JP2003013259A - Metal-ceramic multilayered structure member and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve such a problem that propagation of exfoliation fracture due to sintering/grain growth, and characteristics change or the like of heat conductivity or the like, occur when using a conventional heat insulating material/thermal-barrier coating material based on zirconium oxide at a comparatively high temperature. SOLUTION: The multilayered structure member comprises a metal layer and a ceramic layer laminated thereon. The ceramic layer includes at least one stabilizer selected from yttrium oxide, cerium oxide and magnesium oxide; zirconium oxide including the second phase oxide consisting of at least one selected from aluminum oxide, spinel of magnesium oxide and aluminum oxide, zinc oxide, nickel oxide, cobalt oxide and zirconium oxide as main phases; and fine cracks or pores.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal-ceramic laminated structural member having excellent toughness / strength at room temperature and high temperature, strength / durability at thermal shock, and heat insulating property, and is used in the field of application of conventional oxide-based ceramics. The present invention relates to a metal-ceramic laminated structure member which can be widely applied in various industrial fields such as a heat insulating material, jig tool parts for heat treatment furnaces, corrosion resistant parts, and thermal barrier coating, and a method for manufacturing the same.

[0002]

2. Description of the Related Art As a zirconia-based sintered body having excellent strength and toughness, an aluminum oxide-added zirconia-based sintered body (K. Tsukuma, Am. Ceram. Soc.Bull., 64 [2], 31
0-313 (1985)) or SiC whiskers formed by mixing SiC whiskers and zirconia, pressurizing, molding and sintering.
Zirconia-based sintered body (N. Claussen, J. Am. Ceram. Soc., 69
[4], (1986)) has been reported.

Further, JP-A-1-188467 discloses a zirconia-based sintered body in which single crystal β-SiC particles are compounded, and JP-A-63-129066 discloses zirconium oxide, aluminum oxide and titanium oxide. A high-hardness and high-strength ceramics made of, for example, is disclosed.

On the other hand, the low thermal conductivity of zirconia ceramics has been utilized, and it has been widely used as a heat insulating material or a thermal barrier coating material.

[0005]

In the zirconia-based sintered bodies disclosed in the above two papers and Japanese Patent Laid-Open No. 1-188467, the stabilizer added to the base zirconia is yttria. Is a rare earth element oxide typified by No. 1, which is sintered at a relatively low temperature using finely sinterable raw material powder, and the ratio of tetragonal crystals in the zirconia phase is high at about 90 vol% or more. It is a material that has high strength and high toughness by keeping the body particle size fine and high density, and does not mention the possibility of use at high temperatures such as in the vicinity of 800 ° C to the sintering temperature.

In Japanese Patent Laid-Open No. 63-129066, there is M
A material based on gO-stabilized zirconia and containing a third component such as titanium oxide in combination with a second component such as alumina is disclosed, but it is also clear that the material can be used at high temperatures. It has not been.

On the other hand, regarding zirconia ceramics applied to heat insulating materials and thermal barrier coating materials, although there are some reports on the influence of the type of stabilizer on the possibility of use at high temperatures, the second particles, And / or the effect of trace additives has not yet been clarified.

The present invention is based on Y ₂ O ₃ , MgO or Ce.
Targeting materials based on zirconia with O ₂ as a stabilizer, the second particles are dispersed to sinter when used at high temperatures.
Its main purpose is to suppress grain growth, suppress peeling fracture by increasing the bonding force in the direction parallel to the stack, and reduce microstructural changes to stabilize at high temperatures. Based on conventional zirconia It is intended to solve the problems of the heat insulating material and the thermal barrier coating material, such as the progress of peeling fracture due to sintering and grain growth and the change in characteristics such as thermal conductivity, which are problems in using at a relatively high temperature.

[0009]

The metal-ceramic laminated structure member of the present invention is a laminated structure member comprising a metal layer and a ceramic layer laminated thereon, wherein the ceramic layer is yttrium oxide, cerium oxide and magnesium oxide. Zirconium oxide containing at least one stabilizer selected from the main phase and containing fine cracks or pores.

The metal-ceramic multilayer structure member of the present invention comprises a ceramic layer containing zirconium oxide as a main phase containing at least one stabilizer selected from yttrium oxide, cerium oxide and magnesium oxide,
Further, by providing this ceramic layer with at least fine cracks or pores, not only room temperature but also 800
The strength and toughness in the vicinity of ℃ to the sintering temperature are also improved.

It is preferable that at least one kind of second-phase oxide other than yttrium oxide, cerium oxide and magnesium oxide is dispersed in the ceramic layer. These second phase oxides have the effect of suppressing sintering and grain growth. In the present invention, by including such a second phase oxide, it is possible to suppress sintering and grain growth during use at high temperature and suppress characteristic changes such as thermal conductivity.

It is preferable that a large amount of such a second phase oxide is present in at least one site selected from the periphery of the main phase mass, the vicinity of the fine cracks and the periphery of the pores in the main phase mass. Further, the distribution of the second phase oxide is high in the vicinity of the surface on the side where the ceramic layer is exposed, and is low on the side opposite to the vicinity of the surface and in the vicinity of the metal layer close to the metal layer. Is preferred.

The density of the ceramics layer is high in the vicinity of the surface where the ceramics layer is exposed, and is low on the side opposite to the surface and near the metal layer near the metal layer. It is preferable.

Examples of the second phase oxide include aluminum oxide, magnesium oxide-aluminum spinel, zinc oxide, nickel oxide, cobalt oxide and zirconium oxide, or a composite oxide thereof.
These are preferably contained in the ceramic layer in an amount of 0.2 to 20 wt%.

Further, an intermediate layer is provided between the metal layer and the ceramic layer to relieve stress due to a difference in thermal expansion coefficient between these layers or to effectively protect the ceramic layer from oxidation. It is preferably formed.

The method for manufacturing a metal-ceramic laminated structure member according to the present invention includes, for example, thermal spraying, CVD (chemical vapor deposition), P
At least one method selected from VD (physical vapor deposition) and sputtering is used to produce the metal-ceramic laminated structure member.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.

FIG. 1 shows a sectional view of the metal-ceramic laminated structure member of the present invention. The metal-ceramics laminated structure member 1 of the present invention is a laminated structure member composed of a metal layer 2 and a ceramics layer 3 laminated thereon. Ceramics layer 3
Contains zirconium oxide as a main phase and contains at least one stabilizer selected from yttrium oxide, cerium oxide and magnesium oxide.

The ceramic layer 3 is composed of, for example, flat main phase lumps 4, and at least pores 5 are present between the main phase lumps 4, or fine cracks 6 are present in the main phase lumps 4. ing.

Since at least the ceramic layer 3 has pores 5 or fine cracks 6, when used as a heat insulating material, the pores 5 or fine cracks 6 block heat and damage the metal layer 2 due to the heat. Can be prevented.

The porosity of the ceramic layer 3 due to the pores 5 and the fine cracks 6 is preferably 5 to 25.
It is preferably within the range of vol%. Porosity is 5v
If it is less than ol%, the effect of blocking heat is low and the metal layer 2 may be damaged. Also, the porosity is 25 vol.
If it exceeds%, the strength and the like may decrease.

In addition to the above-mentioned yttrium oxide, cerium oxide and magnesium oxide, it is preferable that such a ceramic layer 3 contains a second phase oxide different from these. Examples of the second phase oxide include at least one selected from aluminum oxide, magnesium oxide-aluminum spinel, zinc oxide, nickel oxide, cobalt oxide, and zirconium oxide, or a mixture thereof.

These second phase oxides can suppress the progress of sintering and grain growth at high temperature, and the pores 5 and fine cracks 6 existing in the ceramic layer 3 are reduced by sintering and grain growth. It can be suppressed from disappearing.
Therefore, even when it is used at high temperature, it is possible to suppress deterioration of properties such as heat insulation.

The second phase oxide 7 may exist in the fine cracks 6 in the main phase block 4 as shown in FIG. 2, or on the surface of the main phase block 4 as shown in FIG. Or may exist around the pores 5 formed between the main phase agglomerates 4 as shown in FIG.

As shown in FIG. 2, when the second phase oxide 7 exists in the fine cracks 6 in the main phase block 4, the sintering of this portion is suppressed and the fine cracks 6 are prevented from disappearing. be able to. In addition, when it exists on the surface of the main phase lump 4 as shown in FIG. 3 or as shown in FIG.
When it exists around the pores 5 formed between each other,
It is possible to prevent the pores 5 from disappearing by suppressing the sintering and grain growth of the main phase mass 4. By suppressing the decrease and disappearance of the pores 5 and the fine cracks 6, it is possible to suppress the deterioration of the properties such as the heat insulating property even when used at high temperature.

The main phase of the constituent crystal layer of zirconium oxide is preferably tetragonal or cubic. It is preferable that these are appropriately selected and used according to the use conditions of the metal-ceramic laminated structure member, for example, the use temperature is 130
When the temperature is lower than 0 ° C., the tetragonal crystal having excellent strength is preferably used as the main phase, and when the working temperature is higher than 1300 ° C., the cubic phase which can stably exist even at this temperature is preferably used as the main phase.

The ceramic layer 3 in the metal-ceramic laminated structure member 1 of the present invention has a bulk density of 5.0.
5 to 5.70 g / cm ³ , Young's modulus of 20 to 80 GP
a, It is preferable that the three-point bending strength is 30 to 220 MPa.

Next, another embodiment of the present invention will be described. In FIG. 5, the intermediate layer 8 is provided between the metal layer 2 and the ceramic layer 3. Since the thermal expansion of the metal layer 2 and the thermal expansion of the ceramic layer 3 are different, peeling or the like may occur when these are simply laminated. Therefore, by forming the intermediate layer 8 having a coefficient of thermal expansion between the coefficient of thermal expansion of the metal layer 2 and the coefficient of thermal expansion of the ceramic layer 3 between the metal layer 2 and the ceramic layer 3, peeling or the like can be achieved. Can be suppressed. Moreover, it is possible to prevent the metal layer 2 from being oxidized at a high temperature by preferably making the intermediate layer 8 resistant to oxidation.

It is preferable that the ceramic layer 3 has a low density on the metal layer 2 side and a density on the opposite surface (front surface side) higher than that of the metal layer 2. As a method of changing the density of the ceramics layer 3, for example, FIG.
As shown in FIG. 3, the main phase mass 4 in the metal layer vicinity portion 9 which is a portion near the metal layer 2 of the ceramics layer 3 is made large so that the pores 5 become large, and the surface in contact with the metal layer 2 is formed. There is a method of reducing the size of the main phase lumps 4 on the opposite surface, that is, the surface vicinity portion 10 which is the vicinity of the surface where the ceramics layer 3 is exposed, to reduce the pores 5.

By increasing the density on the surface side in this way,
It becomes possible to prevent the fine particles and the like in the gas from colliding with the ceramic layer 3 during use and causing the ceramic layer 3 to be worn or damaged.

The fine cracks 6 in the main phase mass 4 are preferably formed in the direction perpendicular to the surface of the metal layer 2. FIG. 7 is a diagram showing a structural change when the fine cracks 6 are formed in a direction perpendicular to the surface of the metal layer 2. In the state of the main phase mass 4 before heat is applied, the intervals of the fine cracks 6 are narrowed as shown on the left side of the figure. When heat is applied to this, as shown on the right side of the figure, the metal layer 2 thermally expands, so that the intervals between the fine cracks 6 formed in the main phase block 4 become wider. Thus, when the fine cracks 6 are formed in the direction perpendicular to the surface of the metal layer 2, the thermal expansion of the metal layer 2 can be relaxed by the fine cracks 6 formed in the main phase block 4. When the fine cracks 6 are formed in the direction perpendicular to the surface of the metal layer 2, the separated main phase lumps 4a, 4b, 4c can maintain contact with the metal layer 2, respectively. It is possible to prevent the ceramic layer 3 from peeling off.

On the other hand, when the fine cracks 6 are formed in the horizontal direction with respect to the surface of the metal layer 2 as shown in FIG. 8, the main phase lump 4 is formed as shown on the left side of FIG.
d and 4e exist without being separated, but when they are separated by some load, the main phase mass 4d which is in contact with the metal layer 2 remains without being separated as shown in the right side of the figure. However, the main phase block 4e peels off from the ceramic layer 3. If a plurality of main phase lumps 4 are stacked on the main phase lump 4e, all of them are also separated from the ceramic layer 3, so that relatively large-scale damage occurs in the ceramic layer 3. To do.

Therefore, the fine cracks 6 in the main phase mass 4
Is formed in the direction perpendicular to the surface of the metal layer 2, the difference in the coefficient of thermal expansion between the ceramic layer and the metal layer is mitigated, partial peeling of the ceramic layer 3 is prevented, and the heat insulating property is improved. It is possible to suppress deterioration of characteristics.

Next, a method of manufacturing the metal-ceramic laminated structure member of the present invention will be described. FIG. 9 shows a method for manufacturing a metal-ceramic laminated structure member of the present invention. What is used for producing a ceramics layer in a ceramics laminated structure member is a zirconia powder as a main phase and a stabilizer added thereto. Preferably, a second phase oxide is added to these.

Examples of the stabilizer include yttrium oxide, cerium oxide and magnesium oxide, and it is preferable to add about 1 to 15 wt% to the zirconia powder.

The second-phase oxides are other than yttrium oxide, cerium oxide and magnesium oxide, and are selected from, for example, aluminum oxide, magnesium oxide-aluminum spinel, zinc oxide, nickel oxide, cobalt oxide and zirconium oxide. It is preferable to use at least one kind, and it is preferable to add 0.2 to 20 wt%.

These powders are mixed by wet or dry mixing, and laminated on a metal base material by a method such as thermal spraying, CVD, PVD or sputtering. In addition to these methods, a step of impregnating and firing a sol, a precursor solution and a powder slurry may be added. If necessary, heat treatment or the like may be performed without pressure or while applying pressure in a predetermined direction.

The formation of pores and fine cracks in the ceramic layer can be carried out by appropriately selecting the thermal spraying conditions and the heat treatment conditions. In order to form the fine cracks in the direction perpendicular to the metal surface, it can be performed, for example, by adjusting cooling conditions after the heat treatment. Further, when partially changing the density of the ceramics layer 3 as shown in FIG. 6, it is possible to adopt a method of changing the thermal spraying conditions during the formation of the ceramics layer by thermal spraying.

[0039]

Embodiments of the present invention will be described below with reference to embodiments.

(Examples 1 to 18) Examples 1 and 2 A ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer was used as a second phase oxide having an average particle diameter of 1.0 μm.
A thermal spray coating was formed on a metal base material by an atmospheric pressure plasma method using a raw material powder to which 5 or 10 wt% of 1 ₂ O ₃ particles was added.

Examples 3 to 6 For ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer, M having an average particle size of 1.0 μm was used as the second phase oxide.
A thermal spray coating was formed on a metal base material by an atmospheric pressure plasma method using a raw material powder to which 5 or 10 wt% of gAl ₂ O ₄ , ZnO, NiO or CoO particles was added.

Examples 7 and 8 18wt% CeO as a stabilizer_TwoOr 10 wt% M
ZrO containing gO _TwoAs the second phase oxide for the powder
With an average particle size of 1.0 μm_TwoO_ThreeAdd 10 wt% of particles
Using the raw material powder prepared by
A thermal spray coating was prepared.

Example 9 ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer was used, and A having an average particle size of 1.0 μm was used as a second phase oxide.
CV was used with the raw material powder added with 10 wt% of 1 ₂ O ₃ particles.
A film was formed on the metal substrate by method D.

Example 10 ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer was used, and A having an average particle size of 1.0 μm was used as a second phase oxide.
A raw material powder containing 10% by weight of 1 ₂ O ₃ particles was used to form a sprayed coating on a metal base material by an atmospheric pressure plasma method, and then impregnated with alumina sol and baked to form a coating on the metal base material. .

Example 11 8wt% Y as stabilizer_TwoO_ThreeContaining ZrO_Twopowder
On the other hand, as the second phase oxide, A having an average particle size of 1.0 μm
l_TwoO_ThreeUsing the raw material powder with 10 wt% of particles added,
A thermal spray coating is produced on a metal substrate by the pressure plasma method, and then
40 kg / cm ^Two1200 ° C while applying the pressure of
× 5 hours heat treatment to form a film on the metal substrate
It was made.

Example 12 ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer was used, and A having an average particle size of 1.0 μm was used as the second phase oxide.
A raw material powder containing 10 wt% of 1 ₂ O ₃ particles was used to form a thermal spray coating on a metal substrate by an atmospheric pressure plasma method. In addition, in the thermal spraying process, Gd ₂ is formed so as to have a thickness of about 1 to 2 μm each time the coating is formed to a thickness of 150 μm.
O ₃ particles were sprayed and laminated in multiple layers.

Example 13 To ZrO ₂ powder containing 8Y ₂ O ₃ stabilizer,
It was produced under the same conditions as in Example 1 except that the raw material powder to which the second phase oxide was not added was used.

Example 14 To ZrO ₂ powder containing 8Y ₂ O ₃ stabilizer,
It was produced under the same conditions as in Example 1 except that the raw material powder added with 20 wt% of Al ₂ O ₃ was used as the second phase oxide.

Example 15 For ZrO ₂ powder containing a stabilizer of 8Y ₂ O ₃ ,
It was produced under the same conditions as in Example 11 except that the raw material powder added with 20 wt% of MgAl ₂ O ₄ was used as the second phase oxide.

Example 16 To ZrO ₂ powder containing 8Y ₂ O ₃ stabilizer,
It was manufactured under the same conditions as in Example 11 except that the raw material powder added with 20 wt% of ZnO was used as the second phase oxide.

Example 17 A ZrO ₂ powder containing a stabilizer of 8Y ₂ O _{3 was} prepared.
It was produced under the same conditions as in Example 11 except that the raw material powder added with 20 wt% of NiO was used as the second phase oxide.

Example 18 For ZrO ₂ powder containing 8Y ₂ O ₃ stabilizer,
It was manufactured under the same conditions as in Example 11 except that the raw material powder added with 20 wt% of CoO was used as the second phase oxide.

The metal-ceramic laminated structure members of Examples 1 to 18 include at least one of fine cracks and pores in the ceramic layer.

Next, the strength, elastic modulus, dimensional change and peeling life of the metal-ceramic laminated structure members of Examples 1 to 19 were measured. The strength and elastic modulus were evaluated from a three-point bending test at room temperature after cutting out a test piece of 3 × 4 × 40 mm from the ceramic layer.
The dimensional change is the result of the volumetric shrinkage amount after heat treatment in air at 1300 ° C. for 100 hours. Also, the peeling life is room temperature ← → 1200 ° C in the burner heating tester.
Is a result of examining the peeling state of the coating every 10 times by applying the heat cycle of. The results are shown in Table 1 and Table 2, in which the type and amount of the stabilizer of each example, the type and amount of the second phase oxide,
Shown together with process conditions.

[Table 1]

[Table 2]

(Examples 19 to 36) Example 19 ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer, two kinds of thermal spray raw material powders were used, and the ZrO ₂ powder was applied onto a metal substrate by an atmospheric pressure plasma method. Sprayed coating (ceramics sprayed layer)
Was produced. The thermal spray coating uses a granulated powder type raw material powder on the metal base material side and has a porosity of about 20 vol% and a thickness of 250 μ.
m and a dense layer having a porosity of about 10 vol% and a thickness of 50 μm using a pulverized powder type raw material powder on the surface layer side.

Example 20 A ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer was used, and A having an average particle size of 1.0 μm was used as a second phase oxide.
A spray coating was produced on a metal base material by an atmospheric pressure plasma method using a granulated powder type raw material powder in which 1 and 5 wt% of 1 ₂ O ₃ particles were added. The thermal spray coating has a porosity of about 17 vol.
%, A layer having 1 wt% of Al ₂ O ₃ particles added to the metal substrate side is 250 μm, and a layer of Al ₂ O ₃ particles is 5 wt% to the surface layer side.
An added layer was formed.

Example 21 ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer was used, and A having an average particle size of 1.0 μm was used as the second phase oxide.
A sprayed coating was produced on a metal substrate by an atmospheric pressure plasma method using raw powders of a granulated powder type and a pulverized powder type in which 1 and 5 wt% of 1 ₂ O ₃ particles were added. The thermal spray coating has a porous layer with a porosity of about 17 vol% of 250 μm in which 1 wt% of Al ₂ O ₃ particles is added on the metal base side, and A on the surface layer side.
A dense layer having a porosity of 10 vol% and containing 5 wt% of 1 ₂ O ₃ particles was formed.

Examples 22 to 26 For ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer, M having an average particle diameter of 1.0 μm was used as the second phase oxide.
gAl ₂ O ₄ , ZnO, NiO, CoO or ZrSi
A sprayed coating was produced on a metal base material by an atmospheric pressure plasma method using raw powders of a granulated powder type and a pulverized powder type in which 1 and 5 wt% of O ₄ particles were added. The thermal spray coating has a porosity of 10 to 12 vo with a porous layer having a porosity of 15 to 21 vol% with 1 wt% of the second phase oxide added to the metal base material side and a surface layer having 5 wt% of the second phase oxide of 250 μm.
A 1% dense layer was formed.

Examples 27 and 28 18wt% CeO as a stabilizer_TwoOr 10 wt% M
ZrO containing gO _TwoAs the second phase oxide for the powder
With an average particle size of 1.0 μm_TwoO_Three1 and 5w particles
Granulated powder type and crushed powder type raw material powder with t% added
Powder on the metal base material by atmospheric pressure plasma method
It was made. The thermal spray coating is Al on the metal substrate side._TwoO_ThreeParticles
A porous layer with a porosity of about 19 vol% added with 1 wt%
250 μm, Al on the surface layer side_TwoO_ThreeAdd 5 wt% of particles
A dense layer having a porosity of 11 vol% was formed.

Example 29 8wt% Y as stabilizer_TwoO_ThreeContaining ZrO_TwoI
Ngot and Al _TwoO_ThreePVD using ingot
A film was formed on the metal substrate by the method. The coating is on the metal substrate side
To Al_TwoO_ThreePorosity of about 18v with 1wt% of dispersed phase added
ol% porous layer 250 μm, Al on the surface layer side_TwoO
_ThreeDense layer with porosity of 9 vol% with 5 wt% of dispersed phase added
Was formed.

Example 30 ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer was used, and A having an average particle size of 1.0 μm was used as the second phase oxide.
A spray coating was produced on a metal base material by an atmospheric pressure plasma method using a granulated powder type raw material powder in which 1 and 5 wt% of 1 ₂ O ₃ particles were added. The thermal spray coating has a porosity of about 17 vol.
%, A layer having 1 wt% of Al ₂ O ₃ particles added to the metal substrate side is 250 μm, and a layer of Al ₂ O ₃ particles is 5 wt% to the surface layer side.
The added layer is formed, and then the alumina sol is impregnated and fired.

Example 31 A ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer was used, and A having an average particle size of 1.0 μm was used as a second phase oxide.
A spray coating was produced on a metal base material by an atmospheric pressure plasma method using a granulated powder type raw material powder in which 1 and 5 wt% of 1 ₂ O ₃ particles were added. The thermal spray coating has a porosity of about 17 vol.
%, A layer having 1 wt% of Al ₂ O ₃ particles added to the metal substrate side is 250 μm, and a layer of Al ₂ O ₃ particles is 5 wt% to the surface layer side.
The added layer is formed, and then impregnated with the plate-like β-alumina slurry is carried out in a direction perpendicular to the stacking direction under a high magnetic field, followed by drying and firing.

Example 32 For ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer, Al ₂ having an average particle diameter of 4 μm was used as the second phase oxide.
It was produced under the same conditions as in Example 21 except that O ₃ powder was used.

Example 33 A ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer was used, except that a raw material powder obtained by adding 10 and 20 wt% of MgAl ₂ O ₄ as a second phase oxide was used. It was produced under the same conditions as in Example 21.

Example 34 ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer was added to ZnO 10 and 20 as a second phase oxide.
It was produced under the same conditions as in Example 21 except that the raw material powder added at wt% was used.

Example 35 With respect to ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer, NiO as the second phase oxide and 10 and 20 were used.
It was produced under the same conditions as in Example 21 except that the raw material powder added at wt% was used.

Example 36 ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer was used, and CoO was used as a second phase oxide in an amount of 10 and 20.
It was produced under the same conditions as in Example 21 except that the raw material powder added at wt% was used.

Example 37 Example 37 was used, except that 10 and 20 wt% of ZrSiO ₄ was added as the second phase oxide to ZrO ₂ powder containing 8 wt% Y ₂ O ₃ as a stabilizer. Two
It was produced under the same conditions as No. 1.

Next, the amount of blast damage, dimensional change, and peeling life of the metal-ceramic laminated structure members of Examples 19 to 37 were measured.

The amount of blast wear was expressed as a relative value based on Example 19 as the amount of thinning (depth) in blasting under a constant condition with alumina particles. The dimensional change is the result of the volumetric shrinkage amount after heat treatment in air at 1300 ° C. for 100 hours.

The peeling life is the result of examining the peeling state of the coating every 10 times by applying a heat cycle from room temperature to 1200 ° C. in a burner heating tester. The results are shown in Tables 3 and 4 together with the type and amount of the stabilizer for each example, the type and amount of the second phase oxide, the process conditions and the like.

[Table 3]

[Table 4]

[0072]

According to the present invention, Y ₂ O ₃ , MgO or C is used.
By forming pores or fine cracks in the zirconia-based ceramic layer having eO ₂ as a stabilizer, it is possible to improve heat insulation and prevent peeling due to thermal expansion and the like. Further, by dispersing the second particles in the ceramic layer, it is possible to suppress sintering and grain growth during use at high temperature, reduce structural change, and stabilize at high temperature.

In the present invention, due to the above-mentioned constitution, there is a problem with the conventional zirconia-based heat insulating material / heat-shielding coating material, that is, peeling due to sintering and grain growth when used at a relatively high temperature. It is possible to solve the progress of destruction and the change in characteristics such as thermal conductivity.

[Brief description of drawings]

FIG. 1 is a sectional view showing an example of a metal-ceramic multilayer structure member of the present invention.

FIG. 2 is a cross-sectional view showing a case where a second phase oxide exists around a fine crack in a main phase block.

FIG. 3 is a cross-sectional view showing a case where a second phase oxide is present in the peripheral portion of the main phase mass.

FIG. 4 is a cross-sectional view showing a case where a second-phase oxide is present around the pores formed by the main-phase mass.

FIG. 5 is a cross-sectional view showing an example in which an intermediate layer is formed between a metal layer and a ceramic layer in the metal / ceramic multilayer structure member of the present invention.

FIG. 6 shows that the density of the ceramic layer is increased near the surface,
Sectional drawing which showed the case where it lowered in the metal layer vicinity part.

FIG. 7 is a cross-sectional view showing the effect when fine cracks perpendicular to the metal layer are formed in the main phase block.

FIG. 8 is a cross-sectional view showing the influence when fine cracks parallel to the metal layer are formed in the main phase block.

FIG. 9 is a diagram showing a manufacturing process of the metal-ceramic multilayer structure member of the present invention.

[Explanation of symbols]

1 ... Metal-ceramic laminated structure member 2 ... Metal layer 3 ... Ceramics layer 4 ... Main phase block 5 ... Pores 6 ... Fine cracks 7: Second phase oxide 8: Middle class 9 ... near the metal layer 10 ... near the surface

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yutaka Ishiwata             2-4 Suehiro-cho, Tsurumi-ku, Yokohama-shi, Kanagawa               Toshiba Keihin Office (72) Inventor Yoshiyasu Ito             2-4 Suehiro-cho, Tsurumi-ku, Yokohama-shi, Kanagawa               Toshiba Keihin Office F term (reference) 4G031 AA03 AA07 AA08 AA12 AA22                       AA23 AA26 AA29 AA39 CA03                       CA04 CA07                 4K029 AA02 BA43 BB02                 4K044 AA01 BA12 BA19 BB01 BB03                       BB11 BC07 CA13 CA14 CA22                       CA44

Claims (8)

[Claims] 1. A laminated structural member comprising a metal layer and a ceramics layer laminated thereon, wherein the ceramics layer contains zirconium oxide containing at least one stabilizer selected from yttrium oxide, cerium oxide and magnesium oxide. A metal-ceramic laminated structure member having a main phase and containing fine cracks or pores. 2. The multilayer ceramic structure according to claim 1, wherein at least one kind of second phase oxide other than yttrium oxide, cerium oxide and magnesium oxide is dispersed in the ceramics layer. Element. 3. Zirconium oxide containing at least one stabilizer selected from yttrium oxide, cerium oxide and magnesium oxide, which is the main phase of the ceramics layer, is in the shape of a flat lump, and the second phase oxide is the main phase lump. During,
3. The metal-ceramic multilayer structure member according to claim 2, wherein a large amount is present in at least one or more locations selected from the vicinity of the peripheral portion of the main phase mass, the fine cracks and the periphery of the pores. 4. The density of the ceramics layer is high in the vicinity of the surface where the ceramics layer is exposed, and is low in the vicinity of the surface and on the side opposite to the surface and near the metal layer. Claim 2 or 3 characterized in that
The metal-ceramic laminated structure member described. 5. The distribution of the second phase oxide is high in the vicinity of the surface where the ceramics layer is exposed, and is low in the vicinity of the metal layer and on the opposite side of the surface near the metal layer. The metal-ceramic laminated structure member according to any one of claims 2 to 4, wherein 6. The second phase oxide is aluminum oxide,
Magnesium oxide-aluminum spinel, zinc oxide,
Nickel oxide, cobalt oxide and zirconium oxide,
Alternatively, it is composed of at least one selected from these complex oxides, and its content in the ceramic layer is 0.2.
% To 20 wt%, The metal-ceramic laminated structure member according to any one of claims 2 to 5, wherein 7. The metal-ceramic multilayer structure member according to claim 1, wherein an intermediate layer is formed between the metal layer and the ceramic layer. 8. Thermal spraying, CVD (chemical vapor deposition), PVD
A metal-ceramic laminated structure member according to any one of claims 1 to 7, which is produced by using at least one method selected from (physical vapor deposition) and sputtering. Production method.