JP2008274357A - Thermal barrier coating member with columnar structure having excellent durability and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermal barrier member which, when being used, e.g., in the temperature range of ≥900°C, is inhibited from causing cracking and peeling in its barrier layer and has excellent heat resistance (heat cycle durability), and to provide a method for producing the same. <P>SOLUTION: The thermal barrier member 1 is equipped with: an alloy base material 11; an oxidation resistant layer 12 arranged at the surface of the alloy base material 11 and suppressing the oxidation of the alloy base material 11; and a thermal barrier layer 13 composed of a ceramic columnar body with a periodic C type structure and arranged at the surface of the oxidation resistant layer 12, wherein the axial periodic interval of the C type structure is ≤1 μm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a heat shield member excellent in heat resistance and a method for producing the same. More specifically, the present invention relates to a heat shield member useful as a high-temperature member such as a gas turbine part, a combustion equipment part, a jet engine part, and the like, and a manufacturing method thereof.

  In recent years, in order to improve the thermal efficiency of power generation gas turbines and aircraft gas turbines, research into increasing the temperature of combustion gases has been actively conducted, and the base materials such as moving blades and stationary blades that constitute gas turbines are heat resistant. A member formed by forming a ceramic layer on the surface of the substrate is known. Such a member is obtained, for example, by adopting a thermal barrier coating (TBC) system, and the inlet temperature of the combustion gas is increased to 1500 ° C. together with the improvement of the cooling technology of the member. Has realized a gas turbine that surpassed.

Patent Document 1 includes La ₂ O ₃ having a metal substrate, a metal bonding layer (MCrAlY alloy or the like) formed on the surface of the metal substrate, and a columnar structure formed on the surface of the metal bonding layer. A thermal barrier coating member having a Zr-based ceramic layer is disclosed, and this ceramic layer is formed by electron beam physical vapor deposition (EB-PVD).

JP 2004-270032 A

According to the conventional heat shield member, the higher the operating temperature, the more the ceramic heat shield layer is cracked or peeled off, and there is a problem that durability and reliability in the heat shield effect cannot be obtained.
The object of the present invention is, for example, when used in a high temperature range of 900 ° C. or higher, the occurrence of cracking or peeling of the heat shielding layer is suppressed, and the heat shielding member is excellent in heat resistance (thermal cycle durability). And a manufacturing method thereof.

  The present inventor formed a heat shield layer on the surface of a substrate having a poor regularity such as a turbine blade while rotating the substrate. As shown in FIG. It was found that the ceramic columnar body 131 has a C-shaped structure, and that the obtained heat shield member has heat resistance (thermal cycle durability) depending on the axial interval of the C-shaped structure. The invention has been completed.

The present invention is shown below.
1. An alloy substrate, an oxidation resistant layer disposed on the surface of the alloy substrate and suppressing oxidation of the alloy substrate, and a ceramic columnar body disposed on the surface of the oxidation resistant layer and having a periodic C-type structure A heat-shielding member comprising a heat-shielding layer comprising: a heat-shielding member having an axial periodic interval of the C-type structure of 1 μm or less.
2. _2. The heat shield member according to 1 above, wherein the ceramic columnar body is made of a ZrO ₂ ceramic containing a rare earth element.
3. The heat-shielding layer is disposed on the base-side heat-shielding layer including the first ceramic columnar body made of ZrO ₂ -3 to ₅ mol% Y ₂ O ₃ and the base-side heat-shielding layer. The structure is different from that of the ceramic columnar body, and at least one selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. The heat-shielding member according to 1 or 2 above, comprising a surface-side heat-shielding layer comprising a second ceramic columnar body made of a ZrO ₂ -based ceramic containing a rare earth element.
4). The ZrO ₂ ceramics constituting the second ceramic columnar body are Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. 4. The heat shielding member according to 3 above, containing at least two selected rare earth elements.
5. The oxidation-resistant layer forming step for forming an oxidation-resistant layer on the surface of the alloy substrate, and the surface of the oxidation-resistant layer while rotating the alloy substrate with the oxidation-resistant layer in the same direction with the ceramic evaporated by electron beam irradiation. A method of manufacturing a heat shield member, comprising:
When the heat shielding layer forming step is set to x (rpm) and y (μm / sec), respectively, the number of rotations of the alloy base material with an oxidation resistant layer and the film forming speed of the ceramic, respectively, The manufacturing method of the thermal-insulation member characterized by progressing on condition of this.
0 <y ≦ 0.017x
5 ≦ x ≦ 60
6). 6. The method for producing a heat shield member according to 5 above, wherein the rotational speed x of the alloy substrate with an oxidation resistant layer is 15 rpm or more and 40 rpm or less.

According to the heat shield member of the present invention, when used in a high temperature range of 900 ° C. or higher, preferably 1000 ° C. to 1500 ° C., the occurrence of cracks in the heat shield layer is suppressed, and the application of the above temperature When the application of a low temperature such as cooling is repeated, the stress associated with this thermal cycle is unlikely to act on the heat shield layer, so peeling does not occur easily, heat resistance (thermal cycle durability) is excellent, and long-term High reliability for use over a wide range. In addition, the said effect can be acquired also when it uses at the temperature of the range of 300 to 900 degreeC.
When the ceramic columnar body is made of a ZrO ₂ -based ceramic containing a rare earth element, it has low thermal conductivity and is particularly excellent in heat resistance (thermal cycle durability).
Further, the thermal barrier _layer, ZrO 2 _-3~5mol% Y 2 and _{O 3} barrier substrate side including the first ceramic columnar body made of a thermal layer, and disposed on the substrate side thermal barrier layer, the The structure is different from the first ceramic columnar body and is selected from La, Sc, Y, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. In the case of comprising a surface side heat shield layer including a second ceramic columnar body made of ZrO ₂ -based ceramics containing at least one kind, the heat shield characteristics are further enhanced, and the heat resistance and durability are excellent.

  According to the method for producing a heat shield member of the present invention, a uniform heat shield layer can be formed regardless of the shape of the alloy substrate, and it is used in a high temperature range of 900 ° C. or higher, preferably 1000 ° C. to 1500 ° C. In such a case, it is possible to efficiently produce a heat shield member that is suppressed in cracking and peeling of the heat shield layer and is excellent in heat resistance (thermal cycle durability).

1. Heat-shielding member The heat-shielding member of the present invention is disposed on the surface of the alloy substrate, the oxidation-resistant layer disposed on the surface of the alloy substrate and suppressing oxidation of the alloy substrate, and the surface of the oxidation-resistant layer. A heat shield member comprising a heat shield layer made of a ceramic columnar body having a periodic C-shaped structure, wherein the periodic interval in the axial direction of the C-shaped structure is 1 μm or less.
An example of a cross-sectional structure of the heat shield member of the present invention is shown in FIG. 1 includes an alloy member 11, an oxidation resistant layer 12 disposed on the surface of the alloy base 11, and a heat shielding layer comprising a ceramic columnar body disposed on the surface of the oxidation resistant layer 12. 13.

The alloy base material may be a member selected from a nickel-based alloy, a cobalt-based alloy, an iron-based alloy, and the like.
As the nickel-based alloy, an alloy containing 35% by mass or more of Ni and having a maximum mass ratio of Ni is preferable. Examples of other constituent elements include Co, Cr, Al, W, Mo, Ti, and Fe. Among these, only 1 type may be contained and 2 or more types may be contained.
As the nickel-based alloy, Inconel (registered trademark), Nimonic (registered trademark), Rene '(registered trademark), or the like can be used.
As the cobalt-based alloy, an alloy containing 30 mass% or more of Co and having a maximum mass ratio of Co is preferable. Examples of other constituent elements include Ni, Cr, Al, W, Mo, Ti, and Fe. Among these, only 1 type may be contained and 2 or more types may be contained.
As the cobalt-based alloy, Haynes (registered trademark), Nozzaloy (registered trademark), Stellite (registered trademark), Ultimate (registered trademark), or the like can be used.
As the iron-based alloy, stainless steel having a maximum mass ratio of Fe is preferably used.

  The shape of the alloy base material is not particularly limited, and may be a regular shape or an irregular shape without regularity. Examples of the alloy substrate include a moving blade, a stationary blade, and a rotating blade.

The oxidation resistant layer is disposed on the surface of the alloy base material and suppresses oxidation of the alloy base material. The constituent material of the oxidation resistant layer is not particularly limited, but MCrAlX alloy (where M is one or more elements selected from Co, Ni and Fe, and X is Y, Ta, Hf, Ce, One or more elements selected from La, Pt, Cs, W, Si, Mn and B), nickel aluminide (NiAl), nickel aluminide doped with Hf (NiAl (Hf)), nickel doped with Zr Examples include aluminide (NiAl (Zr)), platinum aluminide (PtAl), and the like. Of these, MCrAlX alloys are preferred.
The oxidation-resistant layer may be a single layer made of one kind of constituent material or a multilayer. Moreover, the multilayer (two or more layers) which consists of a different structural material may be sufficient.

  The thickness of the oxidation resistant layer is usually 50 to 200 μm, preferably 100 to 150 μm. If this thickness is in the above range, the oxidation resistance to the alloy substrate is excellent. If the thickness is too thick, there is no further effect, and if it is too thin, sufficient oxidation resistance is not exhibited.

Next, the heat shield layer is formed of a ceramic columnar body that is disposed on the surface of the oxidation resistant layer and has a periodic C-type structure. When the heat-shielding member of the present invention is observed at a low magnification of about 5000 times, the heat-shielding layer is structured by a large number of ceramic columnar bodies formed perpendicularly and linearly to the surface of the alloy base material. However, if the magnification is further increased, as shown in FIG. 3, a large number of ceramic columnar bodies 131 are wavy and substantially perpendicular to the surface of the alloy base material. Yes. The “periodic C-shaped structure” means this continuous wavy line shape. The adjacent ceramic columnar bodies 131 are usually in partial contact with each other, and the non-contact portions are pores 133. The volume ratio of the pores 133 in the heat shield layer is usually 15 to 30%.
In the present invention, the ceramic columnar body 131 constituting the heat shielding layer has a periodic interval (see FIG. 3) in the axial direction (length direction) of the C-type structure of 1 μm or less, preferably 0.1 to 0. 0.7 μm, more preferably 0.2 to 0.6 μm, still more preferably 0.25 to 0.5 μm. By having this periodic interval in the above range, the pores 133 have a structure in which the pores 133 are uniformly and finely dispersed, and the heat shield member of the present invention is excellent in heat resistance (thermal cycle durability). On the other hand, if the period interval is too long, the Young's modulus in the heat shield layer tends to increase, and cracks and the like are likely to occur. Further, if the above periodic interval is too long, the pores become large, and the occurrence and development of cracks are further promoted.In addition, every time the heat shield member of the present invention is used, the contact portions of the adjacent ceramic columnar bodies 131 are joined. It becomes stronger, the Young's modulus in the heat shield layer further increases, and cracks and the like are likely to occur.

  The ceramic columnar body 131 may have the same outer diameter or may have different outer diameters throughout. The outer diameter is usually 0.05 to 30 μm, preferably 0.1 to 10 μm. In the present invention, the C-type structure is periodically seen in the entire heat shield layer, while the heat shield layer has a structure in which the outer diameter of the ceramic columnar body 131 increases as it approaches the surface. It can be. For example, the ratio of the outer diameter of the ceramic columnar body 131 in the surface layer of the heat shield layer to the outer diameter of the ceramic columnar body 131 in the surface layer of the oxidation resistant layer is preferably 50 to 1000, more preferably 100 to 500. It can be set as the thermal insulation layer which has a certain structure.

The constituent material of the ceramic columnar body is not particularly limited, but is preferably ZrO ₂ based ceramic because of its low thermal conductivity and excellent heat resistance. Particularly preferable constituent materials are Sc (scandium), Y (yttrium), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Pm (promethium), Sm (samarium), Eu (europium). , Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Yb (ytterbium) and Lu (lutetium) ZrO ₂ -based ceramics containing As this rare earth element, Y, Yb, Er and the like are preferable. The composition of the ZrO ₂ -based ceramics containing the rare earth element is preferably ZrO ₂ -2 to 8 mol% Re ₂ O ₃ , more preferably ZrO ₂ -3 to ₆ mol% Re ₂ when the rare earth element is represented by Re. O _3. Within this range, the thermal shock resistance is excellent.

  The thermal conductivity of the heat shield layer is usually 1 to 2 W / (m · K). This thermal conductivity can be measured by a laser flash method or the like.

  The heat shield layer may be a single layer made of one kind of constituent material or may be a multilayer. Moreover, the multilayer (two or more layers) which consists of a different structural material may be sufficient. Even if the thermal barrier layer has a multilayer structure, the ceramic columnar body has a periodic C-type structure over the entire thermal barrier layer, and an axial period of the C-type structure. The interval is 1 μm or less.

  The thickness of the heat shield layer is usually 50 to 500 μm, preferably 100 to 300 μm. If this thickness is within the above range, when used in a high temperature range of 900 ° C. or higher, preferably 1000 ° C. to 1500 ° C., the occurrence of cracking and peeling of the thermal barrier layer is suppressed, and heat resistance (thermal cycle durability) ).

When the heat-shielding layer has a two-layer structure made of different constituent materials, the base material includes a first ceramic columnar body that is disposed on the surface of the oxidation-resistant layer and made of ZrO ₂ -3 to ₅ mol% Y ₂ O _3. It is arranged on the side heat shield layer and the base material side heat shield layer, and has a different structure from the first ceramic columnar body, and Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu A surface-side thermal barrier layer comprising a second ceramic columnar body made of ZrO ₂ -based ceramics containing at least one rare earth element selected from Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, It is preferable to become. In addition, as a rare earth element contained in the 2nd ceramic columnar body which comprises the said surface side thermal insulation layer, Y, Nd, and Gd are preferable.

In the second ceramic columnar body constituting the surface side heat shield layer, the composition is preferably ZrO ₂ -2 to 50 mol% Re ₂ O ₃ , more preferably ZrO ₂ -3 when the rare earth element is represented by Re. ˜15 mol% Re ₂ O ₃ . Within this range, the heat shielding properties are excellent.

In the present invention, the surface-side heat shield layer is selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. It is particularly preferable to include a second ceramic columnar body made of ZrO ₂ -based ceramics containing at least two kinds of rare earth elements. In this case, the rare earth element can be Y, La, or the like. In addition, when the said rare earth elements are Y and La, these content rate (mass ratio) becomes like this. Preferably it is Y: La = (1-5): 1, More preferably, it is (3-5): 1.

  The thickness and ratio of the base material side heat shield layer and the surface side heat shield layer are not particularly limited. About both thickness, the said base-side thermal insulation layer and the said surface side thermal-insulation layer can respectively preferably be 50-150 micrometers and 50-200 micrometers, More preferably, they can be 50-100 micrometers and 100-200 micrometers.

  When the heat shield layer is a single layer, the cross-sectional structure of the heat shield member of the present invention is shown in FIG. Moreover, when the said heat insulation layer is two layers, the cross-section of the heat insulation member of this invention is shown by FIG. 2 includes an alloy member 11, an oxidation resistant layer 12 disposed on the surface of the alloy base 11, and a first ceramic columnar body disposed on the surface of the oxidation resistant layer 12. And a surface-side heat shield layer 13b made of a second ceramic columnar body disposed on the surface of the substrate-side heat shield layer 13a.

Since the Young's modulus of the heat-shielding member of the present invention is usually as low as 30 to 65 GPa, the thermal stress is low and the thermal cycle durability is excellent. The Young's modulus can be measured by a nanoindentation method or the like.
As described above, since the heat shield member of the present invention is excellent in heat resistance (thermal cycle durability), it should be a high temperature member such as a gas turbine part, a combustion equipment part, a jet engine part or the like having a high heat shield effect. The thermal efficiency can be improved and the life can be extended.

2. Manufacturing method of heat-shielding member The manufacturing method of the heat-shielding member of the present invention comprises an oxidation-resistant layer forming step of forming an oxidation-resistant layer on the surface of an alloy substrate, and a ceramic evaporated by irradiation with an electron beam. A thermal barrier layer forming step of depositing on the surface of the oxidation resistant layer while rotating the attached alloy base material in the same direction, and the thermal barrier layer forming step is performed by rotating the alloy base material with the oxidation resistant layer, And when the film-forming speed | rate of the said ceramic is set to x (rpm) and y (micrometer / second), respectively, it progresses on the conditions of a following formula (refer FIG. 5).
0 <y ≦ 0.017x
5 ≦ x ≦ 60

The oxidation-resistant layer forming step is a step of forming an oxidation-resistant layer on the surface of the alloy substrate, and an oxidation-resistant layer having a thickness of usually 50 to 200 μm, preferably 100 to 200 μm is formed by this step. .
As the above-mentioned alloy base material, a base material having the above-described constituent material, shape, etc. is used. Before forming the oxidation-resistant layer, a known pretreatment such as grit blasting is performed on the surface of the alloy base material. Polishing, chemical cleaning, ultrasonic cleaning, degreasing, or a combination thereof can be performed.
As the oxidation resistant layer forming material used in the oxidation resistant layer forming step, the above-described MCrAlX alloy (where M is one or more elements selected from Co, Ni and Fe, and X is Y, Ta , Hf, Ce, La, Pt, Cs, W, Si, Mn and B), nickel aluminide (NiAl), Hf-doped nickel aluminide (NiAl (Hf)), Zr And nickel aluminide (NiAl (Zr)), platinum aluminide (PtAl) and the like.

Examples of the method for forming the oxidation resistant layer include chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), electron beam physical vapor deposition, cathode arc coating, sputtering, ion plasma coating, and other physical or chemical vapor deposition methods; flame spraying, Examples of the thermal spraying method include plasma spraying and high-speed oxyfuel gas spraying.
In addition, when using a MCrAlX alloy as said oxidation-resistant layer forming material, a low pressure plasma spraying method, a physical vapor deposition method (PVD), etc. are mentioned.
As described above, the oxidation-resistant layer may be a single layer or multiple layers made of one kind of oxidation-resistant layer forming material, or may be a multiple layer (two or more layers) made of different oxidation-resistant layer forming materials. Depending on the purpose and application, the oxidation-resistant layer forming material and thickness are selected.

  The thermal barrier layer forming step is a step of depositing the ceramic evaporated by electron beam irradiation on the surface of the oxidation resistant layer while rotating the alloy substrate with the oxidation resistant layer in the same direction. A large number of ceramic columnar bodies having a periodic C-type structure are formed, and a heat shield layer made of these ceramic columnar bodies is obtained. The thickness of this heat shield layer is usually 50 to 500 μm, preferably 100 to 300 μm.

  A specific method in the thermal barrier layer forming step uses an electron beam physical vapor deposition apparatus 5 shown in FIG. This electron beam physical vapor deposition apparatus 5 is provided with a support portion 51, an electron gun 54, and the like that support and rotate the alloy substrate 2 with an oxidation resistant layer in a chamber in which the internal pressure can be adjusted. In the case of forming the heat shield layer, the electron beam 55 is irradiated continuously or intermittently from the electron gun 54 toward the heat shield layer forming material 3 to melt and vaporize the heat shield layer forming material 3 at the same time. And ceramic vapor. At the same time, by rotating the support portion 51 that supports the alloy base material 2 with an oxidation resistant layer, the surface of the alloy base material can be obtained regardless of the shape of the alloy base material and the surface shape of the alloy base material 2 with an oxidation resistant layer. The film can be uniformly deposited and formed into a film.

As the heat shielding layer forming material, an ingot made of the ZrO ₂ -based ceramic described above is usually used. As this ingot, for example, a material obtained by sintering or electromelting a raw material having a predetermined composition can be used.

  In the present invention, in the thermal barrier layer forming step, when the rotation speed of the alloy substrate with an oxidation-resistant layer and the film formation rate of the ceramic are x (rpm) and y (μm / second), respectively. 0 <y ≦ 0.017x, preferably 0 <y ≦ 0.0083x, more preferably 0 <y ≦ 0.005x, and 5 ≦ x ≦ 60, preferably 10 ≦ x ≦ 50, more preferably The process proceeds under the condition of 15 ≦ x ≦ 40. When y> 0.017x, the periodic interval in the axial direction of the C-shaped structure of the ceramic columnar body exceeds 1 μm. In addition, if 0 <y ≦ 0.005x and 15 ≦ x ≦ 40, a heat shielding layer having a low Young's modulus can be formed.

  The other conditions in the thermal barrier layer forming step are not particularly limited. For example, the pressure in the chamber during film formation is 0.1 to 10 Pa, the atmosphere is a vacuum containing oxygen, the film formation temperature (acid resistance) The temperature of the alloy substrate with a chemical layer can be set to 900 to 1100 ° C or the like.

  Even when the heat-insulating layer is a multilayer, it can proceed under the above conditions.

  When used in a high temperature range of 900 ° C. or higher, preferably 1000 ° C. to 1500 ° C., by the method for manufacturing a heat shielding member of the present invention, generation of cracks in the heat shielding layer is suppressed, application of the above temperature, cooling, etc. When the application of a low temperature is repeated, it is possible to obtain a heat shield member that hardly peels off the heat shield layer and is excellent in heat resistance (thermal cycle durability).

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited at all by these Examples.

Example 1
A film (oxidation resistant layer) having a thickness of 100 μm made of a CoNiCrAlY alloy was formed on the surface of a flat alloy base made of Inconel 738 by low pressure plasma spraying. Thereafter, using an electron beam physical vapor deposition apparatus (chamber internal pressure: 1 Pa) 5 shown in FIG. 4, electrons are transferred from the electron gun 54 by the EB-PVD method while rotating the alloy substrate 2 with an oxidation resistant layer at a rotation speed of 20 rpm. beam (output _45kW), irradiating the ingots 3 consisting of _{ZrO 2 -4mol% Y 2 O 3} , at a deposition temperature of 950 ° C. and the film forming rate of 0.1 [mu] m / sec, the surface oxidation layer, ZrO ₂ - A film (heat shield layer) of 4 mol% Y ₂ O _{3 having} a thickness of about 200 μm was formed to obtain a heat shield member (see Table 1).
When the heat shield member was observed with an electron microscope (see FIG. 6), the heat shield layer was composed of a large number of columnar bodies, and the outer diameter of the columnar bodies was different in the depth direction of the heat shield layer. I understand. FIG. 7 is an enlarged image of a portion including the surface of the alloy substrate, the oxidation resistant layer, and the oxidation resistant layer side heat shielding layer in FIG. 6, and the columnar body constituting the heat shielding layer is oxidized resistant. It can be seen that this is a wavy line that regularly extends from the layer-side heat shield layer toward the surface. In addition, it can be seen from FIG. 7 that the periodic interval of the C-shaped structure of the wavy body is 0.3 μm (see Table 1).

A thermal cycle test and Young's modulus measurement were performed on the obtained heat shield member, and the results are shown in FIGS. Specific operations are shown below.
(1) Thermal cycle test Heat-shielding member is heated in the atmosphere at 1150 ° C for 1 hour, and then cooled with compressed air for 10 minutes as one cycle, and the heat-shielding layer is visually peeled off from the oxidation-resistant layer. The number of cycles (thermal cycle life) until it can be confirmed by was measured.
(2) Young's modulus Using a nanoindentation device (model “H100V”, manufactured by Fischerscope), measurement was performed under conditions of an indentation load of 1 N and a holding time of 60 seconds.

Example 2
A heat shield member was obtained in the same manner as in Example 1 except that the constituent material, thickness, and production conditions of the heat shield layer were as shown in Table 1. The periodic interval of the C-shaped structure of the columnar body constituting the obtained heat shield member was 0.3 μm (see Table 1).
The results of the thermal cycle test and Young's modulus measurement are shown in FIGS.

Example 3
In order to obtain a heat-shielding layer having a two-layer structure, the constituent materials and thicknesses of the base-side heat-shielding layer and the surface-side heat-shielding layer are as shown in Table 1, and the base-side heat-shielding layer and the surface-side heat-shielding layer The heat shielding member was obtained in the same manner as in Example 1 except that the formation conditions were the same (rotary speed of substrate: 20 rpm, film formation speed: 0.1 μm / min). The periodic interval of the C-shaped structure of the columnar body constituting the obtained heat shield member was 0.3 μm (see Table 1).
The results of the thermal cycle test and Young's modulus measurement are shown in FIGS.

Example 4
A heat shield member was obtained in the same manner as in Example 1 except that the constituent material, thickness, and production conditions of the heat shield layer were as shown in Table 1. The periodic interval of the C-shaped structure of the columnar body constituting the obtained heat shield member was 0.4 μm (see Table 1).
The results of the thermal cycle test and Young's modulus measurement are shown in FIGS.

Comparative Example 1
A heat shield member was obtained in the same manner as in Example 1 except that the constituent material, thickness and production conditions of the heat shield layer were as shown in Table 2 (see FIG. 10). The periodic interval of the C-shaped structure of the columnar body constituting the obtained heat shield member was 6.0 μm (see Table 2).
The results of the thermal cycle test and Young's modulus measurement are shown in FIGS.

Comparative Example 2
A heat shield member was obtained in the same manner as in Example 1 except that the constituent material, thickness and production conditions of the heat shield layer were as shown in Table 2. The periodic interval of the C-shaped structure of the columnar body constituting the obtained heat shield member was 1.2 μm (see Table 2).
The results of the thermal cycle test and Young's modulus measurement are shown in FIGS.

Comparative Example 3
A heat shield member was obtained in the same manner as in Example 1 except that the constituent material, thickness and production conditions of the heat shield layer were as shown in Table 2. The periodic interval of the C-shaped structure of the columnar body constituting the obtained heat shield member was 2.4 μm (see Table 2).
The results of the thermal cycle test and Young's modulus measurement are shown in FIGS.

As is clear from the thermal cycle test results in FIG. 8, Comparative Examples 1 to 3 have a thermal cycle life of 60 cycles or less, and as is clear from the Young's modulus measurement results in FIG. Inferior in durability (see Table 2).
On the other hand, Examples 1 to 4 have a thermal cycle life of 70 cycles or more, a Young's modulus of 65 GPa or less, and are excellent in durability (see Table 1).
Further, when comparing cross-sectional images of the heat shield layer taken at the same magnification, in Comparative Example 1 (FIG. 10), the heat shield layer is composed of a ceramic columnar body having a long period interval of a C-type structure, and adjacent ceramic columnar shapes. In contrast to the structure in which the bodies are in close contact with each other without pores, and the pore size is large, in Example 1 (FIG. 6), the heat shield layer is linear throughout. It consists of a ceramic columnar body, and the outer diameter of the ceramic columnar body has a structure that increases as it approaches the surface. In addition, the size of the pores between the columnar bodies is small, and cracks are unlikely to occur and propagate.

  The heat shielding member of the present invention is a gas turbine component (combustor inner cylinder, tail cylinder, transition piece, moving blade, stationary blade, shroud segment, split ring, etc.), combustion equipment for power generation, aircraft use, marine use etc. It is useful as a high-temperature member for parts, jet engine parts, automobile engine parts, and the like.

It is typical sectional drawing which shows an example of the heat insulation member of this invention. It is typical sectional drawing which shows the other example of the heat insulation member of this invention. It is typical sectional drawing which shows the C-type structure of the ceramic columnar body which comprises the thermal insulation layer contained in the thermal insulation member of this invention. It is a schematic diagram which shows an example of the manufacturing apparatus (electron beam physical vapor deposition apparatus) of the thermal insulation member of this invention. It is a graph which shows the conditions of the thermal-insulation layer formation process in the manufacturing method of the thermal-insulation member of this invention. 2 is a cross-sectional image of a heat shield member obtained in Example 1. FIG. 7 is an enlarged image of a portion surrounded by white circles in FIG. 6. It is a graph which shows the result of the thermal cycle life measured in the Example and the comparative example. It is a graph which shows the result of the Young's modulus measured in the Example and the comparative example. 3 is a cross-sectional image of a heat shield member obtained in Comparative Example 1.

Explanation of symbols

1 and 1 '; heat shield member 11; alloy substrate 12; oxidation resistant layer 13; heat shield layer 13a; substrate heat shield layer 13b; surface side heat shield layer 131; ceramic columnar body 133; Alloy base material 3 with a layer; Heat shielding layer forming material (ingot)
31; ceramic vapor 5; electron beam physical vapor deposition device 51; support 54; electron gun 55;

Claims (6)

  An alloy substrate, an oxidation resistant layer disposed on the surface of the alloy substrate and suppressing oxidation of the alloy substrate, and a ceramic columnar body disposed on the surface of the oxidation resistant layer and having a periodic C-type structure A heat-shielding member comprising a heat-shielding layer comprising: a heat-shielding member having an axial periodic interval of the C-type structure of 1 μm or less. The heat shielding member according to claim 1, wherein the ceramic columnar body is made of a ZrO ₂ ceramic containing a rare earth element. The heat-shielding layer is disposed on the base-side heat-shielding layer including the first ceramic columnar body made of ZrO ₂ -3 to ₅ mol% Y ₂ O ₃ and the base-side heat-shielding layer. The structure is different from that of the ceramic columnar body, and at least one selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. The heat-shielding member according to claim 1, comprising a surface-side heat-shielding layer comprising a second ceramic columnar body made of a ZrO ₂ -based ceramic containing a rare earth element. The ZrO ₂ ceramics constituting the second ceramic columnar body are Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. The heat-shielding member according to claim 3, comprising at least two selected rare earth elements. The oxidation-resistant layer forming step for forming an oxidation-resistant layer on the surface of the alloy substrate, and the surface of the oxidation-resistant layer while rotating the alloy substrate with the oxidation-resistant layer in the same direction with the ceramic evaporated by electron beam irradiation. A method of manufacturing a heat shield member, comprising:
When the heat shielding layer forming step is set to x (rpm) and y (μm / sec), respectively, the number of rotations of the alloy base material with an oxidation resistant layer and the film forming speed of the ceramic, respectively, The manufacturing method of the thermal-insulation member characterized by progressing on condition of this.
0 <y ≦ 0.017x
5 ≦ x ≦ 60   The method for producing a heat shield member according to claim 5, wherein the rotation speed x of the alloy base material with an oxidation resistant layer is 15 rpm or more and 40 rpm or less.