JPH09202669A - Joined body of ceramics and joining - Google Patents
Joined body of ceramics and joiningInfo
- Publication number
- JPH09202669A JPH09202669A JP8010284A JP1028496A JPH09202669A JP H09202669 A JPH09202669 A JP H09202669A JP 8010284 A JP8010284 A JP 8010284A JP 1028496 A JP1028496 A JP 1028496A JP H09202669 A JPH09202669 A JP H09202669A
- Authority
- JP
- Japan
- Prior art keywords
- ceramics
- skin layer
- metal
- metal foil
- joined
- 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.)
- Withdrawn
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Ceramic Products (AREA)
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はセラミックスの接合
体および接合方法、特に固体電解質型燃料電池に使用さ
れるセラミックスの接合体および接合方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic joined body and a joining method, and more particularly to a ceramic joined body and a joining method used in a solid oxide fuel cell.
【０００２】[0002]
【従来の技術】最近、例えば空気と水素をそれぞれ、酸
化剤ガスおよび燃料ガスとして、燃料が本来持っている
化学エネルギーを直接電気エネルギーに変換する燃料電
池が、省資源、環境保護の観点から注目されており、特
に固体電解質型燃料電池は発電効率が高く、廃熱を有効
に利用できるなど多くの利点を有するため研究、開発が
進んでいる。2. Description of the Related Art Recently, a fuel cell which directly converts chemical energy originally possessed by a fuel into electric energy by using, for example, air and hydrogen as an oxidant gas and a fuel gas respectively, has attracted attention from the viewpoint of resource saving and environmental protection. In particular, solid electrolyte fuel cells have many advantages such as high power generation efficiency and effective utilization of waste heat, and thus research and development are progressing.
【０００３】固体電解質型燃料電池に燃料ガスと酸化剤
ガスとを供給するため、固体電解質燃料電池のセパレー
タおよび固体電解質層にそれぞれのガスの給排気孔を設
け、この孔から各単電池の各電極面に各ガスを給排気す
るようにしたものを内部マニホールド形式と称してい
る。内部マニホールド形式の平板型固体電解質燃料電池
は、イットリアなどをドープしたジルコニア焼結体（Ｙ
ＳＺ）からなる平板状固体電解質層の両面に、それぞれ
（Ｌａ、Ｓｒ）ＭｎＯ3 の空気極と、Ｎｉ／ＹＳＺサー
メットの燃料極とを配置してなる平板状単電池と、隣接
する単電池同士を電気的に直列に接続し、かつ各単電池
に燃料ガスと酸化剤ガスとを分配するセパレータとを交
互に積層し、燃料極とセパレータの燃料ガス流通路側と
の間に金属メッシュを介在し、単電池の固体電解質層と
セパレータの間にそれぞれシール剤またはスペーサやガ
スケットを介在し、荷重を掛けてスタックに積層したも
のであり、各単電池の各電極面にそれぞれ燃料ガスと酸
化剤ガスとを接触させることにより起電力を発生する。In order to supply the fuel gas and the oxidant gas to the solid oxide fuel cell, the separator and the solid electrolyte layer of the solid electrolyte fuel cell are provided with respective gas supply / exhaust holes, and from these holes, each of the unit cells is provided with a gas supply / exhaust hole. The one in which each gas is supplied to and discharged from the electrode surface is called an internal manifold type. A flat solid electrolyte fuel cell of the internal manifold type is made of a zirconia sintered body (Y
SZ) a flat solid electrolyte layer on both sides of which a (La, Sr) MnO 3 air electrode and a Ni / YSZ cermet fuel electrode are arranged, and adjacent flat cells. Are electrically connected in series, and separators that distribute the fuel gas and the oxidant gas are alternately laminated to each unit cell, and a metal mesh is interposed between the fuel electrode and the fuel gas flow passage side of the separator. , A sealant or spacers or gaskets are respectively interposed between the solid electrolyte layer and the separator of the unit cell, and a load is applied to stack them on the stack, and the fuel gas and the oxidant gas are respectively attached to each electrode surface of each unit cell. An electromotive force is generated by contacting with.
【０００４】セパレータは燃料極と空気極とにそれぞれ
供給される燃料ガスと酸化剤ガスとを分離してそれらの
クロスリークを防止する作用と、単電池同士を電気的に
直列に接続する作用とを有するものである。スタックの
内部で漏洩した燃料ガスと酸化剤ガスが混合すると、燃
料利用率が低下して燃料電池の効率が低下するのは勿
論、両ガスの混合により燃焼して局部的な温度上昇を生
じ、熱応力分布が不均一となり、クラックや歪みを生
じ、スタックの寿命を短縮させる。現在使用されている
代表的なセパレータはストロンチウムをドープしたラン
タンクロマイトのような導電性酸化物板のセラミックス
である。The separator has a function of separating the fuel gas and the oxidant gas supplied to the fuel electrode and the air electrode, respectively, to prevent their cross leak, and a function of electrically connecting the unit cells to each other in series. Is to have. When the fuel gas and the oxidant gas leaking inside the stack are mixed, not only the fuel utilization rate is lowered and the efficiency of the fuel cell is lowered, but also the mixture of both gases causes combustion to cause a local temperature rise, The thermal stress distribution becomes non-uniform, causing cracks and distortions, which shortens the stack life. A typical separator currently used is strontium-doped conductive oxide plate ceramics such as lanthanum chromite.
【０００５】このように、固体電解質型燃料電池の構成
材料の殆どすべてに多種類のセラミックス材料が使用さ
れており、特に、シール性と機械的強度はこれらの材料
に要求される重要な性質である。As described above, many kinds of ceramic materials are used for almost all the constituent materials of the solid oxide fuel cell, and in particular, the sealing property and the mechanical strength are important properties required for these materials. is there.
【０００６】[0006]
【発明が解決しようとする課題】固体電解質型燃料電池
は作動温度が約１０００℃度と高く、その構成材料が室
温からこの高温度まで、高強度および良シール性を連続
的に保持するためには、構成材料である上記セラミック
ス材料を互いに強固に接合し、さらにシール性が良好と
なるように接合する技術の開発が望まれてきた。従来、
異種のセラミックス材料を互いに強固に接合することは
簡単容易であったが、接合部のシール性を良くするよう
に接合することは困難であった。The solid oxide fuel cell has a high operating temperature of about 1000 ° C., and its constituent material is to maintain high strength and good sealing property continuously from room temperature to this high temperature. It has been desired to develop a technique for firmly bonding the above-mentioned ceramic materials, which are constituent materials, to each other, and further, bonding them so that the sealing property becomes good. Conventionally,
It was easy and easy to firmly bond different kinds of ceramic materials to each other, but it was difficult to bond them so as to improve the sealing property of the bonded portion.
【０００７】この問題の解決法として、例えば、特開平
４−１２０６８号に、固体電解質型燃料電池の構成部材
の製作において、接合しようとするセラミックスとセラ
ミックスとの間にアルミニウムのような金属の箔を挿入
し、空気中で１０００℃程度で加熱し、接合する方法が
開示されている。As a solution to this problem, for example, in Japanese Unexamined Patent Publication (Kokai) No. 4-12068, a foil of a metal such as aluminum is provided between ceramics to be joined in the production of a component of a solid oxide fuel cell. There is disclosed a method of inserting a substrate, heating it at about 1000 ° C. in air, and joining it.
【０００８】図３は従来のセラミックス接合体の断面図
である。FIG. 3 is a sectional view of a conventional ceramic bonded body.
【０００９】図３は２枚のセラミックス板１、２の間に
金属の箔を挿入して空気中で１０００℃程度で加熱した
ところ、この金属の箔が溶融し酸化して金属酸化物３と
なったセラミックス接合体の断面状態を示している。す
なわち、焼き上がった後、２枚のセラミックス板１、２
が金属酸化物３を介して接合されている。このように従
来の接合方法では、高温度の空気中で接合作業を行うた
め、セラミックス１、２間に挿入した金属の箔全体が酸
化して金属酸化物（例えば金属がアルミニウムの場合は
アルミナ）３となってしまう。その結果、接合強度は大
きいものの、金属箔の内部まで（表皮層だけでなく）完
全に酸化物、すなわち、セラミックスとなってしまうこ
とから、セラミックス１、２および焼き上がった後完全
に酸化物化されている金属酸化物３のそれぞれの熱膨張
係数の違いにより、これら異種材料（１、２、３）間の
界面に歪みや割れを生じ、そのためシール性が低下し、
実用化できない欠点があった。In FIG. 3, when a metal foil is inserted between two ceramic plates 1 and 2 and heated at about 1000 ° C. in air, the metal foil is melted and oxidized to form a metal oxide 3. The cross-sectional state of the ceramics joined body is shown. That is, after baking, the two ceramic plates 1, 2
Are bonded via the metal oxide 3. As described above, in the conventional joining method, since the joining work is performed in high temperature air, the entire metal foil inserted between the ceramics 1 and 2 is oxidized and a metal oxide (for example, alumina when the metal is aluminum) is used. It will be 3. As a result, although the bonding strength is high, the inside of the metal foil (not only the skin layer) becomes an oxide, that is, a ceramic, so that it is completely oxidized after the ceramics 1 and 2 are baked. Due to the difference in the coefficient of thermal expansion of each of the metal oxides 3 present, distortion or cracking occurs at the interface between these dissimilar materials (1, 2, 3), which reduces the sealing performance,
There was a drawback that could not be put to practical use.
【００１０】本発明は上述の点にかんがみてなされたも
ので、固体電解質型燃料電池の構成部材の製作におい
て、２種のセラミックス間に挿入した金属箔または金属
板が、焼き上がり後にその表皮層、すなわちセラミック
スと該金属箔または金属板との界面のみを酸化物にし、
表皮層以外の中間部分は元の金属箔または金属板の材質
をそのまま残すようにする（従来のように金属箔または
金属板全体が酸化物とならないようにする）セラミック
スの接合方法、およびこの方法により作られた接合強度
が大であり、異材料間に生じる応力が緩和されシール性
が良好である接合体を提供することを目的とする。The present invention has been made in view of the above points, and in manufacturing a component of a solid oxide fuel cell, a metal foil or a metal plate inserted between two types of ceramics has a skin layer after baking. That is, only the interface between the ceramics and the metal foil or metal plate is made an oxide,
For the intermediate part other than the skin layer, the original material of the metal foil or metal plate is left as it is (preventing the whole metal foil or metal plate from becoming an oxide as in the conventional method), a method for joining ceramics, and this method. It is an object of the present invention to provide a joined body which has a high joining strength and is relaxed in stress generated between different materials and has a good sealing property.
【００１１】[0011]
【課題を解決するための手段】上記の第１目的を達成す
るため、本発明のセラミックス接合体はセラミックスが
表皮層のみ酸化された金属箔または金属板により接合さ
れていることを特徴とする。また、前記金属箔がアルミ
ニウムまたはＡｌ−Ｍｇ基合金であることを特徴とす
る。In order to achieve the above first object, the ceramics joined body of the present invention is characterized in that the ceramics is joined by a metal foil or a metal plate in which only the skin layer is oxidized. The metal foil is aluminum or an Al-Mg based alloy.
【００１２】上記の第２目的を達成するため、本発明の
セラミックス接合方法はセラミックスとの間に接触状態
に金属箔または金属板を挿入したものを、該金属箔また
は金属板の表皮層のみ酸化が進行するような条件で７０
０℃以上の温度に加熱することを特徴とする。また、前
記金属箔がアルミニウムまたはＡｌ−Ｍｇ基合金である
ことを特徴とする。In order to achieve the above second object, the ceramics joining method of the present invention is one in which a metal foil or a metal plate is inserted in contact with ceramics and only the skin layer of the metal foil or the metal plate is oxidized. 70 under the condition that
It is characterized by heating to a temperature of 0 ° C. or higher. The metal foil is aluminum or an Al-Mg based alloy.
【００１３】[0013]
【発明の実施の形態】本発明はセラミックスが表皮層の
み酸化された金属箔または金属板により接合されている
ことを特徴とするセラミックスの接合体である。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a bonded body of ceramics, characterized in that the ceramics are bonded together by a metal foil or a metal plate in which only the skin layer is oxidized.
【００１４】本発明で接合される材質としては次のよう
なものがある。 （１）セラミックス同志を接合する。前記セラミックス
の接合面にあらかじめＡｌを蒸着またはスパッタするこ
ともある。 （２）Ａｌ2 Ｏ3 同志を接合する。 （３）Ａｌ−Ｍｇスピネル同志を接合する。 （４）（Ｌａ1-x Ａx ）（Ｃｒ1-y Ｂy ）同志を接合す
る。The materials to be joined in the present invention are as follows. (1) Join ceramics members together. Al may be previously vapor-deposited or sputtered on the bonding surface of the ceramics. (2) Join Al 2 O 3 comrades. (3) Join Al-Mg spinels. (4) Joining (La 1-x A x ) (Cr 1- y By ).
【００１５】ここで、ＡはＳｒ、Ｃａ、Ｂａのうちのい
ずれか一つまたは二つ以上の組合わせ、ＢはＭｎ、Ｎ
ｉ、Ｍｇ、Ｃｏ、Ｚｒ、Ｃｅ、Ｆｅ、Ａｌのうちのいず
れか一つまたは二つ以上の組合わせであり、０≦ｘ≦
０．５０、０≦ｙ≦０．５０である。 （５）Ｙ2 Ｏ3 、ＣａＯ、Ｎｄ2 Ｏ3 、Ｇｄ2 Ｏ3 、Ｙ
ｂ2 Ｏ3 、ＣｅＯ、Ｓｃ2 Ｏ3 のうちのいずれか一つま
たは二つ以上の組合わせをドープしたＹ2 Ｏ3 を接合す
る。 （６）上記（１）（２）（３）（４）（５）の中のいず
れか二つずつを接合する。Here, A is one or a combination of two or more of Sr, Ca and Ba, and B is Mn and N.
Any one of i, Mg, Co, Zr, Ce, Fe and Al, or a combination of two or more thereof, and 0 ≦ x ≦
0.50 and 0 ≦ y ≦ 0.50. (5) Y 2 O 3 , CaO, Nd 2 O 3 , Gd 2 O 3 , Y
b 2 O 3, CeO, joining the Y 2 O 3 was either one or doped two or more combinations of Sc 2 O 3. (6) Join any two of the above (1), (2), (3), (4) and (5).
【００１６】本発明で接合する材質としては次のような
ものがある。 （１）金属箔または金属板 （２）アルミニウム箔または板 （３）Ａｌ−Ｍｇ基合金箔または板 また、本発明はセラミックスとの間に接触状態に金属箔
または金属板を挿入したものを、該金属箔または金属板
の表皮層のみ酸化が進行するような条件で７００℃以上
の温度に加熱することを特徴とするセラミックスの接合
方法である。The materials to be joined in the present invention are as follows. (1) Metal foil or metal plate (2) Aluminum foil or plate (3) Al-Mg-based alloy foil or plate In the present invention, a metal foil or metal plate is inserted in contact with ceramics, The method for joining ceramics is characterized in that heating is performed at a temperature of 700 ° C. or higher under the condition that only the skin layer of the metal foil or the metal plate is oxidized.
【００１７】上記接合方法の中の「金属箔または金属板
の表皮層のみ酸化が進行するような条件」とはセラミッ
クスではさみ込んだ金属箔または金属板をＨ2 、ＣＯの
ような還元性ガス中、Ａｒ、Ｈｅのような不活性ガス
中、Ｎ2 中、さらには高真空中において、７００℃以上
の温度に加熱することをいう。In the above-mentioned joining method, "the condition that the oxidation of only the skin layer of the metal foil or the metal plate proceeds" means that the metal foil or the metal plate sandwiched by the ceramics is reduced with a reducing gas such as H 2 or CO. Heating in an inert gas such as Ar or He, in N 2 , and in a high vacuum to a temperature of 700 ° C. or higher.
【００１８】[0018]
【実施例】図１は本発明によるセラミックス接合体の断
面図である。FIG. 1 is a sectional view of a ceramic bonded body according to the present invention.
【００１９】図１に示すように、セラミックス１とセラ
ミックス２との間に接触状態に金属箔１０を挿入したも
のを、該金属箔または金属板１０の表皮層のみ酸化が進
行するような条件で７００℃以上の温度に加熱すること
により、該金属箔または金属板１０のセラミックス１側
の表皮層に金属酸化物５を形成し、同様に該金属箔また
は金属板１０のセラミックス２側の表皮層に金属酸化物
６を形成し、金属酸化物５と金属酸化物６との間の部分
は金属箔または金属板１０の金属４のまま残っている。
そのため、後で述べるように極めて優れた効果が得られ
る。As shown in FIG. 1, a metal foil 10 inserted between the ceramics 1 and 2 in contact with the ceramics 1 and 2 is treated under conditions such that only the skin layer of the metal foil or the metal plate 10 is oxidized. By heating to a temperature of 700 ° C. or higher, a metal oxide 5 is formed on the skin layer of the metal foil or metal plate 10 on the ceramics 1 side, and the skin layer of the metal foil or metal plate 10 on the ceramics 2 side is similarly formed. The metal oxide 6 is formed on the metal oxide 6 and the portion between the metal oxide 5 and the metal oxide 6 remains as the metal 4 of the metal foil or the metal plate 10.
Therefore, as will be described later, an extremely excellent effect can be obtained.
【００２０】図２は本発明の方法によりアルミニウム箔
でアルミナ同志を接合したセラミックス接合体の漏れ量
の測定結果を示す図である。FIG. 2 is a diagram showing the results of measuring the amount of leakage of a ceramic bonded body in which alumina and aluminum are bonded together by the method of the present invention.
【００２１】図２は横軸にリークガス量（Ｈｅ）（単
位：ｓｃｃｍ／ｃｍ）、縦軸に差圧（単位：ｍｍＨ2
Ｏ）をとり、図中のＡ線は室温における漏れ量を示し、
図中のＢ線は１０００℃における漏れ量を示す。In FIG. 2, the horizontal axis represents the leak gas amount (He) (unit: sccm / cm), and the vertical axis represents the differential pressure (unit: mmH 2).
O), the line A in the figure indicates the amount of leakage at room temperature,
Line B in the figure indicates the amount of leakage at 1000 ° C.
【００２２】この図から、本発明にかかるセラミックス
接合体は室温ならびに固体電解質型燃料電池の運転温度
である１０００℃においても良好なシール性を示すこと
は明白である。From this figure, it is clear that the ceramic bonded body according to the present invention exhibits a good sealing property at room temperature and at 1000 ° C. which is the operating temperature of the solid oxide fuel cell.
【００２３】図２に示すセラミックス接合体の漏れ量測
定は次のような実験条件で実施された。The leakage amount of the ceramic bonded body shown in FIG. 2 was measured under the following experimental conditions.
【００２４】外径１０ｍｍ、内径６ｍｍのアルミナ管の
一端に、このアルミナ管の中心軸線に直角にアルミナ板
を本発明の接合方法により接合した。すなわち、アルミ
ナ管の一端とアルミナ板の間に厚さ０．０１ｍｍのアル
ミニウム箔を挿入し、Ｎ2 −３％Ｈ2 雰囲気中で１００
０℃、２時間加熱することにより接合した。完成したア
ルミナ管をロータリーポンプにより真空引きし、その中
にＨｅガスを導入し、差圧計によりアルミナ管内の圧力
経時変化を測定した。図２のＢ線に示す１０００℃での
測定においては、アルミナ管を管状炉に入れて測定を実
施した。An alumina plate having an outer diameter of 10 mm and an inner diameter of 6 mm was joined to one end of the alumina tube at right angles to the central axis of the alumina tube by the joining method of the present invention. That is, an aluminum foil having a thickness of 0.01 mm was inserted between one end of the alumina tube and the alumina plate, and the aluminum foil was heated to 100 in an atmosphere of N 2 -3% H 2.
Bonding was performed by heating at 0 ° C. for 2 hours. The completed alumina tube was evacuated by a rotary pump, He gas was introduced into it, and the time-dependent change in pressure inside the alumina tube was measured by a differential pressure gauge. In the measurement at 1000 ° C. indicated by the line B in FIG. 2, the alumina tube was put in a tubular furnace to perform the measurement.
【００２５】上記実施例では、本発明の方法をセラミッ
クスとセラミックスとの接合に使用するものとして説明
したが、本発明はセラミックスと金属との接合にも利用
することができる。In the above embodiments, the method of the present invention has been described as being used for joining ceramics to ceramics, but the present invention can also be used for joining ceramics to metals.
【００２６】また、上記実施例では、セラミックスなど
の被接合体に接触状態に挿入するものは金属の箔または
板であるとして説明したが、箔または板の代わりに粉末
などを使用することもできる。Further, in the above-mentioned embodiment, it is described that the object to be inserted into the object to be joined such as ceramics in a contact state is the metal foil or plate, but powder or the like may be used instead of the foil or plate. .
【００２７】[0027]
【発明の効果】本発明のセラミックス接合方法によれ
ば、被接合体であるセラミックスとの間に接触状態に金
属箔または金属板を挿入したものを、該金属箔または金
属板の表皮層、すなわちセラミックスと該金属箔または
金属板との界面のみ酸化が進行するような条件で７００
℃以上の温度に加熱溶融したので、完成した本発明のセ
ラミックス接合体では、金属箔または金属板の表皮層、
すなわちセラミックスとの界面のみ酸化され、金属箔ま
たは金属板の中間部分は元の金属箔または金属板の材質
をそのまま残して接合されているので、次のような極め
て優れた効果が得られる。 （１）セラミックス材料同志を強固に接合できる。 （２）金属箔または金属板の中間部分は元の金属箔また
は金属板の材質がそのまま残り、この部分が延性を有す
るので、被接合体のセラミックスとセラミックスとの間
に生じる応力を緩和することが可能となる。従来のセラ
ミックス接合体では金属箔または金属板すべてが酸化物
すなわちセラミックスに変質し、これが脆弱のため応力
緩和は不可能で、むしろクラックが発生していた。 （３）シール性の極めて優れた接合が可能となる。 （４）上記（１）（２）（３）に記載の効果により、固
体電解質型燃料電池の構成部材に最適のセラミックス接
合体が得られる。According to the ceramic bonding method of the present invention, a metal foil or a metal plate inserted in contact with the ceramic to be bonded is used as a skin layer of the metal foil or metal plate, that is, 700 under the condition that oxidation proceeds only at the interface between the ceramic and the metal foil or metal plate.
Since it has been heated and melted to a temperature of ℃ or more, in the completed ceramic joined body of the present invention, the skin layer of the metal foil or the metal plate,
That is, only the interface with the ceramic is oxidized, and the intermediate portion of the metal foil or metal plate is joined while leaving the original material of the metal foil or metal plate as it is, so that the following excellent effects are obtained. (1) Ceramic materials can be firmly joined together. (2) In the intermediate portion of the metal foil or metal plate, the material of the original metal foil or metal plate remains as it is, and since this portion has ductility, it is necessary to relieve the stress generated between the ceramics of the objects to be joined. Is possible. In the conventional ceramics bonded body, all of the metal foil or metal plate is transformed into an oxide, that is, ceramics, which cannot be relaxed because it is brittle, and rather cracks are generated. (3) Bonding with extremely excellent sealing properties is possible. (4) Due to the effects described in the above (1), (2), and (3), the optimum ceramics joined body can be obtained as a constituent member of the solid oxide fuel cell.
【図１】本発明によるセラミックス接合体の断面図であ
る。FIG. 1 is a cross-sectional view of a ceramic bonded body according to the present invention.
【図２】本発明の方法によりアルミニウム箔でアルミナ
同志を接合したセラミックス接合体の漏れ量の測定結果
を示す図である。FIG. 2 is a diagram showing a measurement result of a leakage amount of a ceramics joined body in which alumina members are joined together by an aluminum foil by the method of the present invention.
【図３】従来のセラミックス接合体の断面図である。FIG. 3 is a cross-sectional view of a conventional ceramic bonded body.
１ セラミックス ２ セラミックス ３ 金属酸化物 ４ 金属 ５ 金属酸化物 ６ 金属酸化物 １０ 金属箔または金属板 1 Ceramics 2 Ceramics 3 Metal Oxide 4 Metal 5 Metal Oxide 6 Metal Oxide 10 Metal Foil or Metal Plate
Claims (8)
属箔または金属板により接合されていることを特徴とす
るセラミックスの接合体。1. A joined body of ceramics, wherein the ceramics are joined by a metal foil or a metal plate in which only a skin layer is oxidized.
であることを特徴とする請求項１に記載のセラミックス
の接合体。2. The joined body of ceramics according to claim 1, wherein the metal foil or the metal plate is aluminum.
合金であることを特徴とする請求項１に記載のセラミッ
クスの接合体。3. The joined body of ceramics according to claim 1, wherein the metal foil or the metal plate is an Al—Mg based alloy.
Ａｌを蒸着またはスパッタすることを特徴とする請求項
１に記載のセラミックスの接合体。4. The bonded body of ceramics according to claim 1, wherein Al is vapor-deposited or sputtered on the bonded surface of the ceramics in advance.
金属箔または金属板を挿入したものを、該金属箔または
金属板の表皮層のみ酸化が進行するような条件で７００
℃以上の温度に加熱することを特徴とするセラミックス
の接合方法。5. A metal foil or a metal plate inserted in a contact state between ceramics to be joined is used under the condition that oxidation proceeds only in the skin layer of the metal foil or the metal plate.
A method for joining ceramics, which comprises heating to a temperature of ℃ or more.
であることを特徴とする請求項５に記載のセラミックス
の接合方法。6. The method for joining ceramics according to claim 5, wherein the metal foil or the metal plate is aluminum.
合金であることを特徴とする請求項５に記載のセラミッ
クスの接合方法。7. The method for joining ceramics according to claim 5, wherein the metal foil or the metal plate is an Al—Mg based alloy.
Ａｌを蒸着またはスパッタすることを特徴とする請求項
５に記載のセラミックスの接合方法。8. The method for joining ceramics according to claim 5, wherein Al is vapor-deposited or sputtered on the joint surface of the ceramics in advance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8010284A JPH09202669A (en) | 1996-01-24 | 1996-01-24 | Joined body of ceramics and joining |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8010284A JPH09202669A (en) | 1996-01-24 | 1996-01-24 | Joined body of ceramics and joining |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09202669A true JPH09202669A (en) | 1997-08-05 |
Family
ID=11746019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8010284A Withdrawn JPH09202669A (en) | 1996-01-24 | 1996-01-24 | Joined body of ceramics and joining |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09202669A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2887687A1 (en) * | 2005-06-28 | 2006-12-29 | Peugeot Citroen Automobiles Sa | BIPOLAR PLATE FOR FUEL CELL WITH INTEGRATED SEALING FUNCTION AND FUEL CELL COMPRISING SUCH PLATES |
| JP2011003343A (en) * | 2009-06-17 | 2011-01-06 | Nippon Telegr & Teleph Corp <Ntt> | Method of manufacturing solid oxide fuel cell |
-
1996
- 1996-01-24 JP JP8010284A patent/JPH09202669A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2887687A1 (en) * | 2005-06-28 | 2006-12-29 | Peugeot Citroen Automobiles Sa | BIPOLAR PLATE FOR FUEL CELL WITH INTEGRATED SEALING FUNCTION AND FUEL CELL COMPRISING SUCH PLATES |
| WO2007003751A1 (en) * | 2005-06-28 | 2007-01-11 | Peugeot Citroen Automobiles S.A. | Fuel cell bipolar plate with integrated sealing and fuel cell comprising such plates |
| JP2011003343A (en) * | 2009-06-17 | 2011-01-06 | Nippon Telegr & Teleph Corp <Ntt> | Method of manufacturing solid oxide fuel cell |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20030401 |