JP3064113B2 - Method for joining ZrO2 ceramics - Google Patents
Method for joining ZrO2 ceramicsInfo
- Publication number
- JP3064113B2 JP3064113B2 JP4216897A JP21689792A JP3064113B2 JP 3064113 B2 JP3064113 B2 JP 3064113B2 JP 4216897 A JP4216897 A JP 4216897A JP 21689792 A JP21689792 A JP 21689792A JP 3064113 B2 JP3064113 B2 JP 3064113B2
- Authority
- JP
- Japan
- Prior art keywords
- zro
- main component
- ceramics
- joining
- ceramic
- 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.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明はＺｒＯ2 を主成分とする
セラミックス同志の接合方法に関し、特に水蒸気電解セ
ル、固体燃料電池などのＺｒＯ2 系セラミックスの接合
に有利に適用される接合方法に関する。The present invention relates to an method of joining ceramics comrades mainly composed of ZrO 2, in particular steam electrolysis cell, relates to a bonding method that are advantageously applicable to the bonding of the ZrO 2 based ceramics such as solid fuel cell.
【０００２】[0002]
【従来の技術】従来より、セラミックス同志の接合方法
としてはガラス質のもので封着する方法、接着剤で接着
する方法、レーザビームで溶接する方法、Ｍｏ・Ｍｎ法
でメタライズしてろう付する方法、Ｔｉなどの活性金属
を含んだろう材でろう付する方法があった。2. Description of the Related Art Conventionally, ceramics have been joined together by a method of sealing with a vitreous material, a method of bonding with an adhesive, a method of welding with a laser beam, and metalizing and brazing with a Mo · Mn method. There has been a method of brazing with a brazing material containing an active metal such as Ti.
【０００３】[0003]
【発明が解決しようとする課題】ガラス質のもので付着
する方法ではガラスが脆くて割れやすいという欠点があ
り、接着剤で接着する方法では有機系接着剤は耐熱性が
なく、せいぜい２００℃以下の温度でしか使用できな
く、無機系接着剤は接着力、気密性に乏しいという欠点
がある。また、レーザで溶接する方法は１，０００℃付
近まで予熱する必要があり、装置上大がかりである上
に、溶接部が溶融組織となって脆くて割れやすいという
欠点があり、Ｍｏ・Ｍｎ法でメタライズしてろう付する
方法では、加湿水素雰囲気で１４００℃に焼成するので
特殊な設備が必要であり、またＭｏが酸化しやすいので
高温酸化雰囲気では使用できないという欠点がある。さ
らに、また、活性金属を含んだろう材でろう付する方法
は一工程でできる簡便な方法であるが、高温酸化雰囲気
中では活性金属が酸化して使用できないという欠点があ
る。The glass-based method has the disadvantage that the glass is brittle and easily breaks, and the method of bonding with an adhesive has no heat resistance in an organic adhesive, and is at most 200 ° C. or less. , And the inorganic adhesive has the disadvantage of poor adhesion and airtightness. In addition, the method of welding with a laser requires preheating to around 1,000 ° C., which is large in equipment and has the disadvantage that the welded portion becomes brittle and easily cracked into a molten structure. The method of metallizing and brazing requires a special facility because it is fired at 1400 ° C. in a humidified hydrogen atmosphere, and has the disadvantage that Mo is easily oxidized and cannot be used in a high-temperature oxidizing atmosphere. Further, the brazing method using a brazing material containing an active metal is a simple method that can be performed in one step, but has a drawback that the active metal is oxidized and cannot be used in a high-temperature oxidizing atmosphere.
【０００４】本発明は上記技術水準に鑑み、上述したよ
うな欠点を克服し、ＺｒＯ2 を主成分とするセラミック
スを高温酸化雰囲気中で使用する時にも信頼性の優れた
接合性が得られるＺｒＯ2 を主成分とするセラミックス
の接合方法を提供しようとするものである。The present invention has been made in view of the above-mentioned technical state, and overcomes the above-mentioned disadvantages. The present invention provides a ZrO 2 having a highly reliable bonding property even when a ceramic containing ZrO 2 as a main component is used in a high-temperature oxidizing atmosphere. An object of the present invention is to provide a method for joining ceramics containing 2 as a main component.
【０００５】[0005]
【課題を解決するための手段】本発明はＺｒＯ2 を主成
分とするセラミックス同志を接合するにあたり、各セラ
ミックスの接合表面にＰｔを主成分とする金属膜を形成
させた後、大気中で１４００℃以上Ｐｔ融点以下の温度
で焼成して該金属膜をセラミックスの接合面に密着さ
せ、該セラミックスの密着金属膜間をＡｕを主成分とす
るろう材でろう付することを特徴とするＺｒＯ2 セラミ
ックスの接合方法である。According to the present invention, in joining ceramics containing ZrO 2 as a main component, a metal film containing Pt as a main component is formed on a joint surface of each ceramic, and then, a metal film having a thickness of 1,400 is formed in the air. ZrO 2 characterized by baking at a temperature not lower than the melting point of the Pt and not more than the melting point of the Pt to bring the metal film into close contact with the bonding surface of the ceramics, and brazing the adhesive metal film of the ceramic with a brazing material containing Au as a main component. This is a method of joining ceramics.
【０００６】本発明でいうＺｒＯ2 を主成分とするセラ
ミックスとは、安定化ＺｒＯ2 として酸素イオン導電性
を利用して、排ガス中の酸素センサ、水素製造装置、ガ
ス精製装置などに使用しうるＺｒＯ2 −８ｍｏｌ％Ｙ2
Ｏ3 ，ＺｒＯ2 −６ｍｏｌ％Ｙ2 Ｏ3 ，ＺｒＯ2 −１５
ｍｏｌ％ＭｇＯ，ＺｒＯ2 −９ｍｏｌ％ＭｇＯ，ＺｒＯ
2 −１５ｍｏｌ％ＣａＯ，ＺｒＯ2 −１１ｍｏｌ％Ｃａ
Ｏなどである。The ceramics containing ZrO 2 as a main component in the present invention can be used for oxygen sensors in exhaust gas, hydrogen production equipment, gas purification equipment, etc. by utilizing oxygen ion conductivity as stabilized ZrO 2. ZrO 2 -8 mol% Y 2
O 3 , ZrO 2 -6 mol% Y 2 O 3 , ZrO 2 -15
mol% MgO, ZrO 2 -9 mol% MgO, ZrO
2 -15mol% CaO, ZrO 2 -11mol % Ca
O and the like.
【０００７】また、本発明で使用するＰｔを主成分とす
る金属膜としては、Ｐｔを主成分とする金属膜のメッ
キ、Ｐｔを主成分とする金属のペースト（ペースト化剤
としては水のほか、アクリル樹脂、フェノール樹脂など
の有機粘結剤をアセトン、アルコールなどの有機溶剤が
使用しうる）、Ｐｔを主成分とする金属の蒸着膜などが
使用しうる。The metal film containing Pt as a main component used in the present invention includes plating of a metal film containing Pt as a main component, a metal paste containing Pt as a main component (a paste agent other than water is used). Organic binders such as an acrylic resin and a phenol resin may be used as an organic solvent such as acetone and alcohol), and a vapor-deposited film of a metal containing Pt as a main component may be used.
【０００８】さらに、本発明で使用しうるＡｕを主成分
とするろう材としては、Ａｕ−Ａｇ合金（全組成使用可
能）、Ａｕ−Ｐｔ合金（Ｐｔ濃度：６５ｍａｓｓ以
下）、Ａｕ−Ｃｕ合金（Ｃｕ濃度：２０ｍａｓｓ以
下）、Ａｕ−Ｎｉ合金（Ｎｉ濃度：２０ｍａｓｓ以下）
などが用いられる。Further, as a brazing material containing Au as a main component, Au-Ag alloy (all compositions can be used), Au-Pt alloy (Pt concentration: 65 mass or less), Au-Cu alloy ( Cu concentration: 20 mass or less), Au-Ni alloy (Ni concentration: 20 mass or less)
Are used.
【０００９】[0009]
【作用】本発明ではＺｒＯ2 セラミックスにＰｔを主成
分とする材料が接しており、これを大気中で１４００℃
以上で焼成することによりＺｒＯ2 セラミックスの粒界
を形成しているガラス質が一部溶融し、Ｐｔと反応して
ＺｒＯ2 セラミックスとＰｔを主成分とする金属膜との
密着力を向上させる作用がある。また、ろう材としてＡ
ｕを主成分とするものを用いて、Ｐｔを主成分とする金
属膜同志をろう付しているので、ろう材と金属膜との密
着力は良好で、信頼性の高いろう付が可能となる。さら
に、ＰｔやＡｕは高温での耐酸化性に優れる材料なの
で、接合体を高温酸化雰囲気で長時間使用しても接合性
能に変化はない。According to the present invention, a material containing Pt as a main component is in contact with ZrO 2 ceramic, which is brought into the air at 1400 ° C.
By virtue of the above sintering, the vitreous material forming the grain boundaries of the ZrO 2 ceramic is partially melted, and reacts with Pt to improve the adhesion between the ZrO 2 ceramic and the metal film containing Pt as a main component. There is. In addition, A
Since the metal films mainly composed of Pt are brazed by using a material mainly composed of u, the adhesion between the brazing material and the metal film is good, and a highly reliable brazing is possible. Become. Further, since Pt and Au are materials having excellent oxidation resistance at high temperatures, there is no change in bonding performance even when the bonded body is used for a long time in a high-temperature oxidizing atmosphere.
【００１０】以下、本発明の一実施態様を図１及び図２
によって説明し、本発明の構成及び作用をより詳しく説
明する。図１は接合された状態を表し、ＺｒＯ2 を主成
分とするセラミックス管１．１，１．２の接合面にＰｔ
を主成分とする金属膜２を形成し、金属膜２同志をＡｕ
を主成分とするろう材３でろう付している。Hereinafter, one embodiment of the present invention will be described with reference to FIGS.
The configuration and operation of the present invention will be described in more detail. FIG. 1 shows a joined state, in which Pt is attached to the joining surface of ceramic tubes 1.1 and 1.2 mainly composed of ZrO 2.
Is formed, and the metal films 2 are connected to each other by Au.
Is brazed with the brazing material 3 having as a main component.
【００１１】この状態のものを製作するための具体的な
手順を図２の工程図に示す。まず、第一工程ではセラミ
ックス管１．１，１．２の接合面にあたる部分にＰｔを
主成分とする粉末をペースト状にして塗布して金属膜２
を形成する。Ｐｔを主成分とする粉末とは純Ｐｔと不可
避の不純物からなる粉末がよい。金属膜２の形成方法と
しては、前記のように粉末をペースト状にして塗布する
他に、蒸着する方法またはメッキする方法も適用し得
る。次に、第二工程では金属膜２を形成したセラミック
ス管１．１，１．２を大気炉４内にセットし、ヒータ５
で１，４００℃以上Ｐｔの融点である１，７６９℃より
低い温度で加熱すると、金属膜２自身が緻密化するとと
もに、ＺｒＯ2 セラミックスの粒界を形成しているガラ
ス質が一部溶融し、Ｐｔと反応してＺｒＯ2 セラミック
ス管１．１，１．２とＰｔを主成分とする金属膜２との
密着力が向上する。次に第三工程では前記セラミックス
管１．１，１．２の金属膜２を形成した部分を互いには
め合い、はめ合い部にＡｕを主成分とするろう材３を置
いて、全体を大気中で炉４の中でヒータ５でろう材の融
点以上の温度に加熱すると、ろう材３は溶融し金属膜２
の表面を濡らしながら隙間を埋め室温まで冷却すると接
合が完了する。A specific procedure for manufacturing the device in this state is shown in the process chart of FIG. First, in a first step, a powder containing Pt as a main component is applied in a paste state to a portion corresponding to a joining surface of the ceramic tubes 1.1 and 1.2 to form a metal film 2.
To form The powder containing Pt as a main component is preferably a powder containing pure Pt and unavoidable impurities. As a method for forming the metal film 2, in addition to applying the powder in paste form as described above, a vapor deposition method or a plating method may be applied. Next, in the second step, the ceramic tubes 1.1 and 1.2 on which the metal film 2 has been formed are set in the atmospheric furnace 4 and the heater 5 is heated.
When heating at a temperature lower than 1,769 ° C., which is the melting point of Pt at 1,400 ° C. or more, the metal film 2 itself is densified and the glassy material forming the grain boundaries of the ZrO 2 ceramic is partially melted. , Pt and the adhesion between the ZrO 2 ceramic tube 1.1, 1.2 and the metal film 2 containing Pt as a main component is improved. Next, in a third step, the portions of the ceramic tubes 1.1 and 1.2 where the metal films 2 are formed are fitted to each other, and a brazing material 3 containing Au as a main component is placed in the fitted portions, and the whole is exposed to the air. When the brazing material 3 is heated to a temperature higher than the melting point of the brazing material by the heater 5 in the furnace 4,
Filling the gaps while wetting the surface of the substrate and cooling to room temperature completes the joining.
【００１２】接合部の形状は図１では、セラミックス管
１．２の一端を押し拡げてはめ合ったような構造になっ
ているが、この他にも図３のようにセラミックス管１．
１，１．２の内外を削ってはめ合わせる構造や、図４の
ように端面で突合わせる構造及び図５のように端面をテ
ーパ状に削ってはめ合わせる構造などが考えられる。図
３〜図５において、図１と同一部には同一符号を付した
ので説明は省略する。また管状のものばかりでなく、棒
状のもの、板状のものあるいはこれらの組合せにも適用
し得る。In FIG. 1, the shape of the joining portion is such that one end of the ceramic tube 1.2 is pushed out and fitted, but in addition, as shown in FIG.
A structure in which the inner and outer surfaces of 1 and 1.2 are cut and fitted, a structure in which the end surfaces are abutted as shown in FIG. 4, and a structure in which the end surfaces are tapered and fitted as shown in FIG. 3 to 5, the same parts as those in FIG. Further, the present invention can be applied to not only a tubular shape but also a rod shape, a plate shape or a combination thereof.
【００１３】[0013]
【実施例】セラミックス管としてＺｒＯ2 −８ｍｏｌ％
Ｙ2 Ｏ3 の成分で、外径２１ｍｍ、内径１８ｍｍ、長さ
５０ｍｍの円管と、同じ成分で一端の長さ１０ｍｍの部
分のみが、前記セラミックス管がはめ合うような形状に
なった外径２１ｍｍ、内径１８ｍｍ、長さ５０ｍｍの円
管を準備し、それぞれのはめ合い面にＰｔと不可避の不
純物からなる粉末をアセトン中にアクリル樹脂を溶か
し、濃度０．５ｍａｓｓ％のペースト状にしたものを塗
布し、大気中で１６００℃で１時間焼成した。焼成後の
セラミックス管を金属膜が互いに向き合うようにはめ合
い、その上に純金の直径０．５ｍｍ、長さ３００ｍｍの
ワイヤーを置き、大気中で１，０８０℃で５分間加熱し
ろう付を行なった。EXAMPLE ZrO 2 -8 mol% as ceramic tube
A Y 2 O 3 component having an outer diameter of 21 mm, an inner diameter of 18 mm, and a length of 50 mm, and an outer diameter having a shape such that only the portion of the same component having a length of 10 mm is fitted with the ceramic tube. A circular tube having a diameter of 21 mm, an inner diameter of 18 mm and a length of 50 mm is prepared, and a powder composed of Pt and unavoidable impurities is dissolved in an acrylic resin in acetone to form a paste having a concentration of 0.5 mass% on each of the fitting surfaces. It was applied and baked at 1600 ° C. for 1 hour in the air. The fired ceramic tube was fitted so that the metal films face each other, a wire of pure gold having a diameter of 0.5 mm and a length of 300 mm was placed on the tube, and heated at 1,080 ° C. for 5 minutes in the air to perform brazing. Was.
【００１４】ろう付後、Ｈｅリークテストで気密性を検
査したところ、検出限界以下の１×１０-9ａｔｏｍ．ｃ
ｃ／ｓｅｃ以下の気密性を有しており、接合面の断面検
査でも欠陥のない良好なろう付がなされていた。After the brazing, the airtightness was inspected by a He leak test. The result was 1 × 10 −9 atom. c
It had an airtightness of c / sec or less, and had good brazing without defects even in a cross-sectional inspection of the bonding surface.
【００１５】[0015]
【発明の効果】本発明を採用することにより次のような
効果が得られた。 （１）Ｐｔを主成分とする金属膜がＺｒＯ2 を主成分と
するセラミックスに密着しており、Ａｕを主成分とする
ろう材で接合しているので、気密性、接合性にすぐれた
接合が可能となった。 （２）接合部を構成する材料が耐酸化性に優れるので、
接合体を高温酸化雰囲気で長時間使用することが可能と
なった。 （３）特殊な用途として、ＺｒＯ2 セラミックス管を電
解質として用い、数本継いで直列に接続する時には、管
の内面から外面へ電気的接続が必要になるが、この場合
でも接合部は金属成分で構成されているので、管の内面
から外面への良好な導電性を示す。According to the present invention, the following effects can be obtained. (1) Since the metal film containing Pt as a main component is in close contact with the ceramic containing ZrO 2 as a main component and is bonded with a brazing material containing Au as a main component, the bonding is excellent in airtightness and bonding properties. Became possible. (2) Since the material constituting the joint is excellent in oxidation resistance,
The bonded body can be used for a long time in a high-temperature oxidizing atmosphere. (3) As a special application, when several ZrO 2 ceramic tubes are used as an electrolyte and connected in series by connecting several tubes, electrical connection is required from the inner surface to the outer surface of the tube. , It shows good conductivity from the inner surface to the outer surface of the tube.
【図１】本発明の一実施態様で得られたＺｒＯ2 セラミ
ックスの接合体の説明図。FIG. 1 is an explanatory view of a joined body of ZrO 2 ceramics obtained in one embodiment of the present invention.
【図２】本発明の一実施態様のＺｒＯ2 セラミックスの
接合方法を示す説明図。FIG. 2 is an explanatory view showing a method of joining ZrO 2 ceramics according to one embodiment of the present invention.
【図３】本発明の一実施態様で得られたＺｒＯ2 セラミ
ックスの接合体の説明図。FIG. 3 is an explanatory view of a joined body of ZrO 2 ceramics obtained in one embodiment of the present invention.
【図４】本発明の他の実施態様で得られたＺｒＯ2 セラ
ミックスの接合体の説明図。FIG. 4 is an explanatory view of a joined body of ZrO 2 ceramics obtained in another embodiment of the present invention.
【図５】本発明のさらに他の実施態様で得られたＺｒＯ
2 セラミックスの接合体の説明図。FIG. 5 shows ZrO obtained in still another embodiment of the present invention.
FIG. 2 is an explanatory view of a joined body of two ceramics.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭64−66097（ＪＰ，Ａ) 「セラミックス接合工学」、岩本信也 ら、日刊工業新聞社発行、155〜173頁、 1990年 (58)調査した分野(Int.Cl.7，ＤＢ名) C04B 37/00 B23K 1/19 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-64-66097 (JP, A) "Ceramic joining technology", Shinya Iwamoto et al., Published by Nikkan Kogyo Shimbun, pages 155-173, 1990 (58) Survey Field (Int. Cl. 7 , DB name) C04B 37/00 B23K 1/19
Claims (1)
志を接合するにあたり、各セラミックスの接合表面にＰ
ｔを主成分とする金属膜を形成させた後、大気中で１４
００℃以上Ｐｔ融点以下の温度で焼成して該金属膜をセ
ラミックスの接合面に密着させ、該セラミックスの密着
金属膜間をＡｕを主成分とするろう材でろう付すること
を特徴とするＺｒＯ2 セラミックスの接合方法。1. When joining ceramics containing ZrO 2 as a main component, P is added to the joining surface of each ceramic.
After forming a metal film containing t as a main component, 14
Baking at a temperature of not less than 00 ° C. and not more than the melting point of Pt to bring the metal film into close contact with the joining surface of the ceramics, and brazing between the adhered metal films of the ceramics with a brazing material containing Au as a main component. bonding method of 2 ceramics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4216897A JP3064113B2 (en) | 1992-08-14 | 1992-08-14 | Method for joining ZrO2 ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4216897A JP3064113B2 (en) | 1992-08-14 | 1992-08-14 | Method for joining ZrO2 ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0656544A JPH0656544A (en) | 1994-03-01 |
| JP3064113B2 true JP3064113B2 (en) | 2000-07-12 |
Family
ID=16695632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4216897A Expired - Lifetime JP3064113B2 (en) | 1992-08-14 | 1992-08-14 | Method for joining ZrO2 ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3064113B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0313902A (en) * | 1989-06-12 | 1991-01-22 | Olympus Optical Co Ltd | Compound optical parts and production thereof |
| JP2002350266A (en) * | 2001-05-24 | 2002-12-04 | Kyocera Corp | Package for pressure detector |
| US8629592B2 (en) * | 2009-06-25 | 2014-01-14 | General Electric Company | Hermetic sealing assembly and electrical device including the same |
| JP6700836B2 (en) * | 2016-02-16 | 2020-05-27 | 三菱重工業株式会社 | Joining structure, combustor, and combustion device |
| US10551261B2 (en) * | 2017-02-28 | 2020-02-04 | Rosemount Inc. | Joint for brittle materials |
| CN114634369A (en) * | 2020-12-15 | 2022-06-17 | 中国科学院大连化学物理研究所 | Ceramic sealing method capable of being used for long time under high-temperature oxidation and reduction atmosphere |
-
1992
- 1992-08-14 JP JP4216897A patent/JP3064113B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| 「セラミックス接合工学」、岩本信也ら、日刊工業新聞社発行、１５５〜１７３頁、１９９０年 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0656544A (en) | 1994-03-01 |
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