JPS61174385A - Ceramic-coated fire resistant member and its production - Google Patents

Abstract

PURPOSE:To maintain stably the bond strength of a ceramic-coated layer for a long period by forming an oxide layer consisting essentially of Al between a bond layer and the coated layer in case of forming the specified bond layer and the ceramic-coated layer on a base material consisting essentially of Ni. CONSTITUTION:A bond layer of an alloy having the high-temp. oxidation resistance and the high-temp. corrosion resistance more excellent than the following base material is formed in 0.03-0.5mm thickness on the base material consisting essentially of at least one kind of Ni, Co and Fe. Then in case of forming a ceramic-coated layer of 0.05-0.8mm thickness consisting of ceramic on the bond layer, an oxide layer consisting essentially of Al is interposed in the boundary of both the layers by forming it in 0.1-20mu thickness. Still more the coated layer consists essentially of ZrO2 and contains one kind or two and more kinds of CaO, MgO and Y2O3 and as the bond layer, Cr and Al are contained in one or kinds of Co or Ni and furthermore one or two and more kinds of Hf, Ta, Y, Si and Zr are contained therein.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a heat-resistant member used in high-temperature or high-temperature corrosive environments and a method for manufacturing the same.

[Background of the invention]

Techniques for increasing the temperature of gas turbines are being studied with the aim of improving the power generation efficiency of gas turbine plants for power generation. With such rising temperatures, it is desired to improve the heat resistance temperature of gas turbine members. Ni group or C
With the development of O-based alloy materials, the temperature resistance of these heat-resistant alloys has improved, but currently it is saturated at about 850C. On the other hand, although ceramic materials are more durable than metal materials in terms of heat resistance, they have problems such as toughness when used as structural materials. Therefore, in order to cope with the increase in the height of such members, many studies are being conducted on methods to prevent the members from becoming hot.

As such methods, various methods of cooling members have been studied. Father, another method is to coat the surface of the metal member with ceramic, which has low thermal conductivity. Such coatings are called thermal barrier coatings (
Thermal Barrier Coating (hereinafter abbreviated as TBC).

TBC becomes more effective when used in combination with various cooling methods. - As an example, the temperature of the metal member that is the base material is 50 to 1
There are reports that it is possible to reduce 00C, and by using such a method, it is possible to improve the reliability of simply formed parts such as high-temperature gas turbines. By the way, the technical issues with TBCs include the adhesion mechanism between the base material and the ceramic coating layer and its reliability, since TBC is a combination of a heat-resistant alloy that constitutes the base material and a ceramic coating layer with different physical properties. There is a problem. In particular, in gas turbines, etc., thermal cycles such as starting and stopping can cause peeling of the ceramic coating layer,
Damage such as falling off may occur.

Therefore, various means have been used to solve this problem. The main method is to provide a bonding layer made of a metal alloy material between the ceramic temporary laminate and the base material, as shown in, for example, Japanese Unexamined Patent Publication No. 55-112804. The purpose of the bonding layer is to alleviate the difference in physical properties between the base material and the ceramic temporary laminate. However, in this case, the adhesion mechanism between the ceramic coating layer and the bonding layer is only a mechanical mechanism, and its strength is 2 to 5 degrees/2.
It is. Furthermore, in addition to the bonding layer, between the bonding layer and the ceramic coating layer, an intermediate layer made of a mixture of an alloy material constituting the bonding layer and a material constituting the ceramic coating layer, and an intermediate layer therebetween, which is made of a mixture of an alloy material constituting the bonding layer and a material constituting the ceramic coating layer. There are those that use multiple layers with different mixing ratios of materials, and those that use the intermediate layer itself in which the mixing ratio is changed continuously from an alloy material to a ceramic material.

These methods are aimed at alleviating the difference in physical properties between the ceramic coating layer and the bond f-, but in either case, the bond state between the ceramic and the alloy material depends on the mechanical bond. Only. Therefore, due to heat cycle etc. D.
If a large thermal stress is generated in the TBC, damage such as peeling or falling off will occur from a portion with weak bonding strength.

Furthermore, the ceramic coating layer bonding layer and intermediate layer used in such TBCs are mainly formed by plasma spraying. The reason for this is that, in addition to the fast fracture formation rate and excellent economic efficiency, the porous structure of the six-shot coating is utilized when it is applied to a ceramic coating layer. That is, by forming pores and fine racks, the pores and cracks are used to alleviate thermal stress. In this respect, ceramic sprayed coatings formed by plasma spraying have better thermal shock resistance due to effects such as thermal cycles than dense ceramic coating layers formed by methods such as sputtering. Because TBCs are used under high-temperature corrosive conditions due to impurities in the fuel, etc., TBCs with such porous ceramic coating layers have problems such as high-temperature oxidation and high-temperature corrosion of the alloy material forming the bonding layer or intermediate layer. There is. Although Ajaku materials have excellent high-temperature oxidation and corrosion resistance, due to the method of forming their alloy coating layers, they do not necessarily exhibit the high-temperature oxidation and corrosion resistance expected from original alloy materials. Conceivable. According to studies conducted by the present inventors, when TBC was subjected to a thermal cycle test after being exposed to a high-temperature oxidation or high-temperature corrosive environment, it was found that its durability was significantly reduced. In this case, it is thought that in addition to the fact that the bond between the ceramic material and the alloy material is originally a mechanical bond and its strength is weak, the surface of the alloy material at the boundary was oxidized or corroded, further reducing the adhesion. It will be done. In this way, in conventional TBC,
It is thought that the bonding strength between the ceramic and the alloy material is low, and that the surface of the alloy material changes due to high-temperature oxidation, high-temperature corrosion, etc., which further reduces the bonding strength of the ceramic alloy material. These problems greatly reduce the reliability of the TBC. On the other hand, in the plasma spraying method, instead of the method of spraying in the atmosphere, spraying is carried out in a reduced pressure atmosphere, which controls the atmosphere around the plasma arc and also controls the atmosphere pressure.

According to such thermal spraying in a reduced pressure atmosphere, the sprayed particles during thermal spraying are not contaminated by oxygen or the like, so that a very good metal alloy bonding layer can be formed. Such a metal alloy bonding layer is used as a coating layer to prevent high temperature oxidation, high temperature, and lambda damage of high temperature gas turbine components. Therefore, in view of the above points, the present inventors conducted various studies focusing on strengthening the bonding mechanism between the ceramic and the alloy material, with the aim of improving the durability of TBC.

The present inventors have discovered that T
We considered BC. For example, a TBC consisting of a ZrCh ceramic J layer and a bonding layer made of a metal alloy material.
A high temperature oxidation test of TBc was carried out using the following. This test took into account the installation of TBCs on gas turbine parts under high temperature conditions or the construction of TBCs on gas turbine parts that become locally hot.3o As a result, conventional TBCs
ro.

It was found that oxidation at the interface between the system coating layer and the bonding layer progressed significantly. The results of determining the adhesion of TBC before and after the test were 1000 tl: '500 hours of oxidation test.
The adhesion strength at the interface between the 0z coating layer and the bonding layer is 1/2 to 1/2.
It was found that the number decreased to 4.

This decrease in adhesion is caused by the thickness of the ZrO2-based coating layer,
Although some differences are observed depending on the porosity and the type and amount of additives added to ZrO, the decrease is remarkable in all cases. There were also some differences in the composition of the alloy material in the bonding layer, but all of them were reduced. Such a decrease in interfacial adhesion becomes more significant as the temperature of the oxidation test increases or as the test time increases. And l100C,10
In the 0 hour test, peeling damage from the interface was observed in some cases. On the other hand, metal alloy material z r o.

'l' using a mixture with other materials as the intermediate layer
In B C, the decrease in adhesion in the oxidation test was even more remarkable. These results also correspond to the results of high-temperature thermal cycle tests conducted by the present inventors. That is, 97011:', 1020c.

Even in a test in which the test piece was held at each temperature of 1070C and 1120C for 30 minutes and cooled down to 150C by air cooling, the number of repetitions until TBC damage occurred decreased significantly as the test temperature increased. Such problems with conventional TBCs become a serious obstacle in obtaining a highly reliable TBC that can cope with the high temperatures of gas turbines. In other words, TB is used for the purpose of preventing the base material temperature of gas turbine parts from increasing and reducing the temperature.
When performing C, it is difficult to sufficiently reduce the base material temperature of parts with conventional TBC because the TBC has low high-temperature durability.

Therefore, the present inventors constructed a TBC with excellent high-temperature durability that can sufficiently reduce the base material temperature of gas turbine components even under high-temperature operating conditions, instead of gas turbine components constructed with conventional TBCs. Gas turbine components were studied.

That is, the inventors of the present invention took the above points into consideration, conducted various studies with the aim of obtaining a TBC sufficient to achieve high temperatures in a gas turbine, and created a TBC with excellent ease of penetration. This led to the invention of gas turbine parts.

[Purpose of the invention]

An object of the present invention is to improve the reliability of TBC. That is, the object is to provide a TBC in which the cohesive force between the ceramic material and the base material is stable over a long period of time, and is less likely to crack or peel.

[Summary of the invention]

The present invention forms a bonding layer of an alloy that has better resistance to 11IIt oxidation and high-temperature corrosion than this substrate on a base material made of a metal material, and forms a ceramic coating layer on the alloy bonding layer. The heat-resistant member is characterized in that an oxide layer containing Al as a main component is formed at the boundary between the alloy bonding layer and the ceramic failure layer.

According to the present invention, the oxide layer containing Al as a main component is stable even in high-temperature atmospheres, prevents the progress of oxidation of the alloy bonding layer, and has strong bonding strength with the ceramic coating layer, so it can last for a long time. Even when used for a period of time, cracking and peeling of the ceramic coating layer can be prevented.

[Embodiments of the invention]

The details of the present invention will be explained below. First, the conventional T
We examined the problems of HC in detail and investigated their causes. The cross-sectional structures of TBCs subjected to various oxidation tests were observed. An example of the results is shown in FIGS. 6 and 7.

These microstructure photographs show the cross section of the bonding layer portion at a magnification of 100 times, and in FIG. 6, defects have occurred at the interface between the Z r 02-based coating layer and the bonding layer. FIG. 7 shows the results of a TBC in which a mixed layer of an alloy material and a Zr01-based material was formed between the bonding layer and the ZrCh-based coating layer. In this case, the alloy material of the intermediate layer is significantly oxidized. These phenomena are also observed in high-temperature thermal cycle tests. That is, T
In BC, the problem of oxidation of the bonding layer or intermediate layer occurs through the Z r Ch-based coating layer having a porous or micro-cracked structure to alleviate thermal stress. Such oxidation significantly reduces the adhesion of the interface, and the TBC may be peeled off from the interface due to thermal stress or the like. The cause of such interface oxidation is that Z
It is believed that one important factor is that the rOR-based material becomes a semiconductor, facilitates the movement of oxygen, and causes an increase in the oxygen partial pressure at the interface. Such oxidation is considered to be promoted when an intermediate layer is formed, for example, because it causes an increase in the area of the interface. As a result of analyzing the state of the interface of a conventional TBC, it was found that an oxide containing Cr as a main component was formed at the interface. Since such Cr-based oxides are unstable at high temperatures, damage occurs from the portion where the oxides are formed. Therefore, in TBCs for high-temperature gas turbines, it is necessary to fully consider oxidation at the interface.

From this viewpoint, the present inventors investigated various methods and found that it is promising to form a densely structured oxide thin film containing Al as a main component at the interface. Al-based oxidized proboscis is stable at high temperatures, and Zr
It does not become a semiconductor at high temperatures like O, type materials. Therefore, a thin film of Al-based oxide is effective as a barrier to prevent internal oxidation. On the other hand, when such an Al-based oxide layer is thick, it becomes a new intermediate layer that reflects the physical properties of the Al-based oxide. As a result, thermal stress etc. 1lA
This will cause damage to the l-based oxide layer.

On the other hand, if it is thin, it cannot serve as a barrier that satisfies the internal antioxidant effect. Therefore, its thickness is 0.1μ
The thickness is desirably greater than or equal to m and less than or equal to 20 μm. The Al-based oxide layer in such a range becomes sufficient as a barrier layer for preventing internal oxidation of the single layer. On the other hand, another important effect of such an Al-based oxide thin film is that ZrC
We have succeeded in improving the adhesion between the h-based ceramic and the bonding layer. In other words, compared to the conventional TBC in which the z r Ox-based ceramic and the metal alloy constituting the bond 1- are mechanically bonded, the ZrO! The adhesion between the ceramic ink and the bonding layer is due to the Al-based oxide and ZrO! The bonding mechanism is extremely strong due to the Al-based oxide generated from the interface between the oxides called ceramic and the Al component in the metal alloy constituting the bonding layer. - As an example, 10 of TBC with such a thin film of Al-based oxide
In the 00c, soo time oxidation test, the bonding layer and Z
The adhesion strength of the Ch-based ceramic coating layer is 7 f/m" or more with almost no decrease. Figure 1 shows the T after the high temperature oxidation test.
This is an example of a cross-sectional structure of BC, and the magnification is 100x.

In FIG. 1, there are no defects at the interface between the ZrOx ceramic coating layer and the bond. Also, 1100C
, 100 hours of oxidation tests showed no decrease in adhesion or occurrence of defects at the interface. Furthermore, 1030C, 1070C, 11201: l', 117
Hold at each temperature of 0C for 30 minutes, air cooling for 15 minutes.
0C'! Table 1 shows the results of the test in which the cooling was manipulated.

Table 1 Samples 201 to 204 in Table 1 are conventional TBCs.

A205-208 are TBCs with a thin film of AL-based oxide
This is the result. As a result, the TBC having a thin film of Al-based oxide required about 3 to 7 times more repetitions to damage the TBC than the conventional TBC. Moreover, as the test temperature becomes higher, the effect becomes more pronounced. in this way,
The TBC having a thin film of Al-based oxide, which was discovered by the present inventors, is particularly effective under high-temperature conditions.

Gas turbine components treated with such TB-C can be stable even under high temperature conditions. Furthermore, in a TBC having a Z r Q z based coating layer bonded via a thin film of an Al based oxide, the adhesion of the zr01 based coating layer is 7 odors/■2 or more. This adhesion is much greater than the adhesion of the Zr01 coating layer of conventional TBCs, which was about 3 to 5 odor/iat. It is also possible to prevent damage to TBCs in parts that rotate at high speeds such as blades.Therefore, we investigated the effects of applying such TBCs.In gas turbine parts, low NOx combustor parts, etc. In parts where the base material temperature becomes high, such as those shown in Figure 1, by applying TBC with excellent high temperature durability to the parts exposed to high temperature combustion gas, it is possible to stably reduce the temperature of the base material. - For example, for a cylindrical low NOx combustor part, combustion is performed by applying TBC with a thin film of Al-based oxide as described above on the inner surface of the cylinder exposed to high-temperature gas. The operating time for the TBC before it was damaged was approximately three times longer than that for parts coated with conventional TBC. This is because it has excellent durability under various conditions.

Therefore, the effect of reducing the base material temperature of the combustor component obtained by applying TBC is stably maintained. On the other hand, in combustor parts to which conventional TBC has been applied, the TBC is damaged in a short period of time, and the damage to the TBC is particularly severe in areas where the base material temperature is high. As a result, the effect of reducing the temperature of the base material by TBC disappears, and the temperature of the base material becomes high, resulting in damage to the parts. Further, in combustor parts, the temperature of the base material is particularly likely to rise in parts where cooling with compressed air or the like cannot be performed sufficiently due to the strength of the parts or the structure such as fixation of the combustor parts. In such parts, TB
The role of C is particularly important. In addition to reducing the temperature of the base material due to the heat shielding effect of TBC, TBC with a ceramic coating layer with low thermal conductivity prevents local temperature rise of the base material,
It also has the effect of making the temperature of the base material uniform. As a result, TBC is extremely important in preventing local temperature increases in parts due to structural or combustion conditions, and in preventing deformation or damage to parts due to local temperature increases in the base material. Become something. However, conventional TBCs have a problem in durability, especially at high temperatures, and in such parts where the temperature of the base material locally increases, the TBCs in those areas are likely to be damaged in a short period of time. In combustor parts, the base material vibrates due to combustion vibrations, so TBCs with reduced adhesion of the ceramic coating layer become more susceptible to damage under high-temperature conditions. Therefore, the most '1
'B It becomes impossible to exert sufficient effect on the areas where the effect of C is necessary. In addition, there is a possibility that the temperature of the base material in the damaged part of THC becomes higher than that in other parts where TBC is 4-all. For example, in parts that are in contact with flame, such as combustor parts, TBC also has the effect of reducing the amount of heat input from the flame to the base material due to the radiation effect of the ceramic coating layer. Therefore, the temperature of the base material in the damaged portion of the TBC may become lower than that without the TBC. As a result, the conventional TB
It is difficult to say that the effect of TBC can be fully demonstrated in gas turbine parts such as FC combustor parts by applying C.
Rather, for areas where the temperature of the base material is high, conventional TB
For parts constructed in C, the reliability of the parts may be impaired. On the other hand, in the gas turbine parts of the present invention in which a TBC having a thin film of A/, type oxide is constructed, for example, in low NOx combustor parts, the temperature of the base material may be localized due to the structure or combustion conditions. Ti
Since 3C is durable, and sometimes even durable at temperature control, damage to the TBC occurs in areas where the temperature of the base material increases. Therefore, in the gas turbine component of the present invention having a thin film of Al-based oxide, even if the temperature of the base material becomes locally high, the heat shielding effect of the TBC is sufficiently maintained, and the TBC
It also has the effect of mitigating the local increase in concealment caused by BC.

As a result, the gas turbine component of the present invention is highly reliable. Here, in parts where the temperature of the base material becomes locally high, TBC containing Al-based oxide is used in that part.
It is also effective to construct

That is, the heat shielding effect of the TBC can prevent a local temperature rise. Furthermore, if there is no TBC in other areas, the radiation effect of the ceramic coating layer of the TBC can reduce the amount of heat input to the base material in the area where the TBC is applied, reducing the heat input to other areas without TBC. It can also be expected to balance the amount of heat and prevent local temperature increases in the base material. In this way, the TBC having a thin film of Al-based oxide can be applied to the entire surface or a portion of the part of the gas turbine component that is exposed to high temperatures, so that its effects can be fully exhibited in either case. As an example of such a local temperature increase in the temperature of the base material, the combustor component has been described, but a similar phenomenon may occur in other gas turbine components. For example, in stationary blades, rotor blades, etc., it is difficult to equalize the temperature of the base material that constitutes the blades due to constraints on the cooling structure of the blades. Further, as gas turbines become hotter, such differences in temperature distribution tend to increase. Therefore, a gas turbine component having a durable TBC with a thin film of Al-based oxide can be highly reliable and enable high temperature gas turbines. Hereinafter, the present invention will be explained in detail using examples.

Example 1 Hastelloy-X (22 wt.
%Cr-1,5wi%Co-9wt%MO-19W
After degreasing and cleaning the surface, the surface was sprayed using a steel grid, and then plasma sprayed to give 19 wt%
Ni-25wt%Cr-7wt%Al-0,6wt%Y
A coating layer of an alloy material consisting of -5 wt% Ta and the balance Co was formed. Plasma spraying uses zoo'rorr pressure A
This was done in r. In this case, the oxygen partial pressure in the atmosphere in which plasma spraying was performed was measured with an oxygen sensor and was found to be 19-satm or less. The plasma output is 40kW. Co with a thickness of 0.01 m under these conditions.

A Ni, Cr, Al, and Y alloy coating layer was formed to serve as a bonding layer for the TBC. Immediately after that, Z
A r02-8% Y2O3 coating layer was formed. The thermal spraying conditions were a plasma output of 50 kW and thermal spraying in the atmosphere. Zr0z
The thickness of the 8% Y2O3 coating is 0.3 mm. Thereafter, a heat treatment was performed in vacuum at 1060C for 10 hours to perform a diffusion treatment between the bonding layer and the base material. For comparison, a TBC made of the same material as the TBC of the present invention and having a coating layer of the same thickness was prepared by a conventional method. As a conventional method, the aforementioned alloy material was thermally sprayed using Ar gas in the atmosphere, and then coated with Zr0z 8% Y2O3 in the same manner as described above. Next, in order to confirm the effects of the TBC of the present invention, various tests described below were conducted. First, an oxidation test was conducted at various temperatures, and after the test, the appearance and cross-sectional structure were observed, and an adhesion test was conducted. Table 2 shows the results of appearance observation and adhesion test.

&1 to A6 in Table 2 are the results of conventional TBC, &7 to A11
is the result of the TBC of the present invention created in this example. In other words, with conventional TBCs, temperatures of 1070C or higher (10
After holding for 0 hours), the ZrO-rich 8% Y2os coating layer peeled off and the TBC was damaged. On the other hand, T of flats 7 to &11 of the present invention
BC has no external damage. On the other hand, the results of the adhesion test of the TBC after the oxidation test also show that the adhesion of the conventional TBCs of 1 to 6 with no damage to the TBC was 2 to 2.
5 Kg/tag 2, the adhesion strength decreases as the oxidation test temperature increases. Furthermore, the fractured portion in the adhesion test was the boundary between the bonding layer and the ZrO, -8% Y2O3 coating layer. On the other hand, in the TBCs of the present invention shown in Nos. 47 to 11, no decrease in the adhesion of the TBC was observed under any of the oxidation test conditions, and the adhesion strength of the adhesive (adhesive strength: 7 h/m")
7 Kg/le, which is the limit value of the adhesion test method using
The value was greater than x”.

Therefore, the broken parts after the test were all adhesive parts. Next, a thermal cycle test was conducted using the test piece after the above oxidation test. Test conditions were 750C.

Hold for 15 minutes, hold in 20-25C water for 15 seconds, and repeat. Table 3 shows the results.

Table 3 Thermal Cycle Test Results The samples in Table 3 are samples after each oxidation test was conducted. Conventional TBC of Table 3 Nakaya 1~&3 is 200~
'lrO* 8% M2 after 500 thermal cycle tests
The O3 coating layer peeled off and the TBC was damaged. On the other hand, the TBCs of the present invention shown in Table 3 Nakaya 7 to &11 showed no damage even after repeated thermal cycles of 1400 to 1700 times, and
Damage to the TBC was observed during the second thermal cycle test. As described above, the TBC of the present invention is a highly durable TBC with excellent high-temperature oxidation resistance or thermal shock resistance compared to conventional TBCs.

Example 2 A TBC was created using the same materials as in Example 1 and under the same thermal spraying conditions as in Example 1. Thereafter, heating was performed in vacuum at 1060C for 3 hours to perform a diffusion treatment between the base material and the bonding layer consisting of the C09Ni, Cr, Al, and Y coating layers. Furthermore, after that, heat treatment was performed in the air at 1000C for 15 hours. The TBC of the present invention produced in this way has Z
rO! -8% Y! 03 Coating layer and Co, Nt.

A boundary layer with a thickness of about 5 μm was formed almost uniformly at the interface with the Cr, T, and Y coating layers. This boundary layer is EPM
As a result of A analysis or X-ray diffraction, it was found that the product was an Al-based oxide. For comparison, a TBC was prepared by a conventional method using the same material as the TBC of the present invention, and further, the TBC was subjected to the same wave number treatment in vacuum and heat treatment in air as the TBC of the present invention. 4101 in Table 3
and Ken 102 are the TBCs of the present invention created in this manner.
These are the results of a heat cycle test similar to that in Example 1 using a conventional TBC for comparison. In Table 3, '
In the conventional TBC of lt 101, the ZrCh-8%M z Os coating layer peeled off after about 500 cycles. on the other hand,
TBC 4102 of the present invention in Table 3 was damaged after about 1500 repetitions. Thus, the TBC of the present invention
It has approximately three times the durability compared to conventional TBC.

Next, FIG. 2 shows an example in which the present invention is applied to a TBC gas turbine combustor.

The construction part of the TBC is the inner surface of the cylindrical part of the combustor liner 1 shown in FIG. The downstream part 1a of the combustor liner 1 has a cooling air opening (hereinafter referred to as louver 2), but since the metal temperature becomes very high, a T
BC was constructed. The material of the base material of the fuel liner 1 is No. 1 STEROY
9%Mo-19%Fe-0,1%C-Remaining Ni)
It is. The TBC containing Al-based oxide was formed using plasma spraying. The details are as follows.

First, the liner was degreased and cleaned, and then plasted using a grid made of Al Snow 03. Immediately after forming a new surface on such a base material surface, 10%Ni-25%Cr-
A bonding layer was formed by plasma spraying an alloy material consisting of 7%At-0.6%Y-5%Ta-balance Co. As conditions for forming such a bonding layer, it is desirable that the plasma output be high and that the atmosphere around the plasma jet during thermal spraying be controlled. In particular, as an element of atmosphere control, the oxygen partial pressure should be reduced, preferably 1
It is preferable to set the pressure to 0-1 atm or less. Further, as another element of atmosphere control, it is desirable to carry out the process in a reduced pressure atmosphere.

By controlling the atmosphere in this manner, it becomes possible to form a bonding layer that is preferable for obtaining the present invention.

In this example, A
r atmosphere and the atmospheric pressure is 200 Torr.
The test was carried out in a controlled atmosphere. Further, in order to obtain the present invention, it is preferable to maintain the substrate temperature during thermal spraying at 500 to 1000C. In this example, the temperature was within the range of 600 to 700C. Under these conditions, the thickness of approximately 0,1■
A thick bonding layer was formed. After that, Zr is applied on top of the bonding layer.
A coating layer of a ceramic material made of Ch-6% Y103 was formed. The coating layer was formed by plasma spraying. Thermal spraying was carried out using a high-power plasma spraying method with an output of 55 kW. The thickness of the cover is about 0.3-. After forming the TBC in this way, the part was heated in a vacuum to perform a diffusion treatment between the bonding layer and the substrate. Such a diffusion process is carried out in a vacuum of about 10-400 m
The conditions were to hold the temperature at 060C for 5 hours. After that, 900c in the atmosphere.

Heat treatment was performed for 20 hours. There are no particular restrictions on the conditions for such diffusion treatment or heat treatment, but it is preferable that the diffusion treatment be carried out at a temperature below the spray body temperature of the base material, at a temperature of 800 C or above, and for a period of 3 hours or more and 100 hours or less; The heat treatment is desirably carried out at a temperature of 600C or more and 1200C or less for 1 hour or more and 200 hours or less. In this way, a TBC4-coated combustor liner of the present invention having a KT-based thin film was produced. The combustor liner 1 has a structure including a cooling looper 2 as shown in FIG. In order for such a louver 2 to exhibit a sufficient cooling effect, its dimensions must fall within a predetermined range. Therefore, if the thickness of the TBC becomes extremely thick in a part of the louver, the cooling effect of that part will be significantly reduced, leading to an increase in the temperature of the base material. Furthermore, when the thickness of the TBC becomes locally thick, the durability of the TBC in that area is significantly reduced. Therefore, in this embodiment, the inner surface 3 is
I decided to do it. By forming a condensation layer or a ZrO*-6% YzOs coating layer under such conditions, a TBC in which the thickness of a portion of the louver was not thick was obtained. The TBC of the combustor liner formed in this way is
Its cross section and structure are almost the same as in Figure 1, with a bonding layer and Zr
A boundary layer made of Al-based oxide and having a thickness of about 3 μm was formed at the interface with the 02-6% Yx Os coating layer. Using a combustor liner with such a TBC, 1000
A heat cycle test was conducted in which the sample was held for 30 minutes and then held in water at 20 to 25C for 5 minutes. For comparison, A
A similar thermal cycle test was conducted using a conventional TBC that did not have a thin film of l-based oxide and was formed in the same manner as the combustor liner of the present invention.

As a result, the combustor liner of the present invention did not cause any fA in the TBC even after 50 repetitions, whereas the conventional TBC
In the case of the combustor liner subjected to this process, TBC damage occurred after approximately 90 cycles.

Combustion tests were conducted under the same conditions using the combustor liner of the present invention produced as described above and a conventional combustor liner produced for comparison. As a result, about 15
In the 00 hour test, damage to the conventional TBC occurred in the area without the cooling louver shown in the area A in FIG. 2. On the other hand, no damage to the TBC was observed in any part of the combustor liner of the present invention. In addition, the combustor liner after the test was cut in the area covered by the person in Figure 2, and the state of the TBC was observed. As a result, observation of the cross-sectional structure revealed that no damage had occurred in any part of the TBC.

Further, in the combustor liner of the present invention, the dimensional change in the liner diameter in the area A in FIG. 2 was about 3% or less. On the other hand, in a conventional combustor with a damaged TBC, the dimensional change was as large as about 5% of the liner diameter. As described above, the effects of the combustor liner TBC of the present invention are maintained over a long period of time, and as a result, there is a sufficient effect in preventing problems such as deformation of the combustor liner.

The test was carried out on a combustor liner having the structure shown in Fig. 4.

In a combustor liner having this structure, the temperature of the base material increases significantly in the range shown in FIG. 4C. Therefore, the combustor liner of the present invention was fabricated by applying TBC to the inner surface of the portion C in FIG. 4 exposed to combustion gas under the same conditions using the same coating layer material as in the case of FIG. 2. . For comparison, the conventional 'I'BC which does not have a thin film of Al-based oxide is shown in the part C of Fig. 4.
A combustor liner was fabricated. Tests were conducted using each of these combustor liners under the same combustion conditions. As a result, in the combustor liner of the present invention, no damage to the TBC was observed even after about 2000 hours of testing, and no deformation of the combustor liner such as a change in liner diameter occurred. On the other hand, in a combustor liner with a conventional TBC, the TBC was significantly damaged after about 2000 hours of testing. In addition, the liner diameter in that area varied greatly, causing deformation of the combustor liner. As described above, the combustor 2 inner according to the present invention, in which TBC is applied only to the portions of the base material where the temperature becomes high, has sufficient durability and reliability. Note that for the combustor liner shown in Fig. 4, the second
Similar to the example shown in the figure, the same effects as in this embodiment can be obtained even when TBC is applied to the entire inner surface of the liner.

Regarding the rotor blade 5 for a gas turbine having the structure shown in FIG. 5, all parts of the blade surface 6 and the shroud 7 part,
A rotor blade of the present invention was fabricated using a TBC having a thin film of an Al-based oxide. The material of the rotor blade 5 is (lNC0NEL-73
8). The material for the TBCt-groove bottom is the same as that shown in FIG. 2, and the manufacturing conditions are also the same as described above. For comparison, a rotor blade with a conventional TBC was also fabricated. A thermal cycle test similar to that described above was conducted for each of these rotor blades. As a result, the number of repetitions required for the rotor blade of the present invention until the TBC was damaged was about 2 to 4 times longer than that of the conventional rotor blade with TBC.

Although the combustor liner and rotor blades have been described in each of the above embodiments, the present invention is also effective for other gas turbine components exposed to high temperature conditions. Furthermore, regarding the bonding layer material constituting the TBC, in any of the conventionally known alloy materials with any composition range, Al is contained as a component in the alloy, especially when the amount is 5%.
It is desirable that the content is 30% or less, and there is no particular restriction as long as it is such an alloy material. Regarding the material constituting the ceramic coating layer, any material containing Zr(h) as the main component may be used, and stabilizers such as CaQ, Mg
Any one of O, Y2O5, etc. or a combination thereof may be used. There is also no particular limit on the thickness of each coating layer, but when considering the heat shielding effect and durability of TBC, the thickness of the bonding layer is 0.03 mm.
Waw or more and 0.5 or less, 1roz type coating layer is 0.0
The length is preferably 5 m or more and 0.8 m or less.

[Effects of the Invention] As explained above, according to the present invention, progress of oxidative corrosion of the bonding layer can be prevented, so that the bonding strength of the ceramic coating layer can be stably maintained over a long period of time.

[Brief explanation of the drawing]

Fig. 1 is a photograph of the cross-sectional structure of a TBC according to the present invention, Fig. 2 is an outline drawing of a gas turbine combustor to which TBe is applied, and Fig. 3 is a cross-sectional view taken along the line XX in Fig. 2. Figure 4 shows TBC
FIG. 5 is an external view of a gas turbine rotor blade, and FIGS. 6 and 7 are photographs of the cross-sectional structure of a conventional TBC after high-temperature oxidation.

Claims (1)

[Claims] 1. A bonding layer of an alloy having superior high-temperature oxidation resistance and high-temperature corrosion resistance than the base material is formed on a base material containing at least one of Ni, Co, and Fe as a main component, A heat-resistant member comprising a ceramic coating layer formed on the bonding layer, characterized in that an oxide layer containing Al as a main component is formed at the boundary between the alloy bonding layer and the ceramic coating layer. . 2. In claim 1, the material constituting the ceramic coating layer contains ZrO_2 as a main component and Ca
A ceramic-coated heat-resistant member characterized by containing any one of O, MgO, and Y_2O_3 or a combination thereof. 3. In claim 1, the material constituting the alloy bonding layer contains Co or Ni or a combination thereof, Cr and Al, and further contains H.
1. A ceramic-coated heat-resistant member characterized in that it contains any one of f, Ta, Y, Si, and Zr or a combination thereof. 4. A ceramic-coated heat-resistant member according to claim 1, wherein the oxide layer has a thickness of 0.1 μm to 20 μm. 5. Claim 4, characterized in that the alloy bonding layer has a thickness of 0.03 mm to 0.5 mm, and the ceramic coating layer has a thickness of 0.05 mm to 0.8 mm. Ceramic coated heat resistant parts. 6. The surface of the base material mainly composed of at least one of Ni, Co, and Fe contains Cr and Al in one of Ni and Co or a combination thereof, and has higher temperature oxidation resistance than the base material. a step of forming a bonding layer of an alloy with excellent properties and high temperature corrosion resistance; a step of forming a coating layer made of ceramic on the surface of the bonding layer; forming a ceramic-coated heat-resistant member. 7. In claim 5, the step of forming the bonding layer of the alloy is performed by plasma spraying in an atmosphere with an oxygen partial pressure of 10^-^3 atm or less. Method of manufacturing parts. 8. In claim 5, the step of forming the oxide layer is performed at a temperature range of 600°C to 1200°C for 1 hour to 1 hour after forming the ceramic bonding layer on the alloy coating layer.
A method for producing a ceramic-coated heat-resistant member, comprising the step of heat treatment in the atmosphere for 200 hours.