JP2000053471A - Production of long-sized sintered body - Google Patents
Production of long-sized sintered bodyInfo
- Publication number
- JP2000053471A JP2000053471A JP10231189A JP23118998A JP2000053471A JP 2000053471 A JP2000053471 A JP 2000053471A JP 10231189 A JP10231189 A JP 10231189A JP 23118998 A JP23118998 A JP 23118998A JP 2000053471 A JP2000053471 A JP 2000053471A
- Authority
- JP
- Japan
- Prior art keywords
- sintered body
- firing
- long
- horizontal
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はセラミックスパイプ
等の長尺の焼結体を製造する方法に関する。特には、曲
がりの少なく、変形の少ない長尺焼結体を歩留まり良く
製造することができる方法に関する。なお、本明細書中
において、焼結体とは焼成の対象となる未焼成の成形体
並びに焼成中及び焼成後の焼結体のいずれをも含む意で
ある。The present invention relates to a method for producing a long sintered body such as a ceramic pipe. In particular, the present invention relates to a method capable of producing a long sintered body with less bending and less deformation with a high yield. In this specification, the term “sintered body” includes both unsintered compacts to be fired and sintered bodies during and after firing.
【０００２】[0002]
【従来の技術】円筒型セルタイプの固体電解質型燃料電
池（以下Ｔ−ＳＯＦＣとも言う）の空気電極や多孔質支
持管を例にとって従来技術を説明する。 Ｔ−ＳＯＦＣ
は特公平１−５９７０５等によって公知である。 Ｔ−
ＳＯＦＣは、多孔質支持管−空気電極―固体電解質―燃
料電極―インタ−コネクタ−で構成される円筒型セルを
有する。空気電極側に酸素（空気）を流し、燃料電極側
にガス燃料（Ｈ2，ＣＨ4）を流してやると、このセル内
でＯ2-イオンが移動して化学的燃焼が起こり、空気電極
と燃料電極の間に電位が生じ発電が行われる。なお、空
気電極が支持管を兼用する形式のものもある。2. Description of the Related Art The prior art will be described by taking as an example an air electrode and a porous support tube of a cylindrical cell type solid oxide fuel cell (hereinafter also referred to as T-SOFC). T-SOFC
Is known from Japanese Patent Publication No. 1-59705. T-
The SOFC has a cylindrical cell composed of a porous support tube-air electrode-solid electrolyte-fuel electrode-interconnector. When oxygen (air) is flown to the air electrode side and gaseous fuel (H 2 , CH 4 ) is flown to the fuel electrode side, O 2− ions move in this cell, causing chemical combustion, and An electric potential is generated between the fuel electrodes to generate power. There is also a type in which the air electrode also serves as a support tube.
【０００３】Ｔ−ＳＯＦＣの空気電極用の材料として、
特公平１−５９７０５では、ＬａＭｎＯ3，ＬａＮｉＯ3
等の酸化物セラミックスが提案されている。その後、特
開平２−２９３３８４によって、Ｌａ1-xＳｒxＭｎＯ3
が、特開平２−２８８１５９によって、 Ｌａ1-xＳｒx
Ｍｎ1-yＡyＯ3が（ＡはＣｕ，Ｚｎ，Ｎｉ，Ｆｅ，Ｃ
ｏ，Ｃｒ，Ａｌ，Ｔｉ，Ｍｇの一以上）が提案された。
この空気電極パイプ（支持管兼用型）の寸法は、一般的
に１０〜２０ｍｍ、厚さ１〜２ｍｍ、長さ１〜２ｍであ
る。As a material for an air electrode of a T-SOFC,
In Japanese Patent Publication No. 1-59705, LaMnO 3 , LaNiO 3
And the like have been proposed. Then, according to JP-A-2-293384, La 1-x Sr x MnO 3
However, according to Japanese Patent Laid-Open No. 2-288159, La 1-x Sr x
Mn 1-y A y O 3 (A is Cu, Zn, Ni, Fe, C
o, Cr, Al, Ti, Mg).
The dimensions of the air electrode pipe (support tube combined type) are generally 10 to 20 mm, a thickness of 1 to 2 mm, and a length of 1 to 2 m.
【０００４】このような長尺のセラミックス焼結体を製
造する際には、横方向の反りが問題となる。長尺焼結体
の反りを少なくする一つの方法として吊り焼成が行われ
る。吊り焼成は、焼結体を長手方向に吊り下げた状態で
焼成を行うものであり、焼結体の自重による引っ張り応
力が焼結体中に働いて焼結体に矯正力が加わるため、反
りの少ない焼結体を得ることができる。When manufacturing such a long ceramic sintered body, warpage in the horizontal direction becomes a problem. Hanging firing is performed as one method of reducing the warpage of the long sintered body. Suspension firing is a method in which firing is performed while the sintered body is suspended in the longitudinal direction. The tensile stress due to the weight of the sintered body acts in the sintered body and a straightening force is applied to the sintered body. Sinter can be obtained.
【０００５】特公平６−１０１１３には、長尺焼結体の
製造方法に関し、セラミックス長尺体を該セラミックス
原料の収縮開始温度以上で横焼成した後、次にそれ以上
の温度で吊り焼成するとの技術が開示されている。同公
報によれば、ＺｒＯ2で長さ１．１ｍ、径２０ｍｍの棒
を、横焼成温度１３００〜１４５０℃、吊り焼成温度を
１４５０℃で焼成して良好な結果が得られたとしてい
る。Japanese Patent Publication No. 6-10113 relates to a method for producing a long sintered body, which comprises horizontally firing a long ceramic body at a temperature equal to or higher than the shrinkage starting temperature of the ceramic raw material, and then hanging and firing the ceramic body at a higher temperature. Is disclosed. According to the publication, a good result was obtained by firing a ZrO 2 rod having a length of 1.1 m and a diameter of 20 mm at a horizontal firing temperature of 1300 to 1450 ° C and a hanging firing temperature of 1450 ° C.
【０００６】[0006]
【発明が解決しようとする課題】しかし、特公平６−１
０１１３で具体的にその対象とされた材質・寸法以外の
長尺焼結体にあっては、吊り焼成前の横焼成の温度を低
くすると、横焼成時に十分に焼結が進まないために高温
強度が不足して、その後の吊り焼成において、自重によ
って焼結体が切れて焼結体が落下するおそれがあるもの
が多い。例えば、ランタンマンガナイトの収縮開始温度
は１０００℃であるが、１０００〜１３５０℃の範囲で
横焼成した焼結体を１３５０℃を越える温度で吊り焼成
する場合、落下の危険性は極めて高い。また、固体電解
質型燃料電池においてはセルをスタック化した際の接触
抵抗を低減するために、空気極支持管の真円度は９７％
以上であることが望ましい。横焼成温度を高くすると、
真円度は低下し、固体電解質型燃料電池用の空気極支持
管として使用することは難しい。[Problems to be solved by the invention]
In the case of a long sintered body other than the material and dimensions specifically targeted in step 0113, if the temperature of the horizontal firing before the hanging firing is lowered, the sintering does not proceed sufficiently during the horizontal firing, so In many cases, the strength is insufficient, and in the subsequent hanging firing, the sintered body may be cut by its own weight and the sintered body may fall. For example, although the shrinkage initiation temperature of lanthanum manganite is 1000 ° C., when a horizontally sintered body sintered in a range of 1000 to 1350 ° C. is suspended and fired at a temperature exceeding 1350 ° C., the danger of falling is extremely high. In a solid oxide fuel cell, the roundness of the cathode support tube is 97% in order to reduce the contact resistance when the cells are stacked.
It is desirable that this is the case. If you increase the horizontal firing temperature,
The roundness is reduced, and it is difficult to use as a cathode support tube for a solid oxide fuel cell.
【０００７】本発明は、長尺焼結体の組成が（Ｌｎ1-x
Ｍx）1-aＭｎＯ3，Ｌｎ：Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓ
ｍの一種以上，Ｍ：Ｓｒ，Ｃａ，０．１≦ｘ≦０．５，
０＜ａ≦０．１の組成からなるセラミックスパイプにお
いて、吊り焼成中の焼結体の落下を防止しつつ、真直性
と真円度に優れた長尺焼結体を得ることのできる製造方
法を提供することを目的とする。According to the present invention, the composition of the long sintered body is (Ln 1-x
M x ) 1-a MnO 3 , Ln: La, Ce, Pr, Nd, S
m: Sr, Ca, 0.1 ≦ x ≦ 0.5,
A method for manufacturing a ceramic pipe having a composition of 0 <a ≦ 0.1, in which a long sintered body having excellent straightness and roundness can be obtained while preventing the sintered body from dropping during hanging firing. The purpose is to provide.
【０００８】[0008]
【課題を解決するための手段】上記課題を解決するた
め、本発明の長尺焼結体の製造方法は、長尺焼結体の組
成が（Ｌｎ1-xＭx）1-aＭｎＯ3，Ｌｎ：Ｌａ，Ｃｅ，Ｐ
ｒ，Ｎｄ，Ｓｍの一種以上，Ｍ：Ｓｒ，Ｃａ，０．１≦
ｘ≦０．５，０＜ａ≦０．１の組成からなるセラミック
スパイプであり、長尺焼結体を長手方向に実質的に引っ
張り応力がかからない状態で焼成する工程（横焼成工
程）と、横焼成の後に長尺焼結体を長手方向に吊した状
態で焼成する工程（吊り焼成工程）と、を含み、横焼成
工程の焼成温度を１４００℃以上として、吊り焼成工程
の焼成温度を横焼成工程の焼成温度よりも高い温度とし
たことを特徴とする。Means for Solving the Problems In order to solve the above problems, a method for producing a long sintered body according to the present invention is characterized in that the composition of the long sintered body is (Ln 1-x M x ) 1-a MnO 3. , Ln: La, Ce, P
at least one of r, Nd, Sm, M: Sr, Ca, 0.1 ≦
a ceramic pipe having a composition of x ≦ 0.5, 0 <a ≦ 0.1, and firing a long sintered body in a state where tensile stress is not substantially applied in a longitudinal direction (horizontal firing step); And baking the long sintered body in a state of being suspended in the longitudinal direction after the horizontal firing (suspending firing step). The firing temperature in the horizontal firing step is set to 1400 ° C. or higher, and the firing temperature in the hanging firing step is set to be horizontal. It is characterized in that the temperature is higher than the firing temperature in the firing step.
【０００９】すなわち、横焼成工程において十分に高い
焼成温度で焼成した後に横焼成温度以上の温度で吊り焼
成するのである。横焼成中における焼結体の姿勢は基本
的には水平置きであるが、問題となるような引張り応力
がかからなければ、それに限定されるものではない。That is, after firing at a sufficiently high firing temperature in the horizontal firing step, hanging firing is performed at a temperature higher than the horizontal firing temperature. The orientation of the sintered body during the horizontal firing is basically horizontal, but is not limited to this as long as a problematic tensile stress is not applied.
【００１０】[0010]
【発明の実施の形態】本発明の長尺焼結体を固体電解質
型燃料電池用の空気極支持管として使用した場合を以下
に説明する。BEST MODE FOR CARRYING OUT THE INVENTION The case where the long sintered body of the present invention is used as an air electrode support tube for a solid oxide fuel cell will be described below.
【００１１】固体電解質型燃料電池の空気極支持管は、
反りが１．０ｍｍ以下、真円度が９７％以上であること
が望ましい。本発明の長尺焼結体の作製方法において
は、（Ｌｎ1-xＭx）1-aＭｎＯ3，Ｌｎ：Ｌａ，Ｃｅ，Ｐ
ｒ，Ｎｄ，Ｓｍの一種以上，Ｍ：Ｓｒ，Ｃａ，０．１≦
ｘ≦０．５，０＜ａ≦０．１の組成からなるセラミック
スパイプの反りが１．０ｍｍ以下、真円度が９７％以上
であるために、長尺焼結体を長手方向に実質的に引っ張
り応力がかからない状態で焼成し、横焼成の後に長尺焼
結体を長手方向に吊した状態で焼成し、横焼成工程の焼
成温度を１４００℃以上として、吊り焼成工程の焼成温
度を横焼成工程の焼成温度よりも高い温度とすることが
望ましい。横焼成温度が１４００℃未満の場合は吊り焼
成時に自重による落下をする危険性が高く製造歩留まり
が悪いからであり、吊り焼成温度が横焼成温度未満の場
合は真円度が９７％未満となるからである。The cathode support tube of the solid oxide fuel cell is
It is desirable that the warpage is 1.0 mm or less and the roundness is 97% or more. In the method for producing a long sintered body of the present invention, (Ln 1-x M x ) 1-a MnO 3 , Ln: La, Ce, P
at least one of r, Nd, Sm, M: Sr, Ca, 0.1 ≦
Since the warp of the ceramic pipe having the composition of x ≦ 0.5, 0 <a ≦ 0.1 is 1.0 mm or less and the roundness is 97% or more, the long sintered body is substantially moved in the longitudinal direction. After the horizontal firing, the long sintered body is fired in a state of being suspended in the longitudinal direction. After the horizontal firing, the firing temperature in the horizontal firing step is set to 1400 ° C. or higher, and the firing temperature in the hanging firing step is set to be horizontal. It is desirable that the temperature be higher than the firing temperature in the firing step. If the horizontal firing temperature is lower than 1400 ° C., the risk of falling due to its own weight during hanging firing is high, and the production yield is low. If the horizontal firing temperature is lower than the horizontal firing temperature, the roundness is less than 97%. Because.
【００１２】上記横焼成工程においては溝付きのセッタ
の溝内に焼結体を置いて焼成を行い、ここで、該溝が、
焼結体の断面プロファイルと実質的に同一の断面プロフ
ァイルを有することが望ましい。横焼成中の変形を極力
防止すべく、上記セッタの溝が変形防止の役割を果たす
のである。In the horizontal firing step, firing is performed by placing a sintered body in a groove of a grooved setter, wherein the groove is
It is desirable to have a cross-sectional profile that is substantially the same as the cross-sectional profile of the sintered body. In order to prevent deformation during horizontal firing as much as possible, the groove of the setter serves to prevent deformation.
【００１３】特にランタンマンガナイトやランタンクロ
マイト系の材料を焼成する場合にはセッタ材料として高
純度アルミナが望ましい。これらの材料は、Ｓｉとの反
応性が高いので、Ｓｉを含まない耐火材料がセッタ材料
として好ましいのである。現状においては、そのような
材料としては高純度アルミナが実用的である。ここで、
好ましいアルミナの純度は９９％以上である。In particular, when sintering lanthanum manganite or lanthanum chromite material, high-purity alumina is preferable as the setter material. Since these materials have high reactivity with Si, a refractory material containing no Si is preferable as the setter material. At present, high-purity alumina is practical as such a material. here,
Preferred alumina purity is 99% or more.
【００１４】また、セッタの溝には、焼成する焼結体と
同一材料のコ−ティングを施すことが好ましい。焼成中
の原子の拡散に起因する焼結体の材質変化を極力防止す
ることができるからである。コーティングの方法として
はスラリ−コ−ト法を採用することができる。コ−ティ
ングの厚さは０．０５〜２．０ｍｍが好ましい。Preferably, the groove of the setter is coated with the same material as the sintered body to be fired. This is because a change in the material of the sintered body due to diffusion of atoms during firing can be prevented as much as possible. A slurry coating method can be used as a coating method. The thickness of the coating is preferably 0.05 to 2.0 mm.
【００１５】[0015]
【実施例】以下、本発明の実施例を説明する。熱分解法
で作製した（Ｌａ0.75Ｓｒ0.25）0.99ＭｎＯ3粉（平均
粒径３０μｍのもの９０％、０．５μｍのもの１０％）
１００部に、有機バインダーを１０部、グリセリンを３
部、水を１０部加えて混練した。これを圧力３０ｋｇｆ
／ｃｍ2、５℃で押し出し成形を行い外径２６ｍｍ、肉
厚２．２ｍｍ、長さ１２００ｍｍのパイプ状成形体を得
た。これを４０℃で乾燥後、１７５℃で脱バインダ−し
た。Embodiments of the present invention will be described below. (La 0.75 Sr 0.25 ) 0.99 MnO 3 powder produced by the pyrolysis method (90% with an average particle size of 30 μm, 10% with 0.5 μm)
100 parts, 10 parts of organic binder and 3 parts of glycerin
And 10 parts of water. The pressure is 30kgf
Extrusion was performed at 5 ° C./cm 2 at 5 ° C. to obtain a pipe-shaped molded body having an outer diameter of 26 mm, a wall thickness of 2.2 mm, and a length of 1200 mm. After drying at 40 ° C., the binder was removed at 175 ° C.
【００１６】セッタとして高純度アルミナ（アルミナ分
９９．５％、密度８５％）に半径１１ｍｍの半円断面ス
レ−ト溝を掘ったものを準備した。溝の表面は、上記成
形体の製造に用いたのと同じ粉末をスラリ−コ−ト法に
より厚さ０．５ｍｍコ−ティングしておいた。A setter was prepared by digging a high-purity alumina (alumina content: 99.5%, density: 85%) with a semi-circular section groove having a radius of 11 mm. On the surface of the groove, the same powder as used in the production of the above-mentioned molded body was coated by a slurry coating method to a thickness of 0.5 mm.
【００１７】上記セッタに上記成形体をのせて、表１に
示す１３００〜１５００℃の各温度で１０ｈｒ横焼成し
た。The above compact was placed on the setter and laterally baked at 1300-1500 ° C. shown in Table 1 for 10 hours.
【００１８】[0018]
【表１】 [Table 1]
【００１９】次に、同表１に示す１３６０〜１５１０℃
の各温度で吊り焼成をした。焼成後の焼結体の寸法は、
ほぼ外径２２ｍｍ、肉厚２．０ｍｍ、長さ１１００ｍｍ
であった。その空孔率は２８〜３９％であった。作製し
た焼結体について反りと真円度の測定を行った。反りは
焼結体を定盤の上に置き焼結体を定盤の間にできる最大
の隙間を隙間ゲ−ジを用いて測定した。真円度は焼結体
の外径の最大径と最小径を測定し、最小径÷最大径×１
００を真円度とした。表１、表２に、焼成の結果を示
す。落下とは、吊り焼成中に焼結体が切れて落下したこ
とを示す。Next, 1360 to 1510 ° C. shown in Table 1
Was fired at each temperature. The dimensions of the sintered body after firing
Almost 22mm in outer diameter, 2.0mm in thickness, 1100mm in length
Met. Its porosity was 28-39%. The warpage and roundness of the produced sintered body were measured. The warpage was measured by placing a sintered body on a platen and measuring the maximum gap between the platens using a gap gauge. The roundness is measured by measuring the maximum and minimum outer diameters of the sintered body, and the minimum diameter divided by the maximum diameter x 1
00 was set as the roundness. Tables 1 and 2 show the results of firing. The term "fall" indicates that the sintered body was cut and dropped during hanging firing.
【００２０】[0020]
【表２】 [Table 2]
【００２１】表１、２において横焼成温度１３００，１
３５０℃においては、吊り焼成時にいずれも焼結体が落
下した。横焼成温度が１４００℃以上の場合は吊り焼成
温度を横焼成温度以上とすることにより、反りが０．４
ｍｍ以下であり、真円度が９７％以上であり、特性を満
足することが可能であった。本実験結果より、固体電解
質型燃料電池の空気極支持管の焼成条件としては、横焼
成温度を１４００℃以上、吊り焼成温度を横焼成温度以
上とすることが望ましい。In Tables 1 and 2, the horizontal firing temperatures 1300, 1
At 350 ° C., any of the sintered bodies fell during hanging firing. When the horizontal firing temperature is 1400 ° C. or higher, the hanging firing temperature is set to be equal to or higher than the horizontal firing temperature, so that the warpage is 0.4%.
mm or less, and the roundness was 97% or more, and the characteristics could be satisfied. According to the results of this experiment, it is desirable that the baking temperature of the air electrode support tube of the solid oxide fuel cell is 1400 ° C. or more and the hanging baking temperature is not less than the transverse baking temperature.
【００２２】[0022]
【発明の効果】以上の説明から明らかなように、本発明
の長尺焼結体の製造方法によれば、真直性と真円度の良
好な長尺焼結体を歩留まり良く製造することができる。As is apparent from the above description, according to the method for manufacturing a long sintered body of the present invention, it is possible to manufacture a long sintered body having good straightness and roundness with good yield. it can.
Claims (2)
ＭｎＯ3，Ｌｎ：Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍの一種
以上，Ｍ：Ｓｒ，Ｃａ，０．１≦ｘ≦０．５，０＜ａ≦
０．１の組成からなるセラミックスパイプであり、長尺
焼結体を長手方向に実質的に引っ張り応力がかからない
状態で焼成する工程（横焼成工程）と、横焼成の後に長
尺焼結体を長手方向に吊した状態で焼成する工程（吊り
焼成工程）と、を含み、横焼成工程の焼成温度を１４０
０℃以上として、吊り焼成工程の焼成温度を横焼成工程
の焼成温度よりも高い温度としたことを特徴とする長尺
焼結体の製造方法。The composition of a long sintered body is (Ln 1-x M x ) 1-a
MnO 3 , Ln: at least one of La, Ce, Pr, Nd, Sm, M: Sr, Ca, 0.1 ≦ x ≦ 0.5, 0 <a ≦
A ceramic pipe having a composition of 0.1, in which a long sintered body is fired in a state where a tensile stress is not substantially applied in a longitudinal direction (horizontal firing step); Baking in a state of being suspended in the longitudinal direction (suspending baking step).
A method for producing a long sintered body, wherein the temperature is set to 0 ° C. or higher and the firing temperature in the hanging firing step is higher than the firing temperature in the horizontal firing step.
であり、真円度が９７％以上であることを特徴とする請
求項１記載の長尺焼結体の製造方法。2. The method for producing a long sintered body according to claim 1, wherein the warp of the long sintered body is 0.4 mm or less and the roundness is 97% or more.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10231189A JP2000053471A (en) | 1998-08-03 | 1998-08-03 | Production of long-sized sintered body |
| US09/673,934 US6692855B1 (en) | 1998-04-21 | 1999-04-19 | Solid electrolyte type fuel cell and method of producing the same |
| AU31713/99A AU3171399A (en) | 1998-04-21 | 1999-04-19 | Solid electrolyte fuel cell and method of producing the same |
| EP99913694A EP1081778A4 (en) | 1998-04-21 | 1999-04-19 | Solid electrolyte fuel cell and method of producing the same |
| PCT/JP1999/002048 WO1999054946A1 (en) | 1998-04-21 | 1999-04-19 | Solid electrolyte fuel cell and method of producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10231189A JP2000053471A (en) | 1998-08-03 | 1998-08-03 | Production of long-sized sintered body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000053471A true JP2000053471A (en) | 2000-02-22 |
Family
ID=16919735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10231189A Pending JP2000053471A (en) | 1998-04-21 | 1998-08-03 | Production of long-sized sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000053471A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003346820A (en) * | 2002-05-30 | 2003-12-05 | Sulzer Hexis Ag | Ink manufacturing method |
-
1998
- 1998-08-03 JP JP10231189A patent/JP2000053471A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003346820A (en) * | 2002-05-30 | 2003-12-05 | Sulzer Hexis Ag | Ink manufacturing method |
| JP4603773B2 (en) * | 2002-05-30 | 2010-12-22 | ヘクシス アクチェンゲゼルシャフト | Ink production method |
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