JP3503997B2 - Thermal barrier coating 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 thermal barrier coating member used in a high temperature oxidizing and corrosive atmosphere and a method for producing the same.

[0002]

2. Description of the Related Art In a gas turbine for power generation, raising the operating gas temperature is effective for improving power generation efficiency.
With this high temperature, blades, vanes, in the high-temperature parts such as the combustor, durable propensity <br/> excellent plan from two viewpoints of heat resistance temperature increase of the cooling characteristic improvement and materials for lowering the temperature of the component materials Is being considered.

First, in order to improve the cooling performance, it is effective to increase the cooling air flow rate. However, when Ru increases the cooling air flow, there is reduction in combustion gas temperature leads to a decrease in power generation efficiency from the surface. Therefore, in order to improve the cooling performance without increasing the flow rate of the cooling air,
Attempts have been made to increase the thermal conductivity between the material and the cooling gas, which is represented by film cooling and impingement cooling, and to increase the contact area between the material and the cooling gas, which is represented by the return flow structure on the inner surface of the blade. There is. These methods have the drawback of complicating the structure of the parts.

On the other hand, as another method for increasing the temperature, materials are being developed to improve the heat resistant temperature. However, although Ni, Co, or Fe-based superalloys have been developed as high-temperature component materials, the heat resistance temperature is at most 900 ° C. in consideration of strength, oxidation resistance, and corrosion resistance. Further, as a material having higher heat resistance, there is a ceramic material having a high melting point and excellent in oxidation resistance and corrosion resistance. However, ceramic materials are significantly inferior to metallic materials in terms of toughness,
It has a drawback of poor workability. Therefore, there is a problem in terms of reliability and shape as a gas turbine component material.

By the way, there is a thermal barrier coating as one means for using a tough metallic material as a strength member. The thermal barrier coating prevents the temperature rise of the metal base material by coating the surface of the metal base material with a ceramic having a low thermal conductivity (the back surface is cooled). The surface temperature of the metal substrate is 5
There is also a report that the temperature can be lowered by 0 to 100 ° C (JP-A-62-62).
-2111387). As a result, the temperature of the gas turbine can be increased without increasing the temperature of the metal base material that is the strength member. Further, in the thermal barrier coating, since the heat flux from the combustion gas side to the cooling gas side can be reduced, there is an effect that the temperature rise of the metal base material can be prevented and the cooling gas flow rate can be reduced.

On the other hand, the problem with the thermal barrier coating is the problem of cracking or peeling of the coated ceramic layer.
This is due to the essential problem that the ceramic layer formed on the surface is extremely fragile, and the fact that the physical properties of the material differ greatly between metal and ceramic, and large thermal stress is generated. In addition, long-term use in a high-temperature oxidizing or high-temperature corrosive atmosphere leads to deterioration of the coating film such as formation of oxides and a decrease in adhesion, which promotes cracking and peeling of the ceramic layer. The cracking or peeling of the ceramic layer lowers the heat shield performance, raises the temperature of the base material, and causes troubles such as melting and destruction of the base material that hinders the operation of the equipment.

Therefore, various measures for reducing cracking and peeling of the ceramic layer in the thermal barrier coating of the gas turbine high temperature component have been studied. These are roughly classified into two types, that is, relaxation of thermal stress and improvement of oxidation resistance and corrosion resistance. As a method for relaxing the thermal stress, there is a method for coating a metal material with a ceramic (Japanese Patent Laid - Open No. 6-
57399 ). This is to apply a compressive stress to a ceramic layer having a small coefficient of linear expansion by subjecting a surface of a metal base material to ceramic coating and then subjecting it to heat treatment. Therefore, the ceramic layer is used in a compressive stress field, and the occurrence of cracking and peeling is reduced. The metal composition changes gradually - some ceramic layer welding method (JP 61- 14
3567 ). This is to control the residual stress by forming a thermal spray coating while continuously increasing the ceramic content from the metal substrate to the ceramic on the surface and gradually increasing the substrate temperature during thermal spraying. As a result, the thermal stress during use is relieved, and the occurrence of cracks and peeling is reduced.

Next, as a material for improving the oxidation resistance and the corrosion resistance, there is a heat resistant ceramic coating (JP-A-57-140876). This is to interpose a Pt alloy having excellent oxidation resistance between the intermediate alloy bond layer and the ceramic layer on the surface of the metal base material. This ensures that,
Oxidation resistance and corrosion resistance at the interface between the alloy bond layer and the ceramic layer are improved, and the durability of the thermal barrier coating is improved.

[0009] Ceramic coated gas turbine combustors and methods of making the same are also well known . In this manufacturing method, an oxide film containing Al as a main component is previously formed on the surface of the alloy bond layer formed on the surface of the metal base material. This oxide layer prevents oxygen from entering the inside, prevents the progress of oxidation and corrosion of the alloy bond layer, and improves its durability.

[0010] not a thermal barrier coating to form a ceramic layer on the surface, with respect to the corrosion-resistant coatings on metal substrates, Ru spray coating alloy products there. This is Ni, C
The present invention relates to a superalloy in which a layer in which ceramics are finely dispersed in a superalloy matrix is formed on a superalloy base material based on o and Fe . This superalloy is more durable than conventional superalloys.

[0011]

As described above, various attempts have been made to prevent the peeling of the ceramic coating in the thermal barrier coating used in a high temperature oxidizing and high temperature corrosive atmosphere such as in a gas turbine. Among them, by improving the deterioration characteristics over time, such as the addition of an oxidation resistant layer,
Some have improved durability.

However, they are mainly composed of Pt or Al ₂ O _{3 on the} surface of the bond layer intermediate between the metal substrate and the ceramic layer.
Another intervening layer having excellent oxidation resistance and corrosion resistance is interposed, and an intermediate layer in which ceramics are finely dispersed in a superalloy matrix is not formed. Further, when forming an intermediate layer in which ceramics are finely dispersed in a superalloy matrix, there is no one that alleviates thermal stress by continuously increasing the ceramic composition ratio from the metal base material to the ceramic layer. .

[0013] The present invention has been made based on the above circumstances, durable, provides a thermal barrier coating member and a manufacturing method peeling is prevented with the superalloy substrate and the ceramic layer.

[0014]

The heat shield of the present inventionCoating
MemberHas excellent high temperature strength of Ni, Co or Fe group
On a superalloy metal substrate,ZrO _Two With Y as the main component
_Two O _Three , MgO, CaO and SiO _Two A few selected from
At least including oneCeramic layer with low thermal conductivityButFormationIt
WasThermal barrier coatingA member,Of the superalloymetal
Base materialThe aboveBetween the ceramic layer, Of the super alloyMetal base
Ni, Co or Fe, which have better oxidation resistance and corrosion resistance than materials
In the base metallic matrixAl _Two O _Three , Y _Two O _Three And
And ThO _Two 1.0 consisting of at least one selected from
SubmicronFinely dispersed ceramicWas doneMiddle class
Is formedIt is characterized by

[0015]

In the thermal barrier coating member of the present invention having the above-described structure , N is formed between the superalloy metal base material and the ceramic layer.
Al _{2 in} a metallic matrix based on i, Co or Fe
At least selected from O ₃ , Y ₂ O ₃ and ThO _2.
A ceramic material of 1.0 micron or less composed of one type
By forming a dispersed intermediate layer, it has excellent durability.
It can be a thermal coating member.

[0016]

1 is a sectional view of an embodiment of a thermal barrier coating member of the present invention. In this figure, Ni, Co,
Alternatively, a metallic base material 1 made of a superalloy based on Fe and excellent in high temperature strength is provided with an intermediate layer 2 in which a ceramic 5 is finely dispersed in a superalloy matrix 4 of Ni, Co or Fe base. is there. The ceramic quality of said,
Etc. _{A l 2 O 3, Y 2} O 3, ThO 2, includes a rigid, yet chemically stable oxide ceramic, which like are used one or more. The size of the ceramic quality is at 1.0μm or less, enhanced and oxidation resistance of the intermediate layer, there as small enough to satisfy the corrosion resistance. The ceramic layer 3 on the surface contains ZrO ₂ as a main component, and Y ₂ O
₃ , which contains at least one of MgO, CaO, and SiO ₂ , and has a low thermal conductivity and a phase stability at high temperatures in order to have a heat shield property.

FIG. 2 is a process drawing of an example of a method for manufacturing the above-mentioned thermal barrier coating member. The first step 6 is a step of producing the raw material powder. By mechanically alloying metallic MCrAlY powder containing Cr, Al, and Y and ceramic Y ₂ O ₃ powder in at least one of Ni, Co, and Fe with an attrik or high-speed ball mill, mechanical energy is applied. The powder is alloyed to prepare a powder in which Y ₂ O ₃ powder is ultrafinely dispersed in MCrAlY powder.
On the other hand, 8 wt% Y by electro-melting pulverization method or chemical deposition method
A ZrO ₂ powder partially stabilized with ₂ O ₃ is prepared.

[0018] From the second step 7 to the sixth step 11, on the superalloy metal substrate is the step of forming a _{powder Y} 2 _{O 3} powder is ultra-fine dispersed in the above MCrAlY powder . First, in the second step 7, a cleaning degreasing metal substrate superalloy, the pretreatment bra swing with subsequent Al ₂ O ₃ grids performed.

In the third step 8, the pre-processed superalloy metal substrate is set in a chamber. Repeat the chamber vacuum and gas replacement to set the oxygen concentration to 1
And 0 ^-2 MPa or less, the ambient pressure and ^{10 -4} P a.

The fourth step 9 is a step of cleaning the surface of the metal base material of the superalloy. By using a transferred arc with a superalloy metal base material as the negative electrode ,
Decomposes oxides on the surface of metal substrates.

The fifth step 10 is a step of preheating the metal base material of the superalloy. Superalloy gold by plasma jet
The genus substrate heated to 800 ° C..

The sixth step 11 is a step of spraying a superalloy of a powder in which Y ₂ O ₃ powder is ultrafinely dispersed in MCrAlY powder prepared by mechanical alloying onto a metal base material. The powder is melted by a plasma jet and solidified by hitting the superalloy metal base material at high speed to form a film.

In the seventh step 12 and the eighth step 13, M
Ceramic 8 wt% Y ₂ 0 with low thermal conductivity and high toughness is formed on a film in which Y ₂ O ₃ powder is ultrafinely dispersed in CrAlY powder.
₃ is a step of forming partially stabilized ZrO ₂ . In the seventh step 12, a superalloy metal substrate having a film in which Y ₂ O ₃ powder is ultrafine and ultrafine dispersed in MCrAlY powder is taken out from the chamber to the atmosphere. Eighth step 13
Then, Zr partially stabilized with 8 wt% Y ₂ O ₃ was formed on a film in which Y ₂ O ₃ powder was ultrafinely dispersed in MCrAlY powder.
O ₂ is melted by a plasma jet and hit at high speed to form a film.

The ninth step 14 is a post-treatment step. An oxygen concentration of 10 was obtained by forming an intermediate layer in which Y ₂ O ₃ powder was ultrafinely dispersed in MCrAlY powder and ZrO ₂ partially stabilized with 8 wt% Y ₂ O ₃ on a metal base material of a superalloy.
^-In an inert gas atmosphere of Ar of ^-2 Pa or less, 1100
Heat treatment is performed at 4 ° C. for 4 hours. As a result, the adhesion between the metal base material of the superalloy and the intermediate layer is improved by element diffusion, and the intermediate layer coating is densified.

FIG. 3 shows steps of another embodiment of the method for manufacturing a thermal barrier coating member of the present invention. In this figure, the first step 15 is a step of producing a raw material powder. In this step, in at least one of Ni, Co, and Fe,
Metallic MCrAlY powder containing Cr, Al, and Y and ceramic Y ₂ O ₃ powder are mechanically alloyed by an strike or a high-speed ball mill to alloy the powder with mechanical energy, and Y is added to the MCrAlY powder. _A powder in which ₂ O ₃ powder is ultrafinely dispersed is prepared. on the other hand,
8 wt% Y ₂ O ₃ by electro-melt pulverization method or chemical deposition method
To produce a partially stabilized ZrO ₂ powder. From the second step 16 to the fifth step 19, on the superalloy metal substrate, a step of solidifying the powder Y ₂ O ₃ powder is ultra-fine dispersed in the above MCrAlY powder.

First, in the second step 16, the superalloy gold is used.
Cleaning degreasing the genus substrate.

Next, in the third step 17, the superalloy gold is used.
Set the genus base material made of SUS304 of the can, superalloys
A powder in which Y ₂ O ₃ is finely dispersed in the above MCrAl powder on a metal substrate and Zr partially stabilized with 8 wt% Y ₂ O _3.
Laminate with O ₂ powder.

In the fourth step 18, the inside of the can in which the powders are laminated has an oxygen concentration of 10 ⁻³ Pa or less and a total pressure of 1
0 ^-1 evacuated to a P a following, vacuum sealing the inside.

In a fifth step 19, a superalloy metal base material and a can in which powder is vacuum-sealed are set at a pressure of 200 MPa,
Hold in an Ar gas atmosphere at a temperature of 1000 ° C. for 2 hours.
As a result, an intermediate layer in which the Y ₂ O ₃ powder is ultrafinely dispersed in the MCrAlY powder and a ZrO ₂ layer partially stabilized with 8 wt% Y ₂ O ₃ on the surface are formed on the surface of the metal substrate of the superalloy.

In the sixth step 20, an intermediate layer in which Y ₂ O ₃ powder was ultrafinely dispersed in MCrAlY powder and ZrO partially stabilized with 8 wt% Y ₂ O ₃ were formed on a superalloy metal substrate.
₂ formed with Ar having an oxygen concentration of 10 ⁻³ Pa or less.
Heat treatment is performed at a temperature of 1100 ° C. for 4 hours in a gas atmosphere. This improves the adhesion between the superalloy metal base material and the intermediate layer due to element diffusion, and makes the coating film of the intermediate layer dense.

There is another embodiment of the method for manufacturing the thermal barrier coating member shown in FIG. First, the first step 6
This is the powder preparation process. Metallic MCrAl containing Cr, Al and Y in at least one of Ni, Co and Fe
The Y powder and the ceramic Y ₂ O ₃ powder are mechanically alloyed by an attritor or a high-speed ball mill to prepare a powder in which the Y ₂ O ₃ powder is ultrafinely dispersed in the MCrAlY powder. At this time, a total of 11 types of mechanical alloy powders in which the composition ratio of the Y ₂ O ₃ powder changed from 0% to 50% at intervals of 5% are prepared. Further, in the sixth step 11, MCrA created by mechanical alloying
In a step of forming a powder in which Y ₂ O ₃ powder is ultrafinely dispersed in 1Y powder on a superalloy metal base material by a thermal spraying method, the 11 types of mechanical alloy powders described above are sequentially arranged from the smallest composition ratio. Spray. In this way
An intermediate layer having an increased composition ratio of Y ₂ O ₃ can be continuously formed from a superalloy metal substrate.

There is another embodiment of the method for manufacturing the thermal barrier coating member shown in FIG. First, the raw material powder creation step of the first step 15. Ni, Co,
In at least one of Fe, Cr, Al, and _Y 2 _{O 3} powder of MCrAlY powder and the ceramic quality of the metallic containing Y, by mechanical alloying by attritor, high-speed ball mill, _Y 2 O in MCrAlY powder _Three
A powder in which the powder is ultrafinely dispersed is prepared. At this time, Y ₂ O
Eleven kinds of mechanical alloy powders in which the composition ratio of the _three powders differ from 0% to 50% at intervals of 5% are prepared. Super alloy
The metal base material is set in a SUS304 can. Then, Y ₂ in MCrAlY powder on the superalloy metal substrate.
When O ₃ is set to powder ultrafine dispersion, wherein the 1
8wt% Y ₂ O on one kind of mechanical alloy powder
_{3 The} powders are laminated in order from the one having the smallest composition ratio. Then, 8 wt% Y ₂ O ₃ was added on the mechanical alloy powder.
The partially stabilized ZrO ₂ powder is laminated. In the fifth step 19, by holding the can containing the powder laminated with the superalloy metal base material in an Ar gas atmosphere at a pressure of 200 MPa and a temperature of 1000 ° C. for 2 h, the superalloy metal base material surface is superposed. a layer of Z r _{O 2} was partially stabilized by the metal substrate of the alloy continuously in _Y 2 _O of the intermediate layer and the surface composition ratio is increased in _{3 8wtY 2} O ₃ is completed.

There is another embodiment. As described above, by a thermal spraying method or a powder solidification method, a metallic MCrAlY containing Cr, Al, and Y in one of Ni, Co, and Fe on a metallic base material of a superalloy , and a ceramic Y ₂ O ₃
The following steps are added after forming the finely dispersed intermediate layer. The superalloy metal base material on which the intermediate layer is formed is packed in a container made of SUS304 together with Al and Al ₂ O ₃ powder, and the temperature is set to 1000 while flowing NH ₄ Cl and H _2.
Hold at 5 ° C for 5 h. As a result, an Al-rich layer having oxidation resistance and corrosion resistance is formed on the surface of the intermediate layer. Further, this is placed in an oxidizing atmosphere at a temperature of 700 to 1100 ° C. for 0.5
By holding for ~ 500h, the Al becomes surface Al ₂
Change to O ₃ .

The operation of each of the above embodiments will be described with reference to FIGS.

First, metallic MCrAlY containing Cr, Al, and Y in at least one of Ni, Co, and Fe.
By mechanically alloying the powder and the ceramic Y ₂ O ₃ powder with an attritor, MCrAlY
A mechanical alloy powder in which Y ₂ O ₃ powder is ultrafinely dispersed can be prepared. In FIG. 4, the horizontal axis represents the rotational speed R × time t as mechanical energy E, and the vertical axis represents the Y ₂ O ₃ powder particle size. The greater the mechanical energy on the horizontal axis, the more Y
It is clear that the ₂ O ₃ particle size r can be reduced. Y ₂ O ₃ powder having an initial particle size r of several tens of μm also has a rotation speed of 500 rp.
If a mechanical alloying process is performed for 10 h at m, Y ₂ O ₃
The powder particle size r can be less than 1 μm. One of the characteristics of mechanical alloy powder is that it has one MCrAl powder.
Fine Y ₂ O ₃ powder is present in a dispersed form in the Y matrix.

Further, Ni, Co, in at least one of Fe, Cr, Al, the MCrAlY containing Y _Y 2 O
By using the intermediate layer in which the _three particles are finely dispersed, the oxidation resistance and the corrosion resistance are improved.

FIG. 5 shows a thermal barrier coating member prepared by using a normal MCrAlY powder, and Y ₂ O ₃ with respect to the oxidation weight increase W when kept in the air at a temperature of 1000 ° C.
It is a comparison with a thermal barrier coating member using an intermediate layer in which particles are finely dispersed by 5%. Than this,
It can be seen that the thermal barrier coating member of the present invention has a significantly small increase in oxidation. This means that the Y ₂ O ₃ particles effectively contribute to the trap of oxygen element. Also,
A 5% Y ₂ O ₃ particles were dispersed on the intermediate surface of A
FIG. 5 shows the case where an l-rich layer is added.
The oxidation increase W is further reduced.

Next, FIG. 6 shows the thermal barrier coating member prepared by using the normal MCrAlY powder and the thermal barrier coating member using the intermediate layer in which Y ₂ O ₃ particles are finely dispersed by 5% in high temperature use. The stress is shown in comparison. In this figure, the thermal stress in the width direction is shown, and in the thermal barrier coating member using the intermediate layer in which 5% of Y ₂ O ₃ particles are dispersed, the toughness is 8 wt% of the surface which is inferior to the base material or the intermediate layer. Y ₂
O ₃ -ZrO ₂ of thermal stress is reduced. This is Y ₂ O
By using an intermediate layer in which ₃ particles are finely dispersed, M
This is because the linear expansion coefficient is smaller and the Young's modulus is larger than when CrAlY is used as it is. That is, this intermediate layer shares a part of the tensile thermal stress acting on 8 wt% Y ₂ O ₃ —ZrO ₂ on the surface due to the difference in the coefficient of linear expansion from the metal base material of the superalloy and the temperature distribution. .

In addition, Y is continuously formed from the metal base material of the superalloy.
By composition ratio of ₂ O ₃ is the increased intermediate layer, further the thermal stress is relaxed. This is 8 wt% of the surface layer and MCrAlY of the matrix of the superalloy metal substrate and intermediate layer.
This is because it is possible to eliminate a rapid change in the linear expansion coefficient of Y ₂ O ₃ —ZrO ₂ . That is, qualitatively, MC
The linear expansion coefficient can be lowered by adding Y ₂ O ₃ to rAlY. However, by continuously increasing the composition ratio of Y ₂ O _{3 in} the intermediate layer, the linear expansion coefficient of the surface of the metal base material of the superalloy can be increased. The linear expansion coefficient is gradually reduced toward 8 wt% Y ₂ O ₃ —ZrO ₂ .

FIG. 7 shows the case where (a) the thermal stress in the plate width direction at the central portion and (b) the thermal stress in the thickness direction at the time of high temperature use, and the Y ₂ O ₃ ratio of the intermediate layer is constant. It shows in comparison with. From this figure, by continuously changing the composition ratio of the intermediate layer Y ₂ O ₃ particles, the tensile stress of the surface 8 wt% Y ₂ O ₃ —ZrO ₂ layer was increased by the thermal stress in the plate width direction at the central portion. In the stress reduction and thermal stress in the thickness direction at the edges, the superalloy metal substrate and the intermediate layer and the intermediate layer and 8 wt% Y ₂ O ₃ -ZrO
It is clear that the thermal stress can be reduced at the interface with the _two layers. According to the present invention described above , by using an intermediate layer in which Y ₂ O ₃ particles are finely dispersed in MCrAlY containing Cr, Al, and Y in at least one of Ni, Co, and Fe, oxidation resistance and corrosion resistance are improved. The property is improved.

Further, by adding a noble metal such as Pt or Ag or an Al-rich layer on the intermediate layer,
Oxidation resistance and corrosion resistance are increased.

[0042] Ni, Co, in at least one of Fe, Cr, Al, by using an intermediate layer of MCrAlY the _Y 2 _{O 3} particles were finely dispersed containing Y, can be reduced thermal stress during high temperature use.

[0043] Ni, Co, in at least one of Fe, Cr, Al, in the intermediate _{layer Y} 2 _{O 3} particles were finely dispersed in MCrAlY containing Y, 8 wt% of the surface of a metal substrate superalloy _{Y 2} O ₃ toward -Zr O _{2 layer, Y} 2 O
₃ it is assumed that the composition ratio of the particles increases continuously
Thus, it is possible to further reduce the thermal stress when using at high temperature.

A hydrocarbon containing a few hundreds of ppm of sulfur or vanadium and oxygen were used as fuels, and the surface temperature of the test piece was 1100 ° C.
The burner rig test was carried out. The test was repeated once a day by returning to room temperature. This allows normal MCrA
In the thermal barrier coating member made using 1Y powder,
Whereas _{8wt% Y 2 O 3 -Zr O} 2 layer surface at about 500 days to peel all <br/> surface, peeling the thermal barrier coating of the present invention did not occur. That is, Ni, Co, Fe
MCr comprising at least in the kind, Cr, Al, Y for
By using an intermediate layer in which Y ₂ O ₃ particles are finely dispersed in AlY, the durability of the thermal barrier coating member is improved.

As is apparent from the above, according to the present invention, a Ni-, Co-, or Fe-based superalloy excellent in high-temperature strength can be obtained .
Ni, C between the metal substrate and the low thermal conductivity ceramic
By using an intermediate layer in which a ceramic is finely dispersed in a metal matrix containing Cr, Al, and Y in at least one of o and Fe , in a component used in a high-temperature oxidizing or corrosive atmosphere such as a gas turbine high-temperature component. It is possible to obtain a thermal barrier coating member having excellent durability.

[0046] Also, only either the ceramic layer from the metal substrate of the superalloy, by the composition ratio of the ceramic electrolyte of the intermediate layer is continuously increased, it is possible to further improve the durability. Furthermore, the durability of the thermal barrier coating member can be further enhanced by adding a layer having excellent oxidation resistance and corrosion resistance, such as noble metals such as Pt and Ag and Al, to the surface of the intermediate layer.

[0047]

According to apparent the present invention from the above, according to the present invention, high temperature oxidation, such as gas turbine hot components, durability rich shielding Netsuko Tin <br/> grayed components used in a corrosive atmosphere It can form, thereby enabling high efficiency of the gas turbine.

[Brief description of drawings]

FIG. 1 is a sectional view of an embodiment of a thermal barrier coating member of the present invention.

FIG. 2 is a process drawing of an example of a method for manufacturing the above thermal barrier coating member.

FIG. 3 is a process drawing of another embodiment of the thermal barrier coating manufacturing method of the present invention.

FIG. 4 shows the rotational speed R × time t as mechanical energy E on the horizontal axis.
Is a graph in which the vertical axis represents the Y ₂ O ₃ powder particle size.

FIG. 5 shows a thermal barrier coating member prepared by using a normal MCrAlY powder and an intermediate layer in which Y ₂ O ₃ particles are finely dispersed by 5% with respect to an increase W in oxidation when kept in the atmosphere at a temperature of 1000 ° C. The figure which compared with the used thermal barrier coating member.

FIG. 6 is a comparison of thermal stress in a high temperature use between a thermal barrier coating member prepared by using a normal MCrAlY powder and a thermal barrier coating member using an intermediate layer in which Y ₂ O ₃ particles are finely dispersed by 5%. FIG.

FIG. 7 compares (a) thermal stress in the plate width direction at the central portion and (b) thermal stress in the thickness direction when used at high temperature with a case where the Y ₂ O ₃ ratio of the intermediate layer is constant. Figure shown.

[Explanation of symbols]

1 ......... superalloy metal substrate 2 ......... intermediate layer 3 ......... ceramic layer 4 ......... metallic 5 ......... ceramic electrolyte

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Hiroshi Ishiwata 4-4, 2 Suehiro-cho, Tsurumi-ku, Yokohama-shi, Kanagawa Toshiba Corporation Keihin Plant (72) Inventor Yoshiyasu Ito 4-4, Suehiro-cho, Tsurumi-ku, Yokohama-shi, Kanagawa Stock company Toshiba Keihin office (56) Reference JP 57-140876 (JP, A) JP 62-210328 (JP, A) JP 1-301848 (JP, A) JP 61- 143576 (JP, A) JP-A-1-195267 (JP, A) Actual development 4-33649 (JP, U) (58) Fields investigated (Int.Cl. ⁷ , DB name) F01D 5 / 28,9 / 02,25 / 00 F02C 7/00 F23R 3/42 C23C 4/00

Claims (6)

(57) [Claims] 1. A Ni, Co or Fe-based superalloy metal base material having excellent high-temperature strength, and ZrO ₂ as a main component and Y ₂
A small amount selected from O ₃ , MgO, CaO and SiO _2.
Ceramic layer of low thermal conductivity comprising one Kutomo is formed
And a thermal barrier coating member, between the superalloy metal substrate wherein the ceramic layer, before
N superior in oxidation resistance and corrosion resistance to the superalloy metal base material
Al _{2 in} a metallic matrix based on i, Co or Fe
At least selected from O ₃ , Y ₂ O ₃ and ThO _2.
A thermal barrier coating member, characterized in that an intermediate layer in which one kind of ceramic material of 1.0 micron or less is finely dispersed is formed . Wherein said <br/> composition ratio of the ceramic membrane in the intermediate layer, the ceramic from the superalloy metal substrate
2. The thermal barrier coating member according to claim 1, wherein the thermal barrier coating member is made to continuously increase in layers so as to eliminate a sudden change in material properties such as a linear expansion coefficient and Young's modulus in the thickness direction. 3. Ni, Co or F serving as a matrix
Al ₂ O ₃ and Y ₂ O ₃ that are dispersoids with the e-based superalloy powder
And mechanically alloying at least one ceramic powder selected from ThO ₂ and
A material obtained by melting the powder obtained in Nikaru alloying to process by plasma or high-temperature gas flame, an intermediate layer on a metal substrate of the superalloy by blowing at high speed on a metal substrate superalloy
And a thermal spraying method or vapor deposition on the surface of the intermediate layer.
Patent in that it comprises a step of forming a ceramic layer by law
The manufacturing method of the thermal barrier coating member. 4. Ni, Co or F serving as a matrix
Al ₂ O ₃ and Y ₂ O ₃ that are dispersoids with the e-based superalloy powder
And a step of mechanical alloying of at least one of the ceramic <br/> click powder selected from the ThO _2, the mechanical aloin on a metal substrate of the superalloy in the mold
Laminating the powder obtained in step graying, high temperature, by keeping under high pressure, the powder solidified to form an intermediate layer on the superalloy metal substrate, thermal spraying on the surface of the intermediate layer or
Or a step of forming a ceramic layer by a vapor deposition method.
A method for manufacturing a thermal barrier coating member, which is characterized by the above . 5. After the step of forming the ceramic layer
In an atmosphere of an inert gas such as Ar or N ₂ under reduced pressure with an oxygen concentration of 10 ⁻² Pa or less, a temperature of 600 ° C. to 1200 °
The method for producing a thermal barrier coating member according to claim 3 or 4 , comprising a step of performing a heat treatment at 0.5 ° C for 100 hours. 6. In the step of mechanically alloying
Of the Ni, Co or Fe-based matrix that becomes the matrix.
Composition of superalloy powder and ceramic powder to be the dispersoid
Prepare several kinds of powders with different ratios and perform a thermal spraying process or powder solidification process to form the intermediate layer.
Prepared in the step of mechanical alloying
Ceramics that become the dispersoid among several types of powders
The superalloy is used in order from the powder with the smallest composition ratio of the powder
The intermediate layer is formed on the metal substrate of
Thermal barrier coating according to any one of claims 3 to 5.
Manufacturing method of parts.