JP2018138498A - Sintering substrate and method for manufacturing sintering substrate - Google Patents

Abstract

[Problem] To provide a sintering base plate that can be manufactured with almost no deformation of a large-sized solid electrolyte member and with a high shrinkage rate during sintering. A floor plate used for sintering a molded body containing a metal oxide having a perovskite crystal structure, wherein at least a surface on which the molded body is placed has a perovskite type oxide as a main component. And a portion other than the layer mainly composed of the perovskite oxide is composed of a plate-like base material mainly composed of zirconia, and the perovskite oxide comprises barium zirconate, One or more selected from the group consisting of strontium zirconate, barium cerate and strontium cerate, or a mixture or solid solution thereof, and an additive, and the thickness of the layer mainly composed of the perovskite oxide is 5 μm This is the floor plate for sintering. [Selection] Figure 1

Description

  The present invention relates to a base plate for sintering and a method for manufacturing a base plate for sintering.

A solid oxide fuel cell (SOFC, hereinafter also referred to as “SOFC”) has advantages such as high power generation efficiency, does not require an expensive catalyst such as platinum, and can use exhaust heat. Development is actively underway.
A fuel cell includes a membrane electrode assembly or a membrane electrode assembly (MEA) composed of a fuel electrode (anode) / solid oxide electrolyte / air electrode (cathode) in a basic part. Further, a fuel electrode current collector that is in contact with the fuel electrode of the MEA and a fuel electrode channel that supplies a fuel gas such as hydrogen to the fuel electrode are provided, and air that is in contact with the air electrode is also formed on the paired air electrode side. An electrode current collector and an air flow path for supplying air to the air electrode are provided.

Barium zirconate to which trivalent elements are added is relatively stable against CO ₂ and H ₂ O among materials exhibiting high proton conductivity, and is expected to be used as a solid electrolyte in medium temperature fuel cells. Has been. Similarly, barium cerate to which a trivalent element is added is known as a material exhibiting higher proton conductivity.
For example, Japanese Patent 2001-307546 (Patent Document 1), as an ion conductor for a fuel cell, _{wherein: BaZr 1-x-y Ce} x M y O 3-p (M is a trivalent substituent element , X and y are each a value greater than 0 and less than 1, x + y is less than 1, and p is a value greater than 0 and less than 1.5).
Further, Japanese Patent 2007-197315 (Patent Document 2), a mixed ionic conductor used for a fuel cell, ^{_{wherein: Ba d Zr 1-x-}} y Ce x M 3 y O 3-t (M 3 Is a trivalent rare earth element, at least one element selected from Bi, Ga, Sn, Sb and In, d is 0.98 or more and 1 or less, x is 0.01 or more and 0.5 or less, y is 0.01 There is described a mixed ionic conductor characterized by being made of a perovskite oxide represented by 0.3 or less and t is (2 + y−2d) / 2 or more and less than 1.5).

JP 2001-307546 A JP 2007-197315 A

  Among the above-mentioned perovskite oxides, yttrium-added barium zirconate (BZY) and yttrium-added barium cerate (BCY) exhibit good proton conductivity even in a temperature range of 700 ° C. or lower, so It is expected as a solid electrolyte member for a fuel cell. Therefore, the present inventors examined the production of a solid electrolyte member in which an anode layer, an electrolyte layer, and a cathode layer are laminated in this order using a perovskite oxide such as BZY or BCY. Specifically, the anode layer material is first molded and then pre-sintered at about 1000 ° C. to produce an anode layer material molded body. Subsequently, the electrolyte layer material is applied to one side of the surface of the anode layer material molded body. Then, co-sintering was performed at about 1450 ° C., and finally, a cathode layer material was applied and sintered at about 1000 ° C. to try to produce a laminated solid electrolyte member. However, when producing a large-sized solid electrolyte member, a problem has been found that the laminate of the anode layer and the electrolyte layer after co-sintering is deformed, and the shrinkage rate is lowered. Furthermore, since the large laminate has a low shrinkage after co-sintering and a dense electrolyte is not completed, the power generation efficiency is low.

As a result of various studies to identify the cause of the deformation of the laminate of the anode layer and the electrolyte layer and the decrease in the shrinkage rate, the present inventors have obtained the following knowledge.
When sintering an anode layer material molded body containing NiO and a metal oxide having a perovskite crystal structure, the anode layer material molded body is usually placed on a floor plate (setter) and sintered at a high temperature. . When a sintered body made of zirconium oxide is used to sinter an anode layer material molded body containing a BaZrO ₃ -based perovskite oxide as a metal oxide, as shown in FIG. It has been found that the BaO contained in the material molded body 42 is absorbed, which causes the sinterability to deteriorate. In particular, warpage occurs at the peripheral portion of the anode layer material molded body 42, sintering proceeds and contracts in the floating portion, and BaO continues to be absorbed in the central portion that remains in contact with the zirconium oxide base plate 41. Sinterability was getting worse. The occurrence of a large warp due to this sinterability variation was more pronounced as the anode layer material compact was made larger. Also in the case of SrZrO ₃ -based perovskite oxides, the zirconium oxide floor plate 41 absorbs SrO contained in the anode layer material molded body 42, so that the problem of deformation and a decrease in the shrinkage rate similarly occurs.
Generally, zirconium oxide flooring is said to have low reactivity with the material to be sintered. However, when a large-sized anode layer material molded body containing BaO or SrO is produced, it is deformed as described above. It has been found that there is a problem of reduction in shrinkage rate.
In addition, when an aluminum oxide base plate is used, the warping and deformation of the laminate of the anode layer and the electrolyte layer can be reduced, but BaO and SrO are absorbed by the aluminum oxide base plate, resulting in poor sinterability. Thus, only a laminate having a small shrinkage rate was obtained.

  The present invention solves the above-described problems, and can sinter a base plate for sintering and a base plate for sintering, which can be manufactured with almost no deformation of a large-sized solid electrolyte member and with a large shrinkage rate during sintering. An object is to provide a manufacturing method.

The sintering base plate according to one aspect of the present invention is
A base plate used for sintering a molded body containing a metal oxide having a perovskite crystal structure,
The floor plate includes at least a surface on which the molded body is placed by a layer containing a perovskite oxide as a main component, and a portion other than the layer containing the perovskite oxide as a main component has zirconia as a main component. It is composed of a plate-like base material that
The perovskite type oxide includes one or more selected from the group consisting of barium zirconate, strontium zirconate, barium cerate and strontium cerate, or a mixture or solid solution thereof, and an additive.
The thickness of the layer mainly composed of the perovskite oxide is 5 μm or more.
It is a floor board for sintering.

The manufacturing method of the floorboard for sintering according to one aspect of the present invention is as follows.
A method for producing a sintering base plate according to one aspect of the present invention,
A perovskite-type oxide layer forming step of forming a layer containing a perovskite-type oxide as a main component on at least one surface of a principal surface of a plate-like base material mainly containing zirconia;
The perovskite type oxide includes one or more selected from the group consisting of barium zirconate, strontium zirconate, barium cerate and strontium cerate, or a mixture or solid solution thereof, and an additive.
The thickness of the layer mainly composed of the perovskite oxide is 5 μm or more.
It is a manufacturing method of the floorboard for sintering.

  According to the above invention, it is possible to provide a floor plate for sintering and a method for manufacturing the floor plate, which can be manufactured with almost no deformation of a large-sized solid electrolyte member and with a high shrinkage rate during sintering. Can do.

It is the schematic showing an example of the floorboard which concerns on embodiment of this invention. It is the schematic showing another example of the floorboard which concerns on embodiment of this invention. The base plate No. produced in the examples was obtained. It is a photograph showing the result of having observed a part of section of 1 with the scanning electron microscope. It is the schematic for demonstrating the process in which a solid electrolyte member deform | transforms in the manufacturing method of the conventional solid electrolyte member.

[Description of Embodiment of the Present Invention]
First, embodiments of the present invention will be listed and described.
(1) The sintering base plate according to one aspect of the present invention is:
A base plate used for sintering a molded body containing a metal oxide having a perovskite crystal structure,
The floor plate includes at least a surface on which the molded body is placed by a layer containing a perovskite oxide as a main component, and a portion other than the layer containing the perovskite oxide as a main component has zirconia as a main component. It is composed of a plate-like base material that
The perovskite type oxide includes one or more selected from the group consisting of barium zirconate, strontium zirconate, barium cerate and strontium cerate, or a mixture or solid solution thereof, and an additive.
The thickness of the layer mainly composed of the perovskite oxide is 5 μm or more.
It is a floor board for sintering.
According to the aspect of the invention described in the above (1), the large-sized solid electrolyte member is hardly deformed and can be manufactured with a large shrinkage rate during sintering, A method for producing a floorboard can be provided. Furthermore, the solid electrolyte member manufactured using the sintering base plate according to the aspect of the invention described in the above (1) is dense due to a large shrinkage ratio before and after sintering, and is used for a fuel cell or the like. In some cases, the power generation efficiency can be further increased.
Note that in the sintering base plate according to one embodiment of the present invention, the “layer containing the perovskite oxide as a main component” refers to a layer containing 50 mass% or more of the perovskite oxide.
In the sintering base plate according to one embodiment of the present invention, “a plate-like base material containing zirconia as a main component” refers to a plate-like base material containing 50% by mass or more of zirconia.

(2) The sintering base plate described in (1) above is
It is preferable that all surfaces are constituted by a layer containing the perovskite oxide as a main component.
According to the aspect of the invention described in the above (2), the molded body is hardly deformed and the sintered body has a large shrinkage rate even if the molded body is placed on any part of the floor plate. Therefore, it is possible to provide a floor plate for sintering.

(3) The sintering base plate according to (1) or (2) above,
The zirconia preferably includes one or more selected from the group consisting of yttrium oxide (Y ₂ O ₃ ), calcium oxide (CaO), magnesium oxide (MgO), and scandium oxide (Sc ₂ O ₃ ).
(4) The sintering base plate according to any one of (1) to (3) above,
The additive is selected from the group consisting of yttrium (Y), ytterbium (Yb), erbium (Er), holmium (Ho), thulium (Tm), gadolinium (Gd), indium (In), and scandium (Sc). It is preferable that it is 1 or more types.
According to the aspects of the invention described in the above (3) and (4), it is possible to provide a sintering base plate having higher strength and toughness.

(5) A method for producing a floorboard according to one aspect of the present invention includes:
A method for producing a sintering base plate according to (1) above,
A perovskite-type oxide layer forming step of forming a layer containing a perovskite-type oxide as a main component on at least one surface of a principal surface of a plate-like base material mainly containing zirconia;
The perovskite type oxide includes one or more selected from the group consisting of barium zirconate, strontium zirconate, barium cerate and strontium cerate, or a mixture or solid solution thereof, and an additive.
The thickness of the layer mainly composed of the perovskite oxide is 5 μm or more.
It is a manufacturing method of the floorboard for sintering.
According to the aspect of the invention described in (5) above, it is possible to provide a method for manufacturing a sintering base plate capable of manufacturing the sintering base plate described in (1) above.
Note that, in the method for producing a sintering base plate according to one embodiment of the present invention, the “layer containing the perovskite oxide as a main component” refers to a layer containing 50 mass% or more of the perovskite oxide. Say.
Moreover, in the method for manufacturing a flooring sheet for sintering according to one aspect of the present invention, the “plate-like base material mainly containing zirconia” refers to a plate-like base material containing 50% by mass or more of zirconia. Say.

(6) The manufacturing method of the floorboard for sintering as described in said (5),
The perovskite oxide layer forming step,
A material containing barium compound, strontium compound, or barium compound and strontium compound, and the perovskite oxide is applied to at least one surface of the main surface of the plate-like base material mainly composed of zirconia, It is preferable to carry out by firing.
According to the aspect of the invention described in (6) above, it is possible to provide a method for manufacturing a sintering base plate capable of manufacturing the sintering base plate described in (1) above.

(7) The manufacturing method of the bottom plate for sintering as described in (5) above,
The perovskite oxide layer forming step,
It is preferable to carry out by placing a plate-like base material containing zirconia as a main component in a material containing barium compound, strontium compound, or barium compound and strontium compound, and the perovskite oxide, followed by firing. .
According to the aspect of the invention described in (7) above, it is possible to provide a method for manufacturing a sintering base plate capable of manufacturing the sintering base plate described in (2) above.

(8) The manufacturing method of the bottom plate for sintering as described in (5) above,
The perovskite oxide layer forming step,
It is preferable to apply the paste containing the perovskite oxide as a main component to at least one surface of the main surface of the plate-like base material containing zirconia as a main component, followed by firing.
According to the aspect of the invention described in (8) above, it is possible to provide a method for manufacturing a sintering base plate capable of manufacturing the sintering base plate described in (1) above.
In the method for producing a sintering base plate according to one aspect of the present invention, the “paste containing the perovskite oxide as a main component” refers to a paste containing 50% by mass or more of the perovskite oxide. Say.

[Details of the embodiment of the present invention]
Specific examples of the floorboard for sintering according to the embodiment of the present invention will be described below in more detail.
In addition, this invention is not limited to these illustrations, is shown by the claim, and intends that all the changes within the meaning and range equivalent to the claim are included.

<Silling board>
The sintering base plate according to the embodiment of the present invention is a base plate used for sintering a molded body including a metal oxide having a perovskite crystal structure (hereinafter, also simply referred to as “metal oxide”).
The said molded object should just be shape | molded by uniaxial shaping | molding, tape shaping | molding, etc., for example. The shape of the molded body is not particularly limited, and may be a desired shape such as a circular shape having a diameter of 50 mm or more and a rectangular shape having a side length of 50 mm or more. In particular, the larger the molded body or the thinner the molded body having a thickness of about 1 mm, the greater the effect obtained when the floorboard according to the embodiment of the present invention is used.

  Examples of the molded body include a molded body of an anode layer material for producing an anode layer of a solid electrolyte member for a fuel cell. The anode layer material only needs to contain NiO and the metal oxide. The content of NiO in the anode layer material is not particularly limited, but considering the balance between the linear expansion coefficient and the power generation efficiency, it is preferably 40% by mass or more and 90% by mass or less, preferably 60% by mass or more, More preferably, it is 90 mass% or less.

The metal oxide may be a metal oxide represented by the following formula [1], a mixture of metal oxides represented by the following formula [1], or a solid solution.
A _a B _b M _c O _3-δ formula [1]
In the above formula [1], A represents at least one element selected from the group consisting of barium (Ba), calcium (Ca), and strontium (Sr).
In the above formula [1], B represents at least one element selected from the group consisting of cerium (Ce) and zirconium (Zr).
In the above formula [1], M is derived from yttrium (Y), ytterbium (Yb), erbium (Er), holmium (Ho), thulium (Tm), gadolinium (Gd), indium (In), and scandium (Sc). At least one element selected from the group consisting of: In particular, when M is yttrium (Y), the proton conductivity of the solid electrolyte member becomes higher.

In the above formula [1], a may be a number satisfying 0.85 ≦ a ≦ 1, more preferably 0.88 ≦ a ≦ 0.98, and 0.90 ≦ a ≦ 0. More preferably, the number satisfies .97. High proton conductivity is exhibited when a is 0.85 or more. Further, when a is 1 or less, chemical stability is improved.
In the above formula [1], b may be any number that satisfies 0.50 ≦ b <1, more preferably 0.70 ≦ b ≦ 0.95, and more preferably 0.75 ≦ b ≦ 0. More preferably, the number satisfies .90. When b is 0.50 or more, precipitation of a phase that inhibits proton conduction can be suppressed. Further, when b is less than 1, the conductivity of the solid electrolyte member is further increased.
In the above formula [1], c is a number satisfying c = 1−b.
In the above formula [1], δ is the amount of oxygen deficiency and is determined according to the numerical values of a and b and the atmosphere.

Below, the structural example of the floorboard for sintering which concerns on embodiment of this invention using FIG.1 and FIG.2 is demonstrated.
As shown in FIG. 1, in the sintering base plate according to the embodiment of the present invention, at least the surface on which the molded body is placed is composed of a layer 11 containing a perovskite oxide as a main component, and the perovskite Portions other than the layer 11 containing a type oxide as a main component are constituted by a plate-like substrate 12 containing zirconia as a main component.
The thickness of the layer 11 containing a perovskite oxide as a main component may be 5 μm or more. When the thickness of the layer 11 containing a perovskite oxide as a main component is 5 μm or more, the molded body can be sintered without reacting the components contained in the molded body with the floorboard. The thickness of the layer 11 containing a perovskite oxide as a main component is preferably as thick as possible, but the thickness may be 50 μm or less from the viewpoint of manufacturing cost. The thickness of the layer 11 containing a perovskite oxide as a main component is more preferably 8 μm or more and 40 μm or less, and further preferably 10 μm or more and 30 μm or less.

  The layer 11 containing a perovskite oxide as a main component only needs to contain 50% by mass or more of the perovskite oxide, more preferably 60% by mass or more, and still more preferably 70% by mass or more. The layer 11 containing the perovskite type oxide as a main component may inevitably contain components other than the perovskite type oxide, and other components intentionally within a range not impairing the effects of the present invention. May be included.

The plate-like base material 12 containing zirconia as a main component only needs to contain 50% by mass or more of zirconia, more preferably 60% by mass or more, and still more preferably 70% by mass or more. The plate-like substrate 12 containing zirconia as a main component may inevitably contain components other than zirconia, and intentionally contains other components as long as the effects of the present invention are not impaired. It may be. Moreover, in the plate-shaped base material which has zirconia as a main component, it is preferable that the zirconia contains the additive. Examples of additives to zirconia include yttrium oxide (Y ₂ O ₃ ), calcium oxide (CaO), magnesium oxide (MgO), and scandium oxide (Sc ₂ O ₃ ). Zirconia is stabilized by adding these additives to become a solid solution, and mechanical properties are improved.

The shape of the plate-like base material 12 containing zirconia as a main component is not particularly limited, and may be appropriately changed according to the size of the molded body to be sintered. For example, a circle having a diameter of 120 mm or more or a rectangle having a side length of 150 mm or more can be employed. Moreover, the thickness of the plate-shaped base material 12 which has zirconia as a main component is not specifically limited, For example, what is necessary is just 0.5 mm or more, it is more preferable that it is 1 mm or more, and it is 1.5 mm or more. More preferably it is.
Since zirconia has a high melting point, it can be preferably used as a plate-like substrate. Among them, yttrium oxide stabilized zirconia and calcium oxide stabilized zirconia are widely distributed and easily available.

  As shown in FIG. 2, in the sintering base plate according to the embodiment of the present invention, all surfaces of the surface of the plate-like base material 22 mainly containing zirconia are mainly composed of perovskite oxide. It may be constituted by the layer 21. Accordingly, a sintering base plate that can be made into a sintered body having a large shrinkage rate with little deformation of the molded body no matter which part of the base plate is placed on the molding body. Can do.

The perovskite oxide is one or more selected from the group consisting of barium zirconate (BZO), strontium zirconate (SZO), barium cerate (BCO), and strontium cerate (SCO), or a mixture or solid solution thereof. Any additive may be used.
Examples of the additive added to the perovskite oxide include yttrium (Y), ytterbium (Yb), erbium (Er), holmium (Ho), thulium (Tm), gadolinium (Gd), indium (In), and scandium. (Sc) and the like.

It is preferable that the perovskite type oxide is appropriately selected according to the composition of the metal oxide contained in the compact to be sintered.
For example, the metal oxide contained in the compact to be sintered is Ba _x Zr _y Y _1-y O _3-δ1 (where x is a number satisfying 0.85 ≦ x ≦ 1, y is 0 .50 ≦ y <1, where δ1 is the amount of oxygen deficiency), the perovskite oxide is yttrium-added barium zirconate, barium zirconate, or yttrium-added barium zirconate and barium zirconate. It is preferable that Thereby, it can suppress more strongly that the metal oxide contained in a molded object and a flooring board react.
Similarly, the metal oxide contained in the molded body is Sr _x Zr _y Y _1-y O _3-δ1 (where x is a number satisfying 0.85 ≦ x ≦ 1, y is 0.50 ≦ y <1. The perovskite oxide is preferably yttrium-doped strontium zirconate, strontium zirconate, or yttrium-doped strontium zirconate and strontium zirconate.
Metal oxides contained in the molded body is _{Ba x Ce y Y 1-y} O 3-δ1 (x number satisfying 0.85 ≦ x ≦ 1, y is a number satisfying 0.50 ≦ y <1, δ1 is The perovskite oxide is preferably yttrium-added barium cerate, barium cerate, or yttrium-added barium cerate and barium cerate.
The metal oxide contained in the molded body is Sr _x Ce _y Y _1-y O _3-δ1 (x is a number satisfying 0.85 ≦ x ≦ 1, y is a number satisfying 0.50 ≦ y <1, and δ1 is The perovskite oxide is preferably yttrium-doped strontium cerate, strontium cerate, or yttrium-doped strontium cerate and strontium cerate.
Because the composition of the metal oxide contained in the molded object to be sintered is the same as that of the perovskite oxide contained on the surface of the floor plate, the metal oxide contained in the molded body is absorbed by the floor plate. Can be further suppressed.

<Manufacturing method of sintering base plate>
A method for manufacturing a sintering base plate according to an embodiment of the present invention is a method for manufacturing the sintering base plate according to the above-described embodiment of the present invention, and is a plate-like substrate mainly composed of zirconia. A perovskite-type oxide layer forming step of forming a layer mainly composed of a perovskite-type oxide on at least one surface of the main surface of the material;
As the plate-like base material containing zirconia as a main component (hereinafter, also simply referred to as “base material”), the same base material as described for the above-mentioned sintering base plate according to the embodiment of the present invention is used. The additive to zirconia may be the same.
What is necessary is just to form the layer which has a perovskite type oxide as a main component so that thickness may become 5 micrometers or more in the surface of at least one of the main surfaces of the said base material.
The perovskite-type oxide may be the perovskite-type oxide described for the sintering base plate according to the above-described embodiment of the present invention, and the same additives may be used.

  Examples of the method for forming a layer containing a perovskite oxide as a main component on at least one surface of the main surface of the substrate include the following first to third embodiments.

(First aspect)
The layer containing a perovskite oxide as a main component is a material containing a barium compound, a strontium compound, or a barium compound and a strontium compound and a perovskite oxide on at least one surface of the main surface of the substrate (hereinafter referred to as “perovskite oxide”). Then, it can be formed by simply applying and baking.
As the perovskite oxide, the perovskite oxide described for the sintering base plate according to the embodiment of the present invention may be used.

In the case where the perovskite oxide includes a perovskite oxide containing Ba, that is, barium zirconate, barium cerate, or the like, the material only needs to contain a perovskite oxide containing Ba and a barium compound. .
In the case where the perovskite oxide includes Sr-containing perovskite oxide, that is, strontium zirconate, strontium cerate, or the like, the material only needs to contain a perovskite oxide containing Sr and a strontium compound. .
In the case where the perovskite oxide is a perovskite oxide containing Ba and Sr, the material may contain a perovskite oxide containing Ba and Sr, a barium compound and a strontium compound.

As the barium compound, for example, BaCO ₃ , BaSO ₄ , BaNO _{3 and the} like can be used.
As the strontium compound, for example, SrCO ₃ , SrSO ₄ , BaNO _{3 and the} like can be used.
The content of the barium compound, the strontium compound, or the barium compound and the strontium compound in the material is preferably 1% by mass or more from the viewpoint of sufficiently diffusing barium or strontium into the base material. From the viewpoint of suppressing the amount of the remaining barium compound or strontium compound, it is preferably 50% by mass or less. The content of the barium compound, strontium compound, or barium compound and strontium compound in the material is more preferably 3% by mass or more and 40% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. Further preferred.

The method for applying the material is not particularly limited, and may be performed, for example, by screen printing or spray coating.
The firing temperature may be about 800 ° C. or more and 1700 ° C. or less, more preferably about 1000 ° C. or more and about 1600 ° C. or less, and further preferably about 1200 ° C. or more and 1500 ° C. or less.
The atmosphere for sintering may be an air atmosphere, an oxygen atmosphere, or the like.

  By applying and baking the material on at least one of the main surfaces of the substrate, the perovskite oxide contained in the material diffuses into the substrate. Further, Ba and Sr contained in the material react with the base material, and the reaction product diffuses into the base material. As a result, a layer containing a perovskite oxide as a main component is formed on the surface of the substrate on which the material is applied.

(Second aspect)
The layer mainly composed of a perovskite oxide may also be obtained by arranging and firing the base material in a material containing a barium compound, a strontium compound, or a barium compound and a strontium compound, and a perovskite oxide. Can be formed.
While the first aspect is a method in which the material is applied to and fired on at least one of the main surfaces of the base material, the second aspect has the base material embedded in the material. It is a method of firing. Therefore, the same base material and material as those described in the first embodiment can be used as the base material and the material. The firing temperature and atmosphere may be the same as in the first aspect.
According to the 2nd aspect, the layer which has a perovskite type oxide as a main component can be formed in the surface of all the surfaces of the said base material.

(Third aspect)
The layer containing the perovskite oxide as a main component is obtained by applying a paste (hereinafter also simply referred to as “paste”) containing the perovskite oxide as a main component to at least one of the main surfaces of the substrate. It can also be formed by firing from.
The paste only needs to contain 50% by mass or more of the perovskite oxide, more preferably 60% by mass or more, and still more preferably 70% by mass or more. As the perovskite oxide, the perovskite oxide described for the sintering base plate according to the embodiment of the present invention may be used.
The paste may be, for example, a paste formed by adding a binder and a solvent to perovskite oxide. As the binder, for example, ethyl cellulose (degree of ethoxylation of about 49%), an acrylic binder, or the like can be used. As the solvent, for example, α-terpineol or BCA (butyl carbitol acetate) can be used.
The method of applying the paste to at least one surface of the main surface of the substrate is not particularly limited, and may be applied by, for example, screen printing or spray coating.
By baking the base material coated with the paste, the perovskite type oxide contained in the paste diffuses into the base material, and the surface of the base material coated with the paste has a perovskite type oxide as a main component. Is formed.
The firing temperature and atmosphere may be the same as in the first embodiment.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, these Examples are illustrations and the flooring board for sintering of this invention, etc. are not limited to these. The scope of the present invention is defined by the terms of the claims, and includes all modifications within the meaning and scope equivalent to the terms of the claims.

[Example 1]
A zirconia plate made of yttrium oxide-stabilized zirconia (containing ZR-Y 150 mm × 150 mm × 1.5 mmt Y10 mol% manufactured by Nikkato Co., Ltd.) was used as a plate-like base material mainly composed of zirconia.
BaCO ₃ powder was used as the barium compound, and BaZr _0.8 Y _0.2 O _2.9 (BZY) powder was used as the perovskite oxide.
A material containing a barium compound and a perovskite oxide was prepared by mixing so that the content of BaCO ₃ powder was 10% by mass and the content of BZY powder was 90% by mass, and the material was made of an alumina container. Filled. Further, the zirconia plate (base material) was embedded in the material.
Then, each alumina container was heat-treated at 1400 ° C. for 10 hours in an air atmosphere, and a sintering base plate No. 1 for sintering was used. 1 was produced.
After the heat treatment, the floor plate No. 1 was taken out from the powder, and the surface was wiped with a cloth moistened with alcohol to remove the powder.

[Example 2]
The same zirconia plate as in Example 1 was used as a plate-like base material mainly composed of zirconia.
BaZr _0.8 Y _0.2 O _2.9 (BZY) powder was used as the perovskite oxide. BZY powder was mixed with binder ethylcellulose (degree of ethoxylation of about 49%) and solvent α-terpineol to form a paste to prepare a paste mainly composed of perovskite oxide.
The paste prepared above was applied to one of the main surfaces of the zirconia plate by screen printing. Subsequently, the binder and the solvent were removed by heating to 750 ° C. and drying. Furthermore, the process of apply | coating the paste produced above by screen printing, heating at 750 degreeC, and removing a binder and a solvent was repeated twice. The thickness of the paste mainly composed of perovskite oxide was set to 20 μm.
The zirconia plate coated with the paste mainly composed of perovskite oxide was heat-treated at 1400 ° C. for 10 hours in an air atmosphere to sinter a base plate for sintering. 2 was produced.

<Evaluation>
(Cross section observation)
Sintering plate No. The cross section of 1 was observed with a scanning electron microscope. The result is shown in FIG. As shown in FIG. 1 had a structure in which a layer 31 mainly composed of a perovskite oxide was formed on the surface of a plate-like substrate 32 mainly composed of zirconia. Further, as a result of elemental mapping of the cross section shown in FIG. 3 using an energy dispersive X-ray analyzer, a plate-like base material 32 mainly composed of zirconia is formed of yttrium oxide-stabilized zirconia, and a perovskite oxide is mainly used. It was confirmed that the layer 31 as a component was formed of yttrium-added barium zirconate. Sintering plate No. Similar results were obtained for 2.

(Shrinkage rate of solid electrolyte member)
Sintering board No. 1 produced in Example 1 and Example 2. 1, no. 2 and a conventional yttrium oxide-stabilized zirconia bed plate, a solid electrolyte member was prepared as follows, and the shrinkage rate was evaluated.
NiO powder and BaZr _0.8 Y _0.2 O _2.9 (BZY) powder of metal oxide having a perovskite crystal structure were used as the anode layer material. The mixing ratio of NiO powder and BZY powder was such that the NiO content was 70% by mass. The anode layer material was mixed as a water slurry by a ball mill and dried. The anode layer material after drying was uniaxially molded so as to have a circular shape with a diameter of 140 mm and a thickness of 500 μm to produce an anode layer material molded body.
The anode layer material compact was sintered at 1400 ° C. in the atmosphere to produce an anode layer. As the floor plate for sintering, the floor plate No. 1 for sintering produced in Example 1 and Example 2 was used. 1, no. 2 and a yttrium oxide-stabilized zirconia base plate for comparison were used.
The diameter of the anode layer produced using each floor was measured, and the shrinkage was calculated by comparing with the diameter of the anode layer material molded body before sintering.
As a result, when a conventional yttrium oxide-stabilized zirconia flooring was used, the shrinkage was 23%, and the flooring No. for sintering according to the embodiment of the present invention was obtained. 1, no. When 2 was used, the shrinkage ratio was improved to 25%.

(Deformation of solid electrolyte member)
When a conventional yttrium oxide-stabilized zirconia laying board was used, the obtained solid electrolyte member (anode layer) was deformed such that the inner part of the outer peripheral part jumped up as shown in FIG. Further, when a conventional yttrium oxide-stabilized zirconia flooring was used, the height of the most jumped position of the obtained anode layer was 4 mm. 1, floorboard No. When 2 was used, the obtained anode layer was not greatly deformed, and the height was 1.4 mm even at the highest portion.

11, 21, 31 Layers mainly composed of perovskite oxide 12, 22, 32 Plate-like base material mainly composed of zirconia 41 Zirconium oxide base plate 42 Anode layer material molded body 43 Electrolyte layer material

Claims (8)

A base plate used for sintering a molded body containing a metal oxide having a perovskite crystal structure,
The floor plate includes at least a surface on which the molded body is placed by a layer containing a perovskite oxide as a main component, and a portion other than the layer containing the perovskite oxide as a main component has zirconia as a main component. It is composed of a plate-like base material that
The perovskite type oxide includes one or more selected from the group consisting of barium zirconate, strontium zirconate, barium cerate and strontium cerate, or a mixture or solid solution thereof, and an additive.
The thickness of the layer mainly composed of the perovskite oxide is 5 μm or more.
Sintering board for sintering. The floor plate is composed of a layer containing all the perovskite oxide as a main component.
The sintering base plate according to claim 1. The zirconia includes one or more selected from the group consisting of yttrium oxide (Y ₂ O ₃ ), calcium oxide (CaO), magnesium oxide (MgO), and scandium oxide (Sc ₂ O ₃ ). Item 3. A sintering base plate according to Item 2.   The additive is selected from the group consisting of yttrium (Y), ytterbium (Yb), erbium (Er), holmium (Ho), thulium (Tm), gadolinium (Gd), indium (In), and scandium (Sc). The sintering base plate according to any one of claims 1 to 3, wherein the sintering base plate is one or more types. A method for producing a sintering base plate according to claim 1, comprising:
A perovskite-type oxide layer forming step of forming a layer containing a perovskite-type oxide as a main component on at least one surface of a principal surface of a plate-like base material mainly containing zirconia;
The perovskite type oxide includes one or more selected from the group consisting of barium zirconate, strontium zirconate, barium cerate and strontium cerate, or a mixture or solid solution thereof, and an additive.
The thickness of the layer mainly composed of the perovskite oxide is 5 μm or more.
A method for producing a base plate for sintering. The perovskite oxide layer forming step includes
A material containing barium compound, strontium compound, or barium compound and strontium compound, and the perovskite oxide is applied to at least one surface of the main surface of the plate-like base material mainly composed of zirconia, Done by firing,
The manufacturing method of the base plate for sintering of Claim 5. The perovskite oxide layer forming step includes
A barium compound, a strontium compound, or a barium compound and a strontium compound, and a perovskite type oxide, and a plate-like base material containing zirconia as a main component in a material containing the perovskite oxide, and firing.
The manufacturing method of the base plate for sintering of Claim 5. The perovskite oxide layer forming step includes
It is carried out by applying a paste containing the perovskite oxide as a main component to at least one surface of the main surface of the plate-like base material containing zirconia as a main component, followed by firing.
The manufacturing method of the base plate for sintering of Claim 5.