[0064] Test piece No.17 is a TBC produced as this, test pieces No.18,19 in TBC comparison shown in FIG. 6, changing the thickness of the ZrO ₂ based ceramic coating layer of the columnar texture It is a thing. The TBC in FIG. 8 is also a TBC prepared for comparison, and is formed by spraying Co-32% Ni-21% Cr-8 on a Ni-base heat-resistant alloy by spraying in a reduced-pressure atmosphere.
% Thermally spraying Al-0.5% Y alloy powder, after forming a coating layer of 100μm thick, ZrO ₂ having a two-layer structure by vapor deposition
A system ceramic coating layer was formed, followed by a heat treatment. The deposition was performed using ZrO ₂ -6% Y ₂ O ₃ as the raw material, the pressure in the film forming chamber was 5 × 10 ⁻⁵ Torr,
At a substrate temperature of 50 ° C., B. After forming a 20 μm coating layer at an output of 10 kW, the substrate temperature was set to 700 ° C., and vapor deposition was further performed to form a further 130 μm coating layer.

In this case, a 20 μm ZrO on the tie layer
_{The two} -layer coating layer has a dense structure, and the 130 μm ZrO ₂ -based layer thereon has a columnar structure. 1000 ° C, 1
After the heat treatment of h, open cracks having a width of 5 to 10 μm are formed along the boundaries of the columnar structures having a size of 50 to 200 μm, and the cracks penetrate the ZrO ₂ -based coating layer having a dense structure. , And reached the boundary with the bonding layer. In this case, a 2 μm Al ₂ O ₃ layer was formed at the boundary between the ZrO ₂ -based coating layer and the bonding layer by the heat treatment. Test piece No. 20 was made of TB
C.

[0066]

[Table 1]

For each of the present invention and the comparative TBC manufactured as described above, a heat load test was performed assuming use under a high heat load condition. FIG. 8 shows a schematic diagram of the test method. In this test, high-frequency induction thermal plasma is used as a heating source to heat the surface of a test piece provided with a TBC and to cool the back face of the test piece. The heat flux, which is a parameter of the heat load, was calculated by embedding. Also TB
The temperature of the ZrO ₂ ceramic coating layer on the surface of C was measured with a radiation thermometer.

In this state, the open / close shutter shown in FIG. 8 was operated to repeat heating, heating and holding, and cooling. The heat flux was determined in the state of heating and holding. The output of the high-frequency induction thermal plasma was 10 kW, and air was used as the plasma gas. The pressure inside the container during heating is 100 Torr. The dimensions of the test piece substrate were φ20 × 3 mm, and various TBCs shown in Table 1 were provided on the surface thereof. The test was determined based on the damage status of the TBC when the cycle was repeated. Table 2 shows the results.

[0069]

[Table 2]

In the test, a repetitive cycle test was conducted using the heat flux as a parameter. If there was no damage after 200 repetitions, it was judged that the heat resistance was excellent (indicated by 〇 in Table 2). As shown in Table 2, the two-layer Z of the present invention
TBC having an rO ₂ -based ceramic coating layer, especially when the thickness of the dense ZrO ₂ -based ceramic coating layer as the lower layer is in the range of 10 μm to 60 μm, is 3.0 to 4.5M.
No TBC damage was observed even under a severe thermal load environment of W / m ² . The thickness of the dense ceramic coating layer is 10
In the case of μm or less, it is considered that the fracture mechanism starting from the tip of a crack generated at the columnar boundary of the columnar ceramic coating layer was not different from that of the conventional example.

As a result, damage progresses along the boundary between the ZrO ₂ ceramic coating layer and the bonding layer (metal layer),
It is presumed that it came off. On the other hand, if the thickness is 6
When the thickness is 0 μm or more, it is considered that the thermal stress in the ZrO ₂ -based coating layer having a dense structure itself is increased, and the coating layer is damaged and peeled under a high heat load condition. Thus, the thickness of the dense tissue ZrO ₂ based ceramic coating layer of a lower layer in the ZrO ₂ based ceramic coating layer having a two-layer structure of the present invention is preferably 60μm or less of the range of 10 [mu] m. Further, the coating layer of the present invention having a ZrO ₂ -based ceramic coating layer having a dense structure in the above range, (columnar structure) /
The thickness ratio of (dense tissue) is also important, and the ratio is 1.
It is desirable that the total thickness of the columnar structure and the dense structure be 400 μm or less.

The TBC of the present invention shown in FIGS.
In any case, no TBC damage was observed even under a large heat flux condition of 3 MW / m ² , and it was found to have excellent heat resistance. On the other hand, it was found that the TBC prepared for comparison causes damage to the TBC under a heat flux condition of 0.8 to 1.0 MW / m ² or more at a repetition cycle of 100 times or less, and has poor heat resistance. Was.

In the above TBC of the present invention, the thickness of the ZrO ₂ -based ceramic coating layer having a columnar structure is not particularly limited, but the thickness of the ceramic coating layer is related to the heat shielding effect. The greater the effect, the greater the heat flux, the greater the thermal barrier effect. Under a large heat flux condition of 1 to 4.5 MW / m ^2, the total thickness of the columnar structure and the dense structure of the ZrO ₂ ceramic coating layer is about 300 μm,
A heat shielding effect of 0 to 200 ° C. is obtained. Therefore, in the TBC of the present invention, the thickness of the ZrO ₂ -based ceramic coating layer having a columnar structure serving as a surface layer is desirably about 300 μm at the maximum.

Example 2 Co-based alloys (FSX-414, Co-3
0% Cr-10% Ni-7% W-1% Mn-1% Si-
Test piece No. 2 in Table 1 of Example 1 using 0.2% C).
Were prepared by the same method and under the same conditions, and the heat load test shown in FIG. 8 was performed. As a result, the heat flux is 4.5 MW / m ²
It was found that the TBC of the present invention was sound without any damage even after the 200 repetitive cycle tests even under the heat load condition of, and showed excellent heat resistance as compared with the conventional TBC in Example 1.

Example 3 A Ni-based unidirectionally solidified material (DS material, Mar
-M247, Ni-16% Cr-1.8% Mo-2.6%
W-3.4% Al-3.4% Ti-1.7% Ta-8.5%
(Co-0.1% C), a test piece No. 1 in Table 1 of Example 1 was prepared in the same manner and under the same conditions, and a heat load test shown in FIG. 8 was performed. As a result, the heat flux is 4.5M
Even under a heat load condition of W / m ² , it was found that the TBC of the present invention was sound without any damage even after 200 repetitive cycle tests, and showed excellent heat resistance as compared with the conventional TBC in Example 1.

Example 4 A Ni-based single crystal material (SC material, CMSX-
4, Ni-6.6% Cr-0.6% Mo-6.4% W-3.
0% Re-5.6% Al-1.0% Ti-6.5% Ta-
Using 9.6% Co), the same method and conditions as in Example 1 were used. In this case, Ni-20 is used as the bonding layer alloy.
% Using a Cr-8% Al-1% Y alloy was used ZrO ₂ -8% Y ₂ O ₃ as the ceramic coating layer. The thickness of each layer of TBC is the same as that of the test piece No. 5 in Table 1. According to the results of the heat load test shown in FIG. 8, the TBC of the present invention was 4.5M.
Even under the heat load condition of a heat flux of W / m ² , it was found that the sample was sound without any damage even after the repetition cycle test of 200 times, and showed excellent heat resistance as compared with the conventional TBC in Example 1.

Embodiment 5 A turbine blade (material, SC material, CMSX-) shown in FIG.
The TBC rotor blade of the present invention in which the TBC of the present invention was applied to the blade surface and the platform portion, which is the portion exposed to the combustion gas, of 4) was produced. The method is the same as that of the first embodiment. First, Ni-20% Cr-8% Al-1% Y alloy is used as a bonding layer.
A thickness of 00 μm, and then ZrO _{2 having} a dense structure
30 μm thick ceramic coating layer and Z of columnar structure
An rO ₂ ceramic coating layer was provided at 150 μm. Their material is ZrO ₂ -8% Y ₂ O ₃ . Thereafter, heating was performed at 1100 ° C. for 4 hours as a heat treatment to form cracks having the same size as in Example 1 in the coating layer of the columnar structure, and a thickness of 3 μm at the boundary between the ZrO ₂ ceramic coating layer and the bonding layer. An Al ₂ O ₃ layer was formed.

Using the turbine blade of the present invention thus manufactured, a heat load test was carried out in a simulated heating test of an actual machine shown in FIG. The test condition is that the combustion gas temperature is up to 1500
C., the cooling air temperature is 170 C. and the pressure is 8 atm.
In this test, the blade base temperature in a heating and holding state was measured with a moving blade in which a thermocouple was embedded in the leading edge of the blade in advance, and the heat flux was obtained. As a result, the maximum was 3.2 MW / m ² . For comparison, a ZrO ₂ -based ceramic coating layer (180) having a columnar structure was prepared in the same manner and under the same conditions as for the test piece No. 17 in Table 1 of Example 1.
μm) and a moving blade provided with a bonding layer (100 μm). The material of the coating layer is Ni-20% Cr-8% Al-1%
Y and ZrO ₂ -8% Y ₂ O ₃ .

When the combustion gas temperature is 1000 ° C. (heat flux: 0.8 MW / m ² ), the TBC of both the turbine blade of the present invention and the comparative turbine blade is reduced to TBC even in a cycle of 10 times of starting, steady holding, and stopping. No damage was observed. However, when the combustion gas temperature was 1300 ° C. (heat flux: 1.5 MW / m ² ), the turbine blade of the present invention was sound after 10 repetition cycles. Delamination damage of the coating layer occurred. Furthermore, when the combustion gas temperature was 1500 ° C. (heat flux 3.2 MW / m ² ), the turbine blade of the present invention was quite sound after 10 repetitions. 13 for the comparative turbine blade
The damage range of the leading edge was larger than that at the time of heating at 00 ° C.

Embodiment 6 A turbine blade (material, DS material, Mar-M) shown in FIG.
-247) A TBC rotor blade of the present invention was provided in which the TBC of the present invention was provided at the blade leading edge portion (the range indicated by aa in FIG. 11) which was exposed to the combustion gas. The method is described in Example 5.
In the same manner as above, Ni-30% Co-20% Cr-8% Al-
A 0.5% Y alloy is provided in a thickness of 50 μm, and thereafter, a ZrO ₂ -based ceramic coating layer having a dense structure is provided only on the leading edge of the wing, and a ZrO ₂ -based ceramic having a columnar structure is provided on the entire wing surface and the platform portion. The coating layer was provided at 130 μm. The material of these ZrO ₂ -based ceramics is ZrO
A ₂ -6% Y ₂ O _3. In the TBC rotor blade of the present invention, the ceramic coating layer has a two-layer structure at the leading edge of the blade where the thermal load is the severest, and the other portion where the thermal load is gentle is only the ceramic coating layer having a columnar structure.

In this case, the thickness of the ceramic coating layer at the leading edge of the blade is 150 μm, and the thickness of the ceramic coating layer is 130 μm on the abdomen side, the back side of the blade, and the platform portion. Is continuously changing.
In the TBC rotor blade of the present invention, oxygen ion irradiation was not performed when forming a dense coating layer only on the leading edge portion, and oxygen ion irradiation was applied only when forming a coating layer having a columnar structure. The irradiation conditions are the same as in the first embodiment. After the ceramic coating layer was provided on the entire surface, the same heat treatment as in Example 5 was performed. As a result of performing a simulated heating test on an actual machine in the same manner as in Example 5 using the TBC rotor blade of the present invention thus manufactured,
When the combustion gas temperature is 1500 ° C (heat flux 3.2 MW /
m ² ), the TBC blade of the present invention was sound without damage such as peeling of the ceramic coating layer.

Embodiment 7 A turbine vane shown in FIG. 13 (material: Ni-base heat-resistant alloy IN)
-939, Ni-23% Cr-2% W-2% Al-3.
The leading edge of the blade, which is a portion exposed to a combustion gas of 7% Ti-1.4% Ta-19% Co-0.15% C) (a-
A TBC stationary blade provided with the TBC of the present invention in the range indicated by a) was manufactured. The method is the same as that of the fifth embodiment. First, Ni-25% Cr-1 is used as a bonding layer on the entire surface of the blade and the upper and lower gas paths.
0% Al-1.2% Y alloy is provided with a thickness of 50 μm,
After that, 30 μm was applied only to the leading edge of the blade in the same manner as in Example 5.
A dense ceramic coating layer having a thickness of m and a ceramic coating layer having a columnar structure having a thickness of 150 μm were further provided. Thereafter, in the TBC vane of the present invention, a SUS masking jig is attached to the leading edge portion provided with the ceramic coating layer and the portion of the film cooling hole, and the plasma spraying method is applied to the blade ventral side, the blade back side and the platform part. As a result, a ZrO ₂ ceramic coating layer was formed to a thickness of 180 μm.

In this case, the plasma forming gas is Ar-10
% H ₂ mixed gas, the flow rate of the mixed gas is 45 liter /
min. Plasma power is 50 kW. Raw material is 10-44
μm ZrO ₂ -based ceramic powder, 55 g / min.
A coating layer was formed at 85 mm. After the TBCs were provided on the leading edge of the blade, on the side of the blade, on the side of the blade, and on the platform in this manner, the same heat treatment as in Example 5 was performed. The ceramic coating material of the TBC blade of the present invention is Zr.
O ₂ -8% Y ₂ O ₃ . Using the TBC vane of the present invention, a simulated actual heating test was performed in the same manner as in Example 5, and as a result, the combustion gas temperature was 1500 ° C. (heat flux of 3.2 M).
W / m ² ), the TBC vane of the present invention was sound without damage such as peeling of the ceramic coating layer.

Example 8 A TBC having a hybridized columnar ceramic-based coating layer on the outermost surface was manufactured and its heat resistance was examined. Ni-base superalloy (Rene'-80: Ni-1)
4% Cr-4% Mo-4% W-3% Al-5% Ti-
9.5% Co 2, and the surface thereof is made of MCrAlY alloy (Co-32% Ni-21% Cr-8% Al-0.5%
Y) A bonding layer was formed from the powder by plasma spraying in a reduced pressure atmosphere. The conditions are such that the above alloy powder is injected into a plasma jet (50 kW) formed using an Ar-7% H ₂ mixed gas and sprayed, and the atmospheric pressure during the spraying is about 50 Torr. As this pretreatment, the test piece base material is degreased and washed, and blasting is performed with Al ₂ O ₃ grit. The thickness of the formed tie layer is 100
μm. The surface roughness of the bonding layer is Rmax.
m.

Thereafter, a hybrid columnar ceramic coating layer of the present invention was formed on the surface of the test piece substrate provided with the bonding layer by using a film forming apparatus having an evaporation source and an ion beam source. ZrO ₂ -6% Y ₂ O ₃ was used as the material of the evaporation source, and oxygen ions were used as the ion beam. First, the surface of the bonding layer was irradiated with an oxygen ion beam (acceleration voltage: 10 keV) to perform sputter cleaning of the surface of the bonding layer with oxygen ions and oxidation of the surface of the bonding layer by oxygen ion implantation. In this case, the pressure of the film forming chamber is 10 ⁻⁵ Torr, and the substrate temperature is about 50 ° C. The measurement of the substrate temperature was performed by providing a thermocouple on the back surface of the substrate. As a result, the surface of the bonding layer was cleaned and Al ₂ O ₃ of about 0.1 μm was formed.

Thereafter, ZrO ₂ -6% Y ₂ O ₃ was vapor-deposited while performing oxygen ion irradiation. The output of the evaporation source was 10 kW, and was measured with
Vapor deposition was performed while ion irradiation was performed to a thickness of. In this case, the pressure of the film forming chamber is 5 × 10 ⁻⁵ Torr.
And the substrate temperature is about 50 ° C. As a result, a mixed layer of Al ₂ O _{3 on} the surface of the bonding layer and ZrO ₂ -6% Y ₂ O _{3 as} the deposition material was formed. As a result of analysis, the thickness of this layer was about 0.1 μm, and a ZrO ₂ -6% Y ₂ O ₃ coating layer of about 0.4 μm was formed thereon.

Then, while continuing the deposition of ZrO ₂ -6% Y ₂ O _3, an oxygen ion beam (acceleration voltage 10 keV)
, And vapor deposition and irradiation were performed simultaneously. In this case, the pressure of the film forming chamber is 7 × 10 ⁻⁵ Torr, and the substrate temperature is about 150 ° C. About 150μ on the dense ZrO ₂ -6% Y ₂ O ₃ coating layer of the continued deposition in this state
m of coating layers were formed. In this case, ZrO ₂ -6% Y ₂
The O ₃ coating layer has a primary and secondary columnar structure, and the width of each column constituting the primary columnar structure is 2 to 5 μm, and the width of the secondary columnar structure composed of the primary columnar structure is 50 to 100 μm.
m.

The primary and secondary columnar structures are formed by ion irradiation. The energy of the irradiated ion beam causes the high melting point material ZrO ₂ —
Even with 6% Y ₂ O ₃ , a columnar structure can be obtained by epitaxial growth. The TBC having the coating layer formed by each of the above-described film forming processes was subjected to a heat treatment as a next step to give a thermal stress, thereby forming a tertiary columnar structure in the ceramic coating layer. The heat treatment is heating in the air at 1050 ° C. for 4 hours.

As a result, cracks having a width of 5 to 20 μm are generated along the boundary of the secondary columnar structure of the ZrO ₂ -6% Y ₂ O ₃ coating layer composed of the primary and secondary columnar structures, and the columnar structures are formed into individual columnar structures. It was divided into.

FIG. 14 is a schematic cross-sectional view of a TBC having the hybridized columnar ceramic coating layer formed as described above on the outermost surface. In addition, the SE of the surface and the fracture surface
M observation was performed. In the TBC manufactured according to the present invention, Zr
The O ₂ -based ceramic coating layer is composed of a primary to tertiary columnar structure. Is a tertiary columnar structure composed of secondary columnar aggregates, and the width of the crack at the tertiary columnar boundary is 5 to 20
μm.

FIGS. 15 to 18 are schematic cross-sectional views of a TBC of the present invention in which a hybrid columnar ceramic coating layer is produced by the production method of the present invention. In the TBC of the present invention shown in FIG. 15, after pretreatment of a Ni-base heat-resistant alloy (Rene '80), Co-spraying is performed under reduced pressure atmosphere under the same conditions as above.
32% Ni-21% Cr-8% Al-0.5% Y and Zr
A mixed powder of O ₂ -6% Y ₂ O ₃ (mixing ratio 1/1) is sprayed to form a coating layer having a thickness of 100 μm. Thereafter, Co-32 is sprayed under reduced pressure atmosphere under the same conditions as above. % N
i-21% Cr-8% Al-0.5% Y 2
A coating layer having a thickness of μm was formed. Thereafter, a hybridized columnar ceramic coating layer was prepared under the same method and conditions as described above. The ceramic is ZrO ₂ -6% Y ₂ O ₃ and its thickness is the same as above. The structure of the obtained hybridized columnar ceramic coating layer is the same as described above.

In the TBC of the present invention shown in FIG. 16, the TBC shown in FIG.
In forming the coating layer on the Ni-based heat-resistant alloy, first, Co-32% Ni-21% Cr-8% Al
-Spray only 0.5% Y alloy powder and then ZrO ₂
The -6% Y ₂ O ₃ finally gradually increasing the amount of powder was 1/1 the mixing ratio of the alloy and the ceramic. Thereafter, the TBC of the present invention was manufactured in the same manner as in the present invention shown in FIG.
In the TBC of the present invention shown in FIG. 17, a Co-32% Ni
After spraying -21% Cr-8% Al-0.5% Y alloy powder to form a 50 μm thick coating layer, FIG.
Each coating layer was produced in the same manner as in TBC. FIG.
In the TBC 8 of the present invention, Co-32% Ni-21 was sprayed on the surface of the Ni-base heat-resistant alloy in the same reduced pressure atmosphere as above.
% Cr-8% Al-0.5% Y alloy powder,
After forming a coating layer having a thickness of μm, the TBC of FIG.
Each coating layer was produced in the same manner as in the above.

Table 3 shows the test pieces provided with the TBC of the present invention shown in FIGS.

[0094]

[Table 3]

Specimens Nos. 21 to 25 are the TBCs of the present invention shown in FIG.
The thickness of the O ₂ -based coating layer was changed variously. Test piece N
o.26 to 29 show the TBC of the present invention shown in FIGS.

For comparison, a TBC shown below was also prepared. Figure 19 is composed of a coupling layer and the ZrO ₂ based ceramic coating layer of columnar structure, Al ₂ O ₃ of about 2μm to the boundary
TBC with layers. This TBC is formed by spraying Co-32% Ni-
Spray 21% Cr-8% Al-0.5% Y alloy
A 0 μm tie layer was formed, after which the surface was polished to a Rmax.10 μm roughness. After that ZrO
The ₂ -6% Y ₂ O ₃ was deposited, is obtained by forming a 150μm coating layer. The deposition conditions are as follows: a pressure of a film forming chamber is 5 × 10 ⁻⁵ Torr; B deposited. In this case, the obtained columnar structure has a columnar shape (primary columnar shape) having a size of 3 to 6 μm. Cracks are formed, and the ceramic coating layer is 0.5 to 1 μm due to the cracks.
m.

Test piece No. 30 is a TBC manufactured in this way, and test pieces Nos. 31 and 32 were obtained by changing the thickness of the ZrO ₂ ceramic coating layer in the comparative TBC shown in FIG. is there.

A heat load test assuming use under a high heat load condition was carried out for each of the present invention and the comparative TBC manufactured as described above, as in FIG. Table 4 shows the results.

[0099]

[Table 4]

In the test, a repetitive cycle test was performed using the heat flux as a parameter, and when there was no damage after 300 repetitions, it was judged that the heat resistance was excellent (in Table 4, ○).
). As shown in Table 4, in the TBC having the hybridized columnar ceramic coating layer of the present invention, 3.0 to 3.0 was obtained.
No TBC damage was observed even under a severe thermal load environment of 4.5 MW / m ² .

The T of the present invention shown in FIGS.
In any case, even in the case of the BC, the TBC was not damaged even under the condition of a large heat flux of 3 MW / m ² , indicating that the BC had excellent heat resistance. On the other hand, it was found that the TBC produced for comparison suffered damage of the TBC at a repetition cycle of 100 or less under a heat flux condition of 0.8 to 1.0 MW / m ² or more, and its heat resistance was not good. .

In the above TBC of the present invention, the thickness of the ZrO ₂ -based ceramic coating layer having a columnar structure is not particularly limited, but the thickness of the ceramic coating layer is related to the heat shielding effect. The greater the effect, the greater the heat flux, the greater the thermal barrier effect. Under a large heat flux condition of 1 to 4.5 MW / m ^2, the thickness of the hybridized ceramic coating layer is about 300 μm, and a heat shielding effect of 90 to 200 ° C. can be obtained. Therefore, in the TBC of the present invention, the thickness of the ZrO ₂ -based ceramic coating layer having a hybridized columnar structure is desirably about 300 μm at the maximum.

Example 9 As a heat-resistant alloy, a Co-based alloy (FSX-414, Co-3
0% Cr-10% Ni-7% W-1% Mn-1% Si-
Test piece No. 21 in Table 3 of Example 8 using 0.2% C).
Were prepared by the same method and under the same conditions, and the heat load test shown in FIG. 8 was performed. As a result, the heat flux is 4.5 MW / m ²
It was found that the TBC of the present invention was sound without any damage even after the 300 repetitive cycle test even under the heat load conditions described above, and exhibited excellent heat resistance as compared with the conventional TBC in Example 8.

Example 10 As a heat-resistant alloy, a Ni-based unidirectionally solidified material (DS material, Mar
-M247, Ni-16% Cr-1.8% Mo-2.6%
W-3.4% Al-3.4% Ti-1.7% Ta-8.5%
(Co-0.1% C), a test piece No. 1 in Table 1 of Example 1 was prepared in the same manner and under the same conditions, and a heat load test shown in FIG. 8 was performed. As a result, the heat flux is 4.5M
Even under a heat load condition of W / m ² , it was found that the TBC of the present invention was sound without any damage even after 300 repeated cycle tests, and showed excellent heat resistance as compared with the conventional TBC in Example 8.

Example 11 A Ni-based single crystal material (SC material, CMSX-
4, Ni-6.6% Cr-0.6% Mo-6.4% W-3.
0% Re-5.6% Al-1.0% Ti-6.5% Ta-
Using 9.6% Co), the same method and conditions as in Example 1 were used. In this case, Ni-20 is used as the bonding layer alloy.
% Using a Cr-8% Al-1% Y alloy was used ZrO ₂ -8% Y ₂ O ₃ as the ceramic coating layer. The thickness of each layer of TBC is the same as that of the test piece No. 21 in Table 1. FIG.
According to the results of the heat load test shown in FIG.
Example 8 Even under a heat load condition of a heat flux of MW / m ² , it was sound without any damage even after 300 repeated cycle tests.
It was found that the material exhibited excellent heat resistance as compared with the conventional TBC.

Embodiment 12 A turbine blade shown in FIG. 9 (material, SC material, CMSX-
The TBC rotor blade of the present invention in which the TBC of the present invention was applied to the blade surface and the platform portion, which is the portion exposed to the combustion gas, of 4) was produced. The method is the same as that of the first embodiment. First, Ni-20% Cr-8% Al-1% Y alloy is used as a bonding layer.
A thickness of 00 μm was provided, and thereafter, a ZrO ₂ -based ceramic coating layer having a primary columnar and secondary columnar hybrid columnar structure was provided at 150 μm. The material is ZrO ₂ -8% Y ₂ O ₃
It is. Thereafter, heating was performed at 1100 ° C. for 4 hours as a heat treatment to form a coating layer of a tertiary columnar structure composed of one secondary column and a plurality of secondary columns.

Using the turbine blade of the present invention thus manufactured, a heat load test was carried out by a simulated heating test of an actual machine shown in FIG. The test condition is that the combustion gas temperature is up to 1500
° C, the cooling air temperature is 170 ° C, and the pressure is 8 atm.
In this test, the blade base temperature in a heating and holding state was measured with a moving blade in which a thermocouple was embedded in the leading edge of the blade in advance, and the heat flux was obtained. As a result, the maximum was 3.2 MW / m ² . For comparison, a ZrO ₂ -based ceramic coating layer (150 μm) and a bonding layer (100 μm) having a columnar structure with a width of 3 to 6 μm were prepared under the same method and conditions as the test piece No. 30 in Table 3 of Example 8. A rotor blade provided with was also manufactured. The material of the coating layer is Ni-20% Cr-8
% Is Al-1% Y and _{ZrO 2 -8% Y 2 O 3} .

When the temperature of the combustion gas is 1000 ° C. (heat flux: 0.8 MW / m ² ), both the turbine blades of the present invention and the comparative turbine blades show the TBC even in the cycle of starting, steady holding, and stopping 10 times. No damage was observed. However, when the combustion gas temperature was 1300 ° C. (heat flux: 1.5 MW / m ² ), the turbine blade of the present invention was sound after 10 repetition cycles. Delamination damage of the coating layer occurred. Furthermore, when the combustion gas temperature was 1500 ° C. (heat flux 3.2 MW / m ² ), the turbine blade of the present invention was quite sound after 10 repetitions. 13 for the comparative turbine blade
The damage range of the leading edge was larger than that at the time of heating at 00 ° C.

Embodiment 13 A turbine blade (material, DS material, Mar-M) shown in FIG.
-247) A TBC rotor blade of the present invention was provided in which the TBC of the present invention was provided at the blade leading edge portion (the range indicated by aa in FIG. 11) which was exposed to the combustion gas. The method is described in Example 5.
In the same manner as above, Ni-30% Co-20% Cr-8% Al-
A 0.5% Y alloy was provided in a thickness of 50 μm, and thereafter, a ZrO ₂ -based ceramic coating layer having a hybridized columnar structure was provided in a thickness of 200 μm only on the leading edge of the blade. ZrO ₂ -8% Y ₂ O ₃ was sprayed on the other wing surfaces and platform portions other than the leading edge by a plasma spraying method to form a coating layer of 200 μm.

In this case, the plasma forming gas is Ar-10
% H ₂ mixed gas, the flow rate of the mixed gas is 45 liter /
min, the plasma power is 50 kW. Raw material is 10-4
4 μm ZrO ₂ ceramic powder, 55 g / min is injected into the plasma jet and the spraying distance is 75
Coverage was formed at ~ 85 mm.

After the ceramic coating layer was provided on the entire surface, the same heat treatment as in Example 12 was performed. Example 12 Using the TBC Blade of the Present Invention Produced in this Way,
When the combustion gas temperature was 1500 ° C. (heat flux of 3.2 MW / m ² ), the TBC rotor blade of the present invention was sound without damage such as peeling of the ceramic coating layer. there were.

Embodiment 14 A turbine vane shown in FIG. 13 (material: Ni-base heat-resistant alloy IN)
-939, Ni-23% Cr-2% W-2% Al-3.
The leading edge of the blade, which is a portion exposed to a combustion gas of 7% Ti-1.4% Ta-19% Co-0.15% C) (a-
A TBC stationary blade provided with the TBC of the present invention in the range indicated by a) was manufactured. The method is the same as that of the fifth embodiment. First, Ni-25% Cr-1 is used as a bonding layer on the entire surface of the blade and the upper and lower gas baths.
0% Al-1.2% Y alloy is provided in a thickness of 50 μm, and then only 150 μm is formed on the leading edge of the blade in the same manner as in Example 5.
A m-thick hybridized columnar structure ceramic coating layer was provided. Thereafter, in the TBC vane of the present invention, a SUS masking jig is attached to the leading edge portion provided with the ceramic coating layer and the portion of the film cooling hole, and the plasma spraying method is applied to the blade ventral side, the blade back side and the platform part. ZrO ₂
A 180-μm thick ceramic coating layer was formed.

In this case, the plasma forming gas is Ar-10
% H ₂ mixed gas, the flow rate of the mixed gas is 45 liter /
min, the plasma power is 50 kW. Raw material is 10-4
4 μm ZrO ₂ ceramic powder, 55 g / min is injected into the plasma jet and the spraying distance is 75
A coating layer was formed at ８５85 mm. After the TBCs were provided on the blade leading edge, the blade ventral side, the blade back side, and the platform in this way, the same heat treatment as in Example 12 was performed. The ceramic coating material of the TBC blade of the present invention is Zr.
O ₂ -8% Y ₂ O ₃ . Using the TBC vane of the present invention, a simulated actual heating test was performed in the same manner as in Example 12, and as a result, when the combustion gas temperature was 1500 ° C. (heat flux 3.2 M
W / m ² ), the TBC vane of the present invention was sound without damage such as peeling of the ceramic coating layer.

Embodiment 15 FIG. 20 is a sectional view of a rotating portion of a gas turbine having gas turbine blades and stationary blades on which a heat-resistant coating layer is formed by the method of Embodiment 8. FIG. 21 shows a specific structure of a moving blade, and FIG. 22 shows a structure of a stationary blade. Example 8 of the rotor blade
The alloy described in Example 14 was used as the stationary blade.

The rotor blade shown in FIG. 21 has a dovetail 40, a wing portion 51, a shank 59, a platform 55, and a seal fin 54 corresponding to implantation into a disk, 53 indicates a trailing portion, and 57 indicates a recess. .

The stationary blade has a wing portion 52, an inner peripheral side 56 and an outer peripheral side 58 of the sidewall. Gas turbine nozzles and blades are immersed in a solution of acrylic resin in methyl ethyl ketone, immersed in a wax model of the shape shown in the figure, air-dried, and immersed in slurry (zircon flower + colloidal silica + alcohol) to form a stack (first layer). Zircon sand, two or more layers of chamotte sand) were sprayed, and this was repeated several times to form a mold. The mold was fired at 900 ° C. after dewaxing. Next, the mold was provided in a vacuum furnace, the alloy was melted by vacuum melting, and cast into a mold in a vacuum. This nozzle has a wing part width between sidewalls of about 74 mm, length 110 mm, and 25 m at the thickest part.
It is a casting having a thickness of 3 to 4 mm, a seal fin cooling hole 59, and a slit 60 for an air passage of about 0.7 mm at the end.

The blade had a wing length of 100 mm and a length after the platform of 120 mm. The blade in this embodiment is a cooling medium so that it can be cooled from the inside,
In particular, cooling holes are provided from the dovetail portion through the wing portion so that air or water vapor can pass. In the trailing edge portion, the outlet of the refrigerant is provided in a slit shape.

The stationary blade is provided with holes for pin fin cooling, impingement cooling, and film cooling on the blade portion. The thickness of the slit at the tip is about 1 mm. In the nozzle, solution treatment is performed by aging treatment in a non-oxidizing atmosphere.

The blades and nozzles of this embodiment are most suitable for the first stage, but can also be provided for the second and third stages.
Particularly, in the second and third stages of the nozzle, a nozzle having one wing portion made of a Co-based alloy is provided. The first-stage nozzle is constrained at both ends, while the second and third stages are single-sided.
The second and third stages have a larger wing width than the first stage.

The SUS304 stainless steel tube having an impingement cooling hole is TIG-welded to the main body over the entire circumference, and cooling air flows in from that portion to prevent air leakage from the welded portion. A hole through which the cooling air exits is also provided inside the combustion gas outlet side. The first-stage nozzle has a structure that is constrained at both ends of the sidewall, but the second and subsequent stages have a structure that is constrained on one side on the outer peripheral side of the sidewall.

In the nozzle made of the Ni-based alloy in this embodiment, the γ ′ phase is precipitated in the γ phase matrix.

30 is a turbine stub shaft, 33 is a turbine rotor blade, 43 is a turbine stacking bolt, 38
Is a turbine spacer, 49 is a distant piece, 40
Is a nozzle, 36 is a compressor disk, 37 is a compressor blade, 38 is a compressor stacking bolt, 39 is a compressor stub shaft, 34 is a turbine disk, and 41 is a hole. In the present invention, the gas turbine has 17 stages of compressor disks 36 and 3 stages of turbine blades 33. The turbine blade 33 may have four stages, and the present invention can be applied to any of the stages.

The gas turbine of the present embodiment is mainly composed of a heavy-tuty type, a single-shaft type, a horizontally split casing, and a stacking type rotor. The compressor is a 17-stage axial flow type, the turbine is a 3-stage impulse type, and , A two-stage air-cooled stationary blade and a combustor having a berth flow type, 16 cans, and a slot cool system.

The distant piece 39, the turbine disk 34, the spacer 38, and the compressor stacking bolt 35 are expressed by weight in the range of C 0.06 to 0.15%, Si 1% or less, Mn 1.5% or less, Cr 9.5 to 12.5%. , Ni
1.5-2.5%, Mo 1.5-3.0%, V0.1-0.1.
3%, Nb 0.03 to 0.15%, N 0.04 to 0.15
%, The whole tempered martensitic steel consisting of the balance Fe is used. As a characteristic in this embodiment, the tensile strength is 90%.
１２０120 kg / mm ² , 0.2% proof stress 70-90 kg / mm ² , elongation 10-25%, draw ratio 50-70%, V notch impact value 5-9.5 kg-m / cm ² , 450 ° C. 10 ^{The 5} h creep rupture strength was 45 to 55 kg / mm ² .

The turbine blade 33 has three stages, the first stage being the one manufactured in Example 8 and having a compressor pressure of 14.7.
, Temperature 400 ℃, first stage rotor blade inlet temperature 1,300 ℃,
The temperature of the combustion gas from the combustor was set at 1450 ° C. The second stage of the turbine rotor blade 33 has a blade length of 280 mm (wing portion: 160 mm, length after the platform portion: 120 mm) made of the same alloy composition, and the third stage has the same alloy composition, and has a blade length of 350 mm. (Wing part 230mm, other 120mm)
Manufactured solid wings. The manufacturing method was a precision casting method using a conventional lost wax method.

The above-described Ni-based alloy was used in the first stage of the turbine nozzle and a known Co-based alloy was used in the second and third stages. Use something. The wing has a length corresponding to the length of the moving blade, and has a pin fin cooling, impingement cooling and film cooling structure. The first stage nozzle is constrained on both sides of the sidewall, while the second and third stages are constrained on one side on the outer peripheral side of the sidewall. The gas turbine is provided with an intercooler.

The power output obtained by this embodiment is 50
MW is obtained, and the thermal efficiency is as high as 33% or more.

FIG. 23 is a schematic diagram showing a single-shaft combined cycle power generation system using the gas turbine of the fifteenth embodiment together with a steam turbine.

In the case of power generation using a gas turbine, in recent years, a gas turbine is driven by using liquefied natural gas (LNG) as a fuel, and a steam turbine is driven by steam obtained by recovering exhaust gas energy of the gas turbine.
There is a tendency to employ a so-called combined power generation system in which a generator is driven by the steam turbine and a gas turbine. In this combined power generation system, the following system configuration enables high thermal efficiency of about 45% or more as compared with the thermal efficiency of 40% in the case of the conventional steam turbine alone. In such a combined cycle power plant, recently, it has been further promoted to use both liquefied natural gas (LNG) and liquefied petroleum gas (LPG), and to realize co-firing of LNG and LPG, thereby facilitating plant operation and economy. The goal is to improve

First, air enters the gas turbine air compressor through the intake filter and the intake siren.
Compress air and send compressed air to low NOx combustor. In the combustor, fuel is injected into the compressed air and burned to produce a high-temperature gas of 1400 ° C. or higher, and the high-temperature gas works in a turbine to generate power.

Exhaust gas of 530 ° C. or higher discharged from the turbine is sent to an exhaust heat recovery boiler through an exhaust silencer,
530 ° C by recovering thermal energy in gas turbine exhaust
The above high-pressure steam is generated. This boiler is provided with a denitration device by dry ammonia catalytic reduction. Exhaust gas is discharged outside from a three-legged chimney with a length of several hundred meters. The generated high-pressure and low-pressure steam is sent to a steam turbine comprising a high-low pressure integrated rotor.

The steam that has exited the steam turbine flows into the condenser, is degassed in a vacuum, and becomes condensed water. The condensed water is pressurized by a condensate pump and supplied as water to the boiler. Then, the gas turbine and the steam turbine each drive a generator from both shaft ends to generate power. For cooling the gas turbine blades used in such combined power generation, steam used in a steam turbine may be used as a cooling medium in addition to air. Generally, air is used as a cooling medium for the blades. However, steam has a much higher specific heat than air, and has a large cooling effect because of its light weight.

With this combined power generation system, a total of 80,000 kW of power can be obtained from a gas turbine of 50,000 kW and a steam turbine of 30,000 kW. The steam turbine in this embodiment is compact, and It is possible to manufacture economically with the same power generation capacity as compared with the above, and there is obtained a great merit that it can be operated economically with respect to fluctuations in the amount of power generation.

The steam turbine according to the present invention is a high-low pressure integrated steam turbine, and the single-unit output of the turbine is increased by increasing the steam pressure at the main steam inlet of the high-low pressure integrated steam turbine at 100 atg and at a temperature of 538 ° C. Can be achieved. Increasing the output of a single unit increases the blade length of the last stage rotor blade by three.
It needs to be increased to 0 inches or more, and the steam flow rate needs to be increased. The steam turbine according to the present invention has 13 or more stages of blades implanted on a high-low pressure integrated rotor shaft, and steam flows through the steam control valve at a high temperature and high pressure of 538 ° C. and 88 atg from the steam inlet as described above. I do. The steam flows in one direction from the inlet, reaches a steam temperature of 33 ° C. and 722 mmHg, and is discharged from the outlet of the blade at the final stage. The high-low pressure integrated rotor shaft according to the present invention is Ni-Cr-Mo.
Forged steel of -V low alloy steel is used. The implanted portion of the blade of the rotor shaft has a disk shape, and is manufactured by being integrally cut from the rotor shaft. The length of the disk portion increases as the length of the blade decreases, so that vibration is reduced.

The high / low pressure integrated rotor shaft according to this embodiment has a C of 0.18 to 0.30%, a Si of 0.1% or less, and a Mn of 0.1%.
3% or less, Ni 1.0 to 2.0%, Cr 1.0 to 1.7%,
Mo is 1.0 to 2.0%, V is 0.20 to 0.3%, and the balance is Fe. After quenching at 900 to 1050 ° C by water spray cooling, it is tempered at 650 to 680 ° C.

The plant has a single-shaft type in which six sets of a power generation system including a gas turbine, an exhaust heat recovery boiler, a steam turbine, and a generator are combined. On the other hand, steam can be obtained by exhaust gas after combining one generator and combining these six sets, so that a multi-shaft type having one steam turbine and one generator can be obtained.

The combined power generation is realized by a combination of a gas turbine that can be easily started and stopped in a short time and a small and simple steam turbine. Therefore, the output can be easily adjusted, and the intermediate load that can respond to a change in demand can be easily adjusted. Ideal for thermal power.

[0138] The reliability of gas turbines has been dramatically increased due to the recent development of technology. In addition, in the case of a combined cycle power plant, since a system is composed of a combination of small-capacity machines, a failure should occur. Even so, the effects can be localized, and the power supply is highly reliable.

[0139]

The ceramic coating layer according to the present invention has a two-layer structure consisting of a columnar ceramic layer having a thermal stress relieving action and a ceramic layer having a crack-free dense structure which is a starting point of fracture due to thermal stress. In the case where a large temperature gradient is generated in the ceramic coating layer because of its body, that is, as a result of being used for high-performance cooling blades or the like where the heat flux is high under thermal conditions, for example, when the combustion gas temperature is high in turbine parts, its excellent performance is obtained. The durability of the ceramic coating layer makes it difficult for damage such as peeling to occur due to the durability, and it is possible to sufficiently maintain the heat shielding effect, which is the original purpose of the ceramic coating layer,
By reducing the temperature of the base metal constituting the component, the reliability of the component is improved, and the life of the component can be extended. Further, since the heat shielding effect can be stably obtained, the amount of air for cooling the blades of the gas turbine blade can be reduced, and the power generation efficiency of the turbine can be increased.

Furthermore, since the hybridized ceramic coating layer of the present invention is composed of ceramics having columnar structures of different sizes from primary to tertiary, when used as a thermal shielding coating, The ability to relieve thermal stress caused by the difference in thermal expansion between the coating layer and the base material is large, and a large temperature gradient occurs in the ceramic coating layer, that is, under heat conditions where the heat flux is large, for example, the combustion gas temperature in turbine parts As a result, the ceramic coating layer is not easily damaged due to its excellent durability.
The shielding effect, which is the original purpose of the ceramic coating layer, can be sufficiently maintained, and the reliability of the component is improved by lowering the temperature of the base metal constituting the component, and the life of the component can be extended. Further, since the heat shielding effect can be stably obtained, the amount of air for cooling the gas turbine blades can be reduced, and the power generation efficiency of the turbine can be increased.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a ceramic coating layer.

FIG. 2 is a schematic sectional view of a ceramic coating layer.

FIG. 3 is a schematic sectional view of a ceramic coating layer.

FIG. 4 is a schematic sectional view of a ceramic coating layer.

FIG. 5 is a schematic sectional view of a ceramic coating layer.

FIG. 6 is a schematic sectional view of a ceramic coating layer.

FIG. 7 is a schematic sectional view of a ceramic coating layer.

FIG. 8 is a structural view of a high heat load heating test apparatus.

FIG. 9 is a perspective view of a ceramic-coated turbine blade.

FIG. 10 is a structural view of an actual machine simulated heating test apparatus.

FIG. 11 is a sectional view of a ceramic-coated turbine blade.

FIG. 12 is a schematic sectional view of a ceramic coating layer.

FIG. 13 is a sectional view of a ceramic-coated turbine vane.

FIG. 14 is a schematic sectional view of a ceramic coating layer.

FIG. 15 is a schematic sectional view of a ceramic coating layer.

FIG. 16 is a schematic sectional view of a ceramic coating layer.

FIG. 17 is a schematic sectional view of a ceramic coating layer.

FIG. 18 is a schematic sectional view of a ceramic coating layer.

FIG. 19 is a schematic sectional view of a ceramic coating layer.

FIG. 20 is an overall configuration diagram of a gas turbine according to the present embodiment.

FIG. 21 is a perspective view of a gas turbine bucket according to the embodiment.

FIG. 22 is a perspective view of a gas turbine stationary blade according to the embodiment.

FIG. 23 is an overall system diagram of the combined cycle power plant according to the present embodiment.

[Explanation of symbols]

1 ... crack, 2 ... columnar texture ZrO ₂ based ceramic layer, 3 ... dense tissue ZrO ₂ based ceramic layer, 4 ... Al ₂
O ₃ layer, 5: metal layer, 6: base material, 7: mixed layer of ceramic and metal, 8: layer whose composition changes from metal to ceramic, 11: high frequency coil, 12: high frequency power supply,
13 gas source, 14 reaction vessel, 15 high-frequency induction thermal plasma, 16 test piece, 17 water-cooled test piece holder, 1
8 Opening / closing shutter, 21 Combustion nozzle, 22 Combustion cylinder, 23 Test blade, 24 Blade holding stand, 25 Heat exhaust duct, 26 Combustion flame, 31 Primary columnar structure, 32 Secondary columnar structure, 33: Tertiary columnar structure, 34: Hybridized columnar ceramic layer, 35: Micro crack, 36: Al
₂ O ₃ layer, 37: metal layer, 38: base material, 39: mixed layer of metal and ceramic, 40: layer whose composition changes from metal to ceramic, 41: columnar ceramic layer, 43
... Turbine stacking bolt, 49 ... Distant piece, 50 ... Tab till, 51, 52 ... Wing, 53 ... Trailing edge, 54 ... Seal fin, 55 ... Platform, 56, 58 ... Side wall, 59 ... Shank, 130 ... Turbine stub shaft, 133 ... rotor blade, 134 ... turbine disk, 135 ... compressor stacking bolt, 136 ... compressor disk,
137: compressor blade, 138: spacer, 1
40 ... Static wing.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Akira Mehata 4026 Kuji-cho, Hitachi City, Ibaraki Prefecture Within Hitachi Research Laboratory, Hitachi, Ltd. (72) Inventor Tetsuo Sasada 3-1-1 Sachimachi, Hitachi City, Ibaraki Stock Hitachi, Ltd. Hitachi Factory (72) Inventor Hajime Toriya 3-1-1, Sachimachi, Hitachi, Ibaraki Pref. Hitachi, Ltd. Hitachi Factory (58) Field surveyed (Int. Cl. ⁶ , DB name) C23C 28 / 00

Claims (13)

(57) [Claims] 1. A heat-resistant member having a heat-resistant coating layer provided on the surface of a heat-resistant alloy base material containing Ni or Co as a main component, wherein the structure of the heat-resistant coating layer is higher than that of the base material. a metal layer made of corrosion oxidation resistance superior alloy provided sequentially thereon, Al ₂ O ₃ ceramic thin film layer, dense ZrO ₂ based ceramic coating layer made of granular tissue and ZrO ₂ based ceramic coating of columnar texture A ceramic-coated heat-resistant member provided with a layer and having cracks in a thickness direction in the ZrO ₂ -based ceramic layer having the columnar structure. 2. A heat-resistant alloy base material containing Ni or Co as a main component.
Of heat-resistant members with heat-resistant coating layer on the surface
Therefore, the surface of the substrate has a higher temperature corrosion resistance and oxidation resistance than the substrate.
Forming a metal layer made of an excellent alloy by plasma spraying
Process, and an Al ₂ O ₃ ceramic thin film layer
Forming process and ZrO ₂ ceramics with dense structure
Forming a layer by an electron beam evaporation method; and a columnar structure Zr.
Electron beam deposition and ion beam deposition of O ₂ ceramics layer
And a step of forming by irradiation simultaneously.
Then, by heating, a film of a columnar structure ZrO ₂ -based ceramic layer is formed.
A method for producing a ceramic-coated heat-resistant member , wherein a crack is formed in a thickness direction . 3. A heat-resistant alloy containing Ni or Co as a main component.
Of gas turbine blades exposed to combustion gas
On the entire surface or a part of the heat-resistant alloy,
A metal layer made of an alloy with excellent corrosion resistance is provided.
In order, Al ₂ O ₃ ceramic thin film layer, dense set
Woven ZrO ₂ -based ceramic coating layer and columnar set
Providing a woven ZrO ₂ -based ceramic layer, and
Cracks develop in the thickness direction of the woven ZrO ₂ ceramic layer
Ceramics-coated gas turbine
Rotor blade. 4. A heat-resistant alloy containing Ni or Co as a main component.
Of gas turbine vanes exposed to combustion gas
On the entire surface or a part of the heat-resistant alloy,
The metal layer is provided consisting of Shoku耐 oxidizing excellent alloy thereof
In order, Al ₂ O ₃ ceramic thin film layer, dense set
Woven ZrO ₂ -based ceramic coating layer and columnar set
Providing a woven ZrO ₂ -based ceramic layer, and
Cracks develop in the thickness direction of the woven ZrO ₂ ceramic layer
Ceramics-coated gas turbine
N wings. 5. A heat-resistant alloy base material containing Ni or Co as a main component.
In a heat-resistant member provided with a heat-resistant coating layer on the surface of
The ZrO ₂ ceramic layer constituting the coating layer is made of ZrO ₂
Of the smallest columnar structure (primary columnar structure) of ceramics
One of the columnar structures (secondary columnar structures) consisting of an aggregate of
Divided by cracks formed in the direction of film thickness
Characterized by having a columnar structure (tertiary columnar structure)
Thermal stress-relieving ceramic coatings. 6. A heat-resistant alloy base material containing Ni or Co as a main component.
Of heat-resistant members with heat-resistant coating layer on the surface
Therefore, the surface of the substrate has a higher temperature corrosion resistance and oxidation resistance than the substrate.
Forming a metal layer made of an excellent alloy by plasma spraying
Process and, on top of that, Al ₂ O ₃ system by ion beam irradiation
Forming a ceramic thin film layer;
20-200μ consisting of primary columnar structure and its aggregate of width
The ZrO ₂ -based ceramic layer with a secondary columnar structure
Method for simultaneous electron beam deposition and ion beam irradiation
And then heating the ZrO ₂ -based
Cracks in the thickness direction of the secondary columnar structure in the ceramic layer
To form a tertiary columnar structure divided by cracks
Thermal stress relaxation type ceramic coating heat resistant
Method of manufacturing components. 7. A heat-resistant alloy containing Ni or Co as a main component.
Of gas turbine blades exposed to combustion gas
On the entire surface or a part of the heat-resistant alloy,
A metal layer made of an alloy with excellent corrosion resistance is provided.
Sequentially above, Al ₂ O ₃ ceramic thin film layer, primary, secondary
And a ZrO ₂ ceramic layer with a tertiary columnar structure
The primary columnar structure has a minimum columnar structure,
A plurality of collection der follows columnar organization the primary pillar-shaped structure
The tertiary columnar structure is in the thickness direction of the secondary columnar structure.
It consists of a columnar structure divided by the resulting cracks.
Thermal stress relaxation type ceramic coating gaster characterized by the following:
Bin bucket. 8. A heat-resistant alloy containing Ni or Co as a main component.
Of gas turbine vanes exposed to combustion gas
On the entire surface or a part of the heat-resistant alloy,
A metal layer made of an alloy with excellent corrosion resistance is provided.
Sequentially above, Al ₂ O ₃ ceramic thin film layer, primary, secondary
And a tertiary columnar structure ZrO ₂ -based ceramic layer,
The primary columnar structure has a minimum columnar structure and the secondary columnar structure
Is a plurality of aggregates of the primary columnar structure,
The tertiary columnar structure was generated in the thickness direction of the secondary columnar structure.
It consists of a columnar structure divided by cracks.
Thermal Stress Relaxation Type Ceramic Coated Gas Turbine Static
Wings. 9. A projection having a wing portion and a flat portion connected to the wing portion.
Platform and shan connected to the platform
And a projection provided on both sides of the shank.
Has fins and dovetails connected to the shank
In a moving blade for a gas turbine, a heat-resistant coating
A cover layer is provided, and the configuration of the heat-resistant cover layer is
In addition, from the alloy excellent in high temperature corrosion resistance and oxidation resistance compared to the base material
A metal layer is formed, and an Al ₂ O ₃ ceramic
Thin film layer, ZrO ₂ -based ceramic with dense granular structure
ZrO ₂ ceramics with mixed coating layer and columnar structure
Providing a coating layer, and a ZrO ₂ -based ceramic having the columnar structure.
In the thickness direction along the boundary of the columnar structure only in the
Gas turbine operation characterized by the formation of racks
Wings. 10. A wing portion and a flat portion connected to the wing portion.
A platform and a chassis connected to the platform
And a projection provided on both sides of the shank.
Fins and a dovetail connected to the shank.
Heat-resistant coating layer on the surface of
ZrO ₂ -based ceramic constituting the heat-resistant coating layer
Layer is the smallest columnar structure of ZrO ₂ ceramics (one
Columnar structure (secondary column)
The one or more aggregate thickness direction of Jo tissue), fine cladding
Formed by columnar structure (tertiary columnar structure) divided by
Gas turbine operation characterized in that it is made of
Wings. 11. A fuel gas compressed by a compressor.
The blades through the stationary blades and impinge on the blades
A gas turbine for rotating the moving blades,
And three or more moving blades, and at least the first stage of the moving blade
Platform having a flat part connected to the wing part
A shank connected to the platform,
Fins consisting of protrusions provided on both sides of the
With a dovetail connected to the
At least one wing surface is provided with a heat-resistant coating layer,
The configuration of the coating layer is higher on the base material than in the base material.
A metal layer made of an alloy with excellent corrosion resistance is provided.
Al ₂ O ₃ ceramic thin film layer, dense granular
ZrO ₂ -based ceramic coating layer and columnar set
Providing a woven ZrO ₂ -based ceramic coating layer, and
The ZrO ₂ -based ceramic layer having a columnar structure
A gas turbine characterized by having a lock. 12. A combustion gas compressed by a compressor.
The blades through the stationary blades and impinge on the blades
In the gas turbine for rotating the rotor blade by the
The gas temperature is 1500 ° C. or more, and the moving blade is three stages or more.
The combustion gas temperature at the first stage inlet of the rotor blade is 130
0 ° C or higher, and the first stage of the rotor blade has a total length of 200 mm or more
In the first stage of the moving blade, a wing portion and a flat portion connected to the wing portion
Platform that has
Shank portion and projections provided on both sides of the shank portion
And a dovetil connected to the shank
At least one of a moving blade and a stationary blade for a gas turbine having
A heat-resistant coating layer is provided on one of the wing surfaces, and the heat-resistant coating layer is
Configured to ZrO ₂ based ceramic layer is ZrO ₂ based ceramic
Many aggregates of the minimum columnar structure (primary columnar structure)
One or more of the columnar structures (secondary columnar structures)
Columnar structure divided by cracks in the film thickness direction (tertiary
Columnar structure)
gas turbine. 13. Driving by combustion gas flowing at high speed
A gas turbine, the combustion exhaust gas of the gas turbine
An exhaust heat recovery boiler for obtaining steam;
Operating steam turbine, and the gas turbine and steam turbine
Combined power generation plan with bin driven generator
In the gas turbine system, the gas turbine includes a moving blade and a stationary blade.
At least three stages, and the inlet temperature of the first stage of the bucket of the combustion gas
Is above 1300 ° C and the temperature of the exhaust gas at the turbine outlet is
560 ° C. or higher, and 53
Obtain steam of 0 ° C or higher, and the steam turbine is integrated with high and low pressure
The steam temperature to the first stage of the steam turbine blade.
Is 530 ° C. or higher, and the power generation capacity of the gas turbine is
50,000 kW or more and steam turbine power generation capacity of 30,000 kW or more
Above, the total thermal efficiency is 45% or more,
The first stage has a total length of 200 mm or more.
Platform having a flat portion and a flat portion connected to the wing portion
A shank portion connected to the platform;
A fin comprising protrusions provided on both sides of the shank portion, and a dovetail connected to the shank portion, wherein a heat-resistant coating layer is provided on at least one of the blade surfaces of the moving blade and the stationary blade, and the heat-resistant coating layer is provided. The ZrO ₂ -based ceramic layer that constitutes is composed of a large number of aggregates of the minimum columnar structure (primary columnar structure) of the ZrO ₂ -based ceramic (secondary columnar structure).
Characterized by a columnar structure (a tertiary columnar structure) divided by cracks in the film thickness direction.