JPH03103385A - Metallization of ceramic and bonding of ceramic to metal - Google Patents
Metallization of ceramic and bonding of ceramic to metalInfo
- Publication number
- JPH03103385A JPH03103385A JP24026389A JP24026389A JPH03103385A JP H03103385 A JPH03103385 A JP H03103385A JP 24026389 A JP24026389 A JP 24026389A JP 24026389 A JP24026389 A JP 24026389A JP H03103385 A JPH03103385 A JP H03103385A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- ceramic
- metallized layer
- layer
- metallizing
- 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
- 239000002184 metal Substances 0.000 title claims abstract description 86
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 86
- 239000000919 ceramic Substances 0.000 title claims abstract description 56
- 238000001465 metallisation Methods 0.000 title abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 230000008646 thermal stress Effects 0.000 claims abstract description 14
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- 229910017945 Cu—Ti Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 33
- 238000005219 brazing Methods 0.000 claims description 19
- 238000007747 plating Methods 0.000 claims description 10
- 230000003139 buffering effect Effects 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 13
- 150000002739 metals Chemical class 0.000 description 11
- 239000010949 copper Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 229910017944 Ag—Cu Inorganic materials 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 plate Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 101150033765 BAG1 gene Proteins 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はセラミックスのメタライズ方法に関し、特に活
性金属を利用する前記メタライズ方法の改良に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for metallizing ceramics, and more particularly to improvements in the metallizing method using active metals.
（従来の技術）
セラミックス材料の耐摩耗性、耐熱性等に優れた特性を
積極的に利用する試みが活発に行われるようになってき
た。しかしながらセラミックスは前記優れた特性を持つ
反面、靭性に乏しいという欠点を有している他、高価で
あるため前記セラミックスを構造材として使用する場合
、高い靭性を持つ金属材料と複合化させ、セラミックス
の特性を要求される部分のみにセラミックスを使用する
ことが多く行われている。(Prior Art) Attempts have been actively made to utilize the excellent properties of ceramic materials, such as wear resistance and heat resistance. However, although ceramics have the above-mentioned excellent properties, they also have the disadvantage of poor toughness and are expensive. Ceramics are often used only in areas where specific properties are required.
前記複合化の方法としては、セラミックスを金属材料に
接合して行うことが一般的であり、従来より種々の技術
が開発されている。たとえば、特開昭６０ − １８８
１８５号公報や、特開昭８２ − ２１７５３３号公報
には、活性金属を含むＡｇ−Ｃｕろう材をセラミックス
と金属の間に介在させ直接加熱してセラミックスと金属
を接合し、接合体とする方法が開示されている。The method for making composites is generally to bond ceramics to metal materials, and various techniques have been developed so far. For example, Japanese Patent Publication No. 1888-1888
No. 185 and Japanese Unexamined Patent Publication No. 82-217533 disclose a method of interposing an Ag-Cu brazing material containing an active metal between ceramics and metals and directly heating the ceramics and metals to form a joined body. is disclosed.
また、セラミックスは金属と濡れ難い性質を有するため
、セラミックスと金属を接合するにあたり、メタライズ
とろう付けを同時に行うと接合界面に気泡状の非接合部
を形成したり、セラミックスのメタライズ反応が十分行
われていない部分を内包した状態がしばしば発生し、セ
ラミックスと金属接合体の接合強度が大きくばらつき、
接合体の信頼性の向上を阻害する要因になっていた。Additionally, since ceramics have the property of not being easily wetted by metals, if metallization and brazing are performed at the same time when joining ceramics and metals, bubble-like non-bonded areas may be formed at the bonding interface, and the metallization reaction of the ceramics may not be sufficiently carried out. This often results in a state where parts that are not bonded are included, and the bonding strength of the ceramic and metal bonded body varies greatly.
This was a factor that hindered the improvement of the reliability of the joined body.
こうした問題を解決する手段として予めセラミックスの
表面にＴｉ， Ｚｒの金属粉末あるいはその混合粉末
を塗布しその上に板ろう材を載置して真空中で加熱して
セラミックスの表面にメタライズ処理層を形或させ、メ
タライズが完全に施されていることを確認した後ろう付
けする方法が、例えば特開昭８３ − １３９０８８号
公報に開示されている。As a means to solve these problems, metal powders such as Ti and Zr or mixed powders of Ti and Zr are coated on the surface of the ceramic in advance, a brazing plate is placed on top of the powder, and the plate is heated in a vacuum to form a metallized layer on the surface of the ceramic. For example, Japanese Unexamined Patent Publication No. 139088/1983 discloses a method in which the material is shaped and brazed after confirming that metallization is completely applied.
これら方法の他、予めＴ１等の活性金属を含むＡｇ−
Ｃｕ系金属粉末を使用してメタライズする方法等も多く
提案されている。これらの従来方法でメタライズされた
セラミックスの、金属とのろう付け接合体は通常の常温
状態での使用には支障のない接合強度にまで達しつつあ
る。In addition to these methods, Ag-
Many methods of metallization using Cu-based metal powder have also been proposed. Ceramics metallized by these conventional methods and brazed joints with metals are reaching a joint strength that does not pose a problem when used under normal room temperature conditions.
しかしながら近年、セラミックスと金属の接合体を設計
する上で、より高い接合強度が要求される場合が多くな
ってきており、加えて、前記接合体を高温下で使用する
ケース、高温の使用状態と室温との間の熱サイクルを受
ける環境下で使用されるケースが多くなっており、前述
した従来方法でメタライズした接合体ではこうした過酷
な要求を十分満足させることができなかった。而して前
述した従来のセラミックスのメタライズ方法より更に熱
間接合強度や耐熱サイクル性に優れたメタライズ方法の
開発が望まれていた。However, in recent years, when designing a ceramic-metal bonded body, higher bonding strength is often required. In many cases, they are used in environments where they are subjected to thermal cycles between room temperature and room temperature, and the bonded bodies metallized by the conventional methods described above have not been able to fully satisfy these severe requirements. Therefore, it has been desired to develop a metallization method that has even better hot bonding strength and heat cycle resistance than the conventional ceramic metallization methods described above.
（発明が解決しようとする課題）
本発明は、活性金属、特にＴｉを含むＡｇ −Ｃｕ系金
属粉、或いはその合金粉末でセラミックスをメタライズ
する方法において、前述した従来のメタライズ方法の問
題点の抜本的な解決を図り、常温接合強度だけでなく熱
間強度特性にも優れたセラミックスのメタライズ方法、
並びにこのようにメタライズされたセラミックスと金属
との接合方法を提供することをその課題とするものであ
る。(Problems to be Solved by the Invention) The present invention is a method of metallizing ceramics using an active metal, particularly an Ag-Cu metal powder containing Ti, or an alloy powder thereof, which completely solves the problems of the conventional metallization method described above. A method for metallizing ceramics that has excellent not only room-temperature bonding strength but also hot strength properties.
Another object of the present invention is to provide a method for bonding metallized ceramics and metals.
（課題を解決するための手段）
前記課題を解決する本発明は、
セラミックス表面にＡｇ− Ｃｕ− Ｔｉ系金属による
メタライズ処理を施し、メタライズ層を形成した後、前
記メタライズ層にＮｉ金属を接触せしめ、真空、或いは
不活性ガス雰囲気中、６５０〜９００℃の温度で加熱処
理し、前記メタライズ層内にＮｉを拡散させることを特
徴とするものである。(Means for Solving the Problems) The present invention for solving the above-mentioned problems is as follows: After metallizing the ceramic surface with an Ag-Cu-Ti metal to form a metallized layer, Ni metal is brought into contact with the metallized layer. The method is characterized in that Ni is diffused into the metallized layer by heat treatment at a temperature of 650 to 900° C. in a vacuum or an inert gas atmosphere.
また、前記Ｎｉ金属がメタライズ層表面に施されたＮｉ
メッキであることを他の特徴とするものである。Further, the Ni metal is applied to the surface of the metallized layer.
Another feature is that it is plated.
さらにまた、セラミックス表面にＡｇ− Ｃｕ−Ｔｉ系
金属によるメタライズ処理を施しメタライズ層を形或し
た後、該セラミックスを金属に接合するにあたり、前記
メタライズ層と金属間に、上下にろう材が貼着され、さ
らに前記メタライズ層と接する表面にＮｉメッキ層を有
する熱応力緩衝材を介在せしめ、しかる後真空、或いは
不活性ガス雰囲気中、６５０〜９００℃の温度で、ＩＯ
分以上加熱することにより前記セラミックスと金属とを
接合することを他の特徴とするものである。Furthermore, after metallizing the ceramic surface with an Ag-Cu-Ti metal to form a metallized layer, when joining the ceramic to the metal, a brazing material is attached above and below between the metallized layer and the metal. Furthermore, a thermal stress buffering material having a Ni plating layer is interposed on the surface in contact with the metallized layer, and then IO is applied at a temperature of 650 to 900°C in a vacuum or an inert gas atmosphere.
Another feature of the present invention is that the ceramic and metal are bonded by heating for more than a minute.
以下、本発明の具体的な構成を詳細に説明する。Hereinafter, a specific configuration of the present invention will be explained in detail.
第１図は、本発明の基本構成を示す断面構造図である。FIG. 1 is a cross-sectional structural diagram showing the basic configuration of the present invention.
図において１はセラミックスであり、２は前記セラミッ
クス１の表面に形或されたメタライズ層、３はＮｉ金属
である。In the figure, 1 is a ceramic, 2 is a metallized layer formed on the surface of the ceramic 1, and 3 is Ni metal.
本発明においては、まずセラミックス１の表面に、Ａｇ
− Ｃｕ−Ｔｉ系金属、例えばＡｇ７１％、Ｃｕ２７％
、Ｔｉ ２％の配合組成の合金粉末を塗布し、８５０℃
の真空中で３０分間、加熱処理するなどしてメタライズ
処理を施し、メタライズ層２を形成する。このメタライ
ズ処理は活性金属メタライズ法として従来より知られて
いる方法であり、ＡＩ２ ０３，Ｚｒ０２などの酸化物
系セラミックス、ｓｔ３Ｎ４，ＡｊｌＮ，ＢＮ等の窒化
物系セラミックス、ＳｉＣ等の炭化物系セラミックス等
に適用できる。In the present invention, Ag is first applied to the surface of the ceramic 1.
- Cu-Ti metal, e.g. Ag71%, Cu27%
, coated with alloy powder with a composition of 2% Ti and heated at 850°C.
The metallized layer 2 is formed by performing metallization treatment such as heat treatment in a vacuum for 30 minutes. This metallization process is a method conventionally known as an active metal metallization method, and is suitable for oxide ceramics such as AI203 and Zr02, nitride ceramics such as st3N4, AjlN, and BN, and carbide ceramics such as SiC. Applicable.
前記メタライズ層２が形成されたら、そのメタライズ層
２にＮＩ金属３を接触せしめ、真空、或いは不活性ガス
雰囲気中で、しかも６５０〜９００℃の温度範囲で、加
熱処理する。この加熱処理によって前記Ｎｉ金属３は、
前記メタライズ層２内に拡散・浸透する。この結果メタ
ライズ層２は接合強度や熱サイクル性等の熱間強度特性
に優れたものとなる。After the metallized layer 2 is formed, the NI metal 3 is brought into contact with the metallized layer 2 and heat-treated in a vacuum or an inert gas atmosphere at a temperature in the range of 650 to 900°C. Through this heat treatment, the Ni metal 3 becomes
It diffuses and permeates into the metallized layer 2. As a result, the metallized layer 2 has excellent hot strength characteristics such as bonding strength and thermal cycleability.
本発明におけるＮｉ金属３は、後述する熱応力緩衝材と
して機能するのではなく、前述したメタライズ層２と接
して加熱処理され、メタライズ層２自体の接合強度を高
くし、しかも熱間特性に優れたメタライズ層組織に改質
することを目的とするものである。そのため熱応力緩衝
材のような厚い板である必要はなく、数坤の厚みでかつ
メタライズ層２の全面を必ずしも被覆する必要がない。The Ni metal 3 in the present invention does not function as a thermal stress buffer as described later, but is heat-treated in contact with the metallized layer 2 described above to increase the bonding strength of the metallized layer 2 itself and have excellent hot properties. The purpose of this is to modify the structure of the metallized layer. Therefore, it does not need to be a thick plate like a thermal stress buffering material, and it is not necessary to have a thickness of several ounces and to cover the entire surface of the metallized layer 2.
従って、本発明ではメタライズ層２に接触させるＮｉ金
属は種々の形状のもの、例えば、箔状、板状或いは粉末
状のＮｉ金属が使用でき、加熱処理方法に最も適した形
状のものを選択してメタライズ層２に接触させて加熱処
理すればよい。しかし、熱処理後のメタライズ層２に接
触させたＮｉ金属３が完全に密着していないと以後のろ
う付け工程で完全なろう付けが不可能となるので、メタ
ライズ層表面に、数一程度の厚みのＮｉメッキを施し、
しかる後、加熱処理する方法がメタライズの作業性やメ
タライズ層の改質反応の面から効果的である。Therefore, in the present invention, the Ni metal to be brought into contact with the metallized layer 2 can be in various shapes, such as foil, plate, or powder, and the shape most suitable for the heat treatment method is selected. The metallized layer 2 may be brought into contact with the metallized layer 2 and heat treated. However, if the Ni metal 3 that has been brought into contact with the metallized layer 2 after heat treatment is not completely adhered, complete brazing will not be possible in the subsequent brazing process. Ni plating is applied,
After that, a method of heat treatment is effective in terms of workability of metallization and modification reaction of the metallized layer.
また、加熱処理は、前述したように真空中あるいは不活
性ガス中で８５０℃以上９００℃以下の温度範囲で行わ
れる。このように加熱処理条件に制約を設けている理由
は、真空あるいは不活性ガス雰囲気以外ではメタライズ
層２が酸化して以後のろう付け工程に支障をきたすため
であり、６５０℃以下の温度ではＮｉ金属の拡散があま
り進行せずメタライズ層２の前述した改質が進まないた
めである。逆に上限の９００℃を越えると予め施してあ
る活性金属によるメタライズ層２から金属成分が蒸発し
、メタライズ層２の組織が変化し、後工程での金属との
良好な接合体が得られなくなる。加熱処理時間は特に限
定するものではないが、あまり短いとＮｉ金属３の拡散
が進行せず、メタライズ層２の改質が進まない。本発明
者らの経験では約ｌＯ分程度の処理時間があれば充分で
あった。Further, as described above, the heat treatment is performed in a vacuum or in an inert gas at a temperature range of 850° C. or higher and 900° C. or lower. The reason why the heat treatment conditions are restricted in this way is that the metallized layer 2 will oxidize in environments other than vacuum or inert gas atmosphere, which will interfere with the subsequent brazing process. This is because the metal diffusion does not proceed much and the above-mentioned modification of the metallized layer 2 does not proceed. On the other hand, if the temperature exceeds the upper limit of 900°C, the metal component will evaporate from the pre-applied active metal metallized layer 2, and the structure of the metallized layer 2 will change, making it impossible to obtain a good bond with metal in the subsequent process. . Although the heat treatment time is not particularly limited, if it is too short, the diffusion of the Ni metal 3 will not proceed and the modification of the metallized layer 2 will not proceed. In the experience of the present inventors, a processing time of approximately 10 minutes was sufficient.
Ｎｉ金属を接触させての加熱処理は、前述したようにＮ
ｉをメタライズ層２内に拡散させ、メタライズ層組織の
改質を図ることを目的とするものであり、この目的は金
属とのろう付けと並行して実施することでも違戊するこ
とが可能である。As mentioned above, heat treatment with Ni metal in contact with N
The purpose is to diffuse i into the metallized layer 2 to improve the structure of the metallized layer, and this purpose can also be achieved by performing it in parallel with brazing with metal. be.
即ち、メタライズ層を形威したセラミックスと金属を接
合するにあたり、例えば周知の炉中ろう付け時に、前記
金属とセラミックスのメタライズ面の間にＮｉ板、また
はＮＩ箔あるいはＮｉ粉末等のＮｆ金属を配してろう付
けを行うことにより、メタライズ層内にＮｉを拡散・浸
透させつつろう付け接合を同時に実施することが可能で
ある。That is, when joining ceramics with a metallized layer and metal, for example, during well-known furnace brazing, an Nf metal such as a Ni plate, Ni foil, or Ni powder is placed between the metallized surface of the metal and the ceramic. By performing brazing, Ni can be diffused and permeated into the metallized layer and brazed joint can be performed at the same time.
第２図は、本発明に基づいて製造されたセラミックスと
金属との接合体の一例を示す断面図である。FIG. 2 is a sectional view showing an example of a joined body of ceramic and metal manufactured according to the present invention.
図において５が金属であり、この金属５とメタライズ層
２が形成されたセラミックス１との間には、例えば銀ろ
う等のろう材６ ａ．． ６ ｂにサンドイッチされた
熱応力緩衝材４が介在されている。In the figure, 5 is a metal, and between the metal 5 and the ceramic 1 on which the metallized layer 2 is formed, there is a brazing material 6 such as silver solder. ．． A thermal stress buffer material 4 sandwiched between 6 b is interposed.
この熱応力緩衝材４は、０．５〜１．０＋ａｍ程度の厚
さの銅板等で構或されでおり、少なくとも前記メタライ
ズ層２に接する側の表面にＮｉメッキ層３ａが形成され
ている。而して第２図に示されるように金属５上に、ろ
う材６ｂ，Ｎｉメッキ層３ａが形成された熱応力緩衝材
４、ろう材６ａ，およびメタライズ層２を有するセラミ
ックス１が順次積層し、次いでこの状態で、真空、或い
は不活性ガス雰囲気の炉中等で、６５０〜９００℃の温
度で加熱することによってメタライズ層２内にＮｉを拡
散・浸透させつつろう付け接合を同時に実施することが
できる。The thermal stress buffering material 4 is made of a copper plate or the like having a thickness of about 0.5 to 1.0+am, and has a Ni plating layer 3a formed on at least the surface in contact with the metallized layer 2. As shown in FIG. 2, a brazing filler metal 6b, a thermal stress buffering material 4 with a Ni plating layer 3a formed thereon, a brazing filler metal 6a, and a ceramic 1 having a metallized layer 2 are sequentially laminated on the metal 5. Next, in this state, Ni can be diffused and penetrated into the metallized layer 2 by heating at a temperature of 650 to 900° C. in a vacuum or in a furnace under an inert gas atmosphere, and brazing can be performed at the same time. can.
尚、前記第２図の例では、熱応力緩衝材４にＮｉ金属を
メッキ層として介在させたが、ろう材６ａにＮｉメッキ
層を形成すること、或いはメタライズ層２と熱応力緩衝
材４の間にＮｉ金属箔や、Ｎｉ金属板等を介在させるこ
とでも同様な効果が得られる。In the example shown in FIG. 2, the thermal stress buffer material 4 is interposed with Ni metal as a plating layer, but it is possible to form a Ni plating layer on the brazing material 6a or to separate the metallized layer 2 and the thermal stress buffer material 4. A similar effect can be obtained by interposing a Ni metal foil, a Ni metal plate, or the like in between.
本発明において活性金属によるメタライズ処理と、メタ
ライズ層表面にＮｉ金属を接触させての加熱処理とを２
段階に分けて実施するのは、予めＮｉ金属を活性金属を
含むＡｇ−Ｃｕ系金属と一緒にメタライズ処理を行った
場合に生じる問題、つまりＮｉがＴｉと選択的に合金相
を形成してセラミックスと接合能を発揮するに必要なＴ
ｉを消費しその結果接合強度を低下させることを防止す
るためである。In the present invention, metallization treatment using an active metal and heat treatment by bringing Ni metal into contact with the surface of the metallization layer are performed in two steps.
The reason for performing the step-by-step process is to solve the problem that occurs when Ni metal is pre-metallized with Ag-Cu metals containing active metals, that is, Ni selectively forms an alloy phase with Ti, resulting in the formation of ceramics. T required to exhibit bonding ability with
This is to prevent consumption of i and resulting reduction in bonding strength.
（作 用）
前述したような問題を有する活性金属によるメタライズ
方法において、本発明は、予めセラミックス表面に、Ａ
ｇ− Ｃｕ− Ｔｉ系金属によるメタライズ処理を施し
、メタライズ層を形威した後、このメタライズ層にＮｉ
金属を接触させて加熱処理を行うだけの簡単な操作でメ
タライズ層中のＴｉの賦存状態を著しく変化させること
により常温接合強度だけでなく、熱間接合強度が高く、
耐熱サイクル性に優れたメタライズ層を形成させること
に成功したものである。(Function) In a metallization method using an active metal that has the above-mentioned problems, the present invention provides a method for applying A to the ceramic surface in advance.
After metallizing with g-Cu-Ti metal to form a metallized layer, Ni is applied to this metallized layer.
By simply bringing the metals into contact and performing heat treatment, the state of Ti in the metallized layer can be significantly changed, resulting in high not only room-temperature bonding strength but also hot bonding strength.
We succeeded in forming a metallized layer with excellent heat cycle resistance.
（実 施 例）
実施例 １
純度９２％のＡｊｌ’２０ｉセラミックス（２０Ｘ２０
Ｘ４ ＊ｔａ ｔ ）の表面に、Ｔｉ５ｖｔ％を含むＢ
Ａｇ−８相当組成の混合金属粉末（− ３２５ａ＋ｅｓ
ｈ）をスクリーンオイルで混練して調製したペーストを
１００ａ＋ｅｓｈのスクリーンで、１［１０ｍｇ印刷塗
布し、真空乾燥した後、１０〜’Ｔｏｒｒ． ８４０℃
の真空炉中で３０分間、加熱処理してメタライズ処理を
施した。このメタライズ層表面に、スクリーンオイルで
混練して調製したＮｉ金属粉末ペースト２５ｍｇを、３
００ｓｅｓｈのスクリーンで印刷、塗布し、真空乾燥さ
せた後、８４０℃のＡｒガス雰囲気炉中で３０分間加熱
処理を行った。(Example) Example 1 Ajl'20i ceramics (20X20
B containing 5vt% Ti on the surface of X4 *ta t )
Mixed metal powder with composition equivalent to Ag-8 (-325a+es
A paste prepared by kneading h) with screen oil was applied by printing on a 100a+esh screen in an amount of 1[10mg], dried under vacuum, and then heated at 10~'Torr. 840℃
Metallization treatment was performed by heat treatment for 30 minutes in a vacuum furnace. 25 mg of Ni metal powder paste prepared by kneading with screen oil was added to the surface of this metallized layer for 30 minutes.
After printing and coating with a 00 sesh screen and vacuum drying, heat treatment was performed for 30 minutes in an Ar gas atmosphere furnace at 840°C.
塗布したＮｉ金属粉末がメタライズ層と一体化したこと
を確認した後、このセラミックスの前記メタライズ層と
ＳＳ４１ｊＭ片の間に、銅熱応力緩衝材（２０ｘ ２０
ｘ Ｏ．５ ｔ ）の上下にＢＡｇ−８の板ろうを介し
て積層し８５０℃のＡｒガス雰囲気炉中で、３０分間、
加熱してろう付けした。このようにしてろう付けした接
合体と、前述したＮｉ金属粉末ペーストの塗布、および
その後の工程を行わない従来の活性金属法でメタライズ
したセラミックスを同一条件でろう付けした比較接合体
との熱間特性を調査した。After confirming that the applied Ni metal powder was integrated with the metallized layer, a copper thermal stress buffer material (20 x 20
xO. 5t) were laminated with BAg-8 solder plates on top and bottom, and heated in an Ar gas atmosphere furnace at 850°C for 30 minutes.
It was heated and brazed. Hot bonding between the thus brazed joined body and a comparative joined body in which ceramics metallized by the conventional active metal method, which does not include the application of the Ni metal powder paste mentioned above and the subsequent steps, are brazed under the same conditions. The characteristics were investigated.
第３図は、その調査結果の一例であり、●が本発明によ
るセラミックスと金属との接合体の熱間接合強度を、Ｏ
が比較材の熱間接合強度を示すものである。この第３図
から明らかなように、本発明に基づく接合体の常温接合
強度は、比較材の常温接合強度９８ＭＰａよりも約１．
５倍高い１４８ＭＰａの接合強度が得られ、熱間でも著
しく高い接合強度を示している。更に、この接合体を室
温と４００℃の間で１００回熱サイクルテストを行った
後、接合強度を比較したところ本発明の接合体には接合
強度の低下はほとんど観察されなかったが、比較材では
テスト前の強度の１／２に低下し、本発明が常温接合強
度のみならず熱間接合強度や耐熱サイクル特性に優れた
メタライズ方法であることが確認できた。Figure 3 shows an example of the investigation results, where ● indicates the hot bonding strength of the ceramic-metal bonded body according to the present invention;
indicates the hot bonding strength of the comparative materials. As is clear from FIG. 3, the room temperature bonding strength of the bonded body based on the present invention is about 1.
A bonding strength of 148 MPa, which is five times higher, was obtained, and the bonding strength is extremely high even in hot conditions. Furthermore, after performing a thermal cycle test on this bonded body 100 times between room temperature and 400°C, the bonding strength was compared. The strength decreased to 1/2 of that before the test, confirming that the present invention is a metallizing method that is excellent not only in room temperature bonding strength but also in hot bonding strength and heat cycle resistance.
実施例 ２
実施例１と同じ条件でメタライズ処理を施したセラミッ
クスを、前述した第２図に示すように予め３ｐの厚みの
Ｎｉメッキを施した銅熱応力緩衝材（２０Ｘ２０ｘＯ．
５ｔ）の上下間にＢＡｇ−８の板ろうを介して、ＳＳ４
１鋼片に積層し８４０℃のＡ『ガス気流の炉中に挿入し
て３０分間、加熱してろう付けした。並行して、同じ条
件で、Ｎｉメッキを施していないＣｕ緩衝材を使用して
製作した接合体を比較材として熱間特性を比較した。得
られた接合体の強度特性は、前記実施例１で製造した本
発明に基づく接合体の特性と殆ど同じであった。Example 2 Ceramic metallized under the same conditions as Example 1 was coated with a copper thermal stress buffer material (20x20xO.
5t) between the top and bottom of the SS4
The pieces were laminated into one steel piece, inserted into a gas flow furnace at 840°C, and heated and brazed for 30 minutes. In parallel, hot characteristics were compared using a bonded body manufactured under the same conditions using a Cu buffer material that was not plated with Ni as a comparison material. The strength characteristics of the obtained bonded body were almost the same as those of the bonded body based on the present invention manufactured in Example 1 above.
実施例 ３
Ｓｔ，Ｎ．セラミックス（２０ｘ２０ｘ４關ｔ）の表面
に、実施例１の仕様と同じＴ１５ｗｔ％を含むＢＡｇ−
８相当組戊の混合金属粉末ペーストをスクリーン印刷し
、真空乾燥した後、１０””Ｔｏｒｒ，８５０℃の真空
炉中で３０ｍＩｎ加熱処理してメタライズ処理した。冷
却後、炉外に取り出したＳｉ３Ｎ４セラミックスをＮｉ
無電解メッキ液に投入して、メタライズ層表面に約３坤
厚みのＮｉメッキを施し、再度８５０℃の真空炉中で３
０ｍｉｎ加熱処理した。Example 3 St,N. BAg- containing T15wt%, which is the same as the specification of Example 1, was applied to the surface of ceramics (20x20x4 pieces).
A mixed metal powder paste of 8 equivalents was screen printed, vacuum dried, and then heat-treated for 30 ml in a vacuum furnace at 10'' Torr and 850° C. for metallization. After cooling, the Si3N4 ceramics taken out of the furnace were
The surface of the metallized layer was plated with Ni to a thickness of about 3 cm by placing it in an electroless plating solution, and then it was plated again in a vacuum furnace at 850°C for 3 cm.
Heat treatment was performed for 0 min.
こうしてメタライズしたセラミックスを銅熱応力緩衝材
（２０Ｘ２０Ｘ０．５ｔ）の上下にＢＡｇ−１の板ろう
材を挿入しＳＳ４１鋼片上に積層させセラミックスの無
処理面より高周波加熱コイルを接近させ、大気中で約３
０秒加熱してろう付けを行った。The metallized ceramics were laminated on SS41 steel pieces by inserting BAg-1 brazing filler metals above and below a copper thermal stress buffer material (20 x 20 x 0.5 tons), and a high-frequency heating coil was brought closer to the untreated surface of the ceramics in the atmosphere. Approximately 3
Brazing was performed by heating for 0 seconds.
並行して同じ条件で製作したＮｉメッキなしメタライズ
セラミックスの接合体の接合強度を比較した。本発明の
接合体の常温接合強度は１２５ＭＰａであり、比較材の
接合強度は７２ＭＰａより著しく高かった。また、この
接合体を室温と４５０℃の間で５０回熱サイクルテスト
を行った後、その接合強度を比較したところ本発明の接
合体の接合強度は７５ＭＰａまで低下したが、比較材で
はテスト中にほとんどの接合体が破壊し強度測定ができ
ず、本発明の有用性が確認された。In parallel, the bonding strengths of metalized ceramic bonded bodies without Ni plating manufactured under the same conditions were compared. The bonding strength at room temperature of the bonded body of the present invention was 125 MPa, and the bonding strength of the comparative material was significantly higher than 72 MPa. In addition, after performing a thermal cycle test on this bonded body 50 times between room temperature and 450°C, the bonding strength was compared, and the bonding strength of the bonded body of the present invention was reduced to 75 MPa, while that of the comparative material was Most of the joined bodies were destroyed and strength measurement was not possible, confirming the usefulness of the present invention.
（発明の効果）
本発明によれば、Ｔ１等の活性金属を用いてセラミック
スをメタライズする方法において、活性金属メタライズ
層にＮｉ金属を介在させて加熱処理するだけの簡単な工
程で常温接合強度や熱間強度が高く、かつ耐熱サイクル
性に優れたメタライズセラミックスならびにセラミック
ス金属接合体を得ることができ工業的に有用である。(Effects of the Invention) According to the present invention, in a method of metallizing ceramics using an active metal such as T1, a simple process of interposing Ni metal in the active metal metallized layer and heat treatment can improve the room-temperature bonding strength. It is possible to obtain metallized ceramics and ceramic-metal joined bodies that have high hot strength and excellent heat cycle resistance, and are industrially useful.
第１図は、本発明の基本構或を示す断面構造図、第２図
は、本発明に基づいて製造されたセラミックスと金属と
の接合体の一例を示す断面図である。
第３図は、本発明に基づく接合体と比較材の熱間強度の
調査結果の一例を示す図表である。
１：セラミックス
３：Ｎｉ金属
４：熱応力緩衝材
６ａ，６ｂ：ろう材
２：メタライズ層
３ａ：Ｎｉメッキ層
５：金属FIG. 1 is a cross-sectional structural view showing the basic structure of the present invention, and FIG. 2 is a cross-sectional view showing an example of a joined body of ceramic and metal manufactured based on the present invention. FIG. 3 is a chart showing an example of the results of a hot strength investigation of a joined body based on the present invention and a comparative material. 1: Ceramics 3: Ni metal 4: Thermal stress buffering materials 6a, 6b: Brazing filler metal 2: Metallized layer 3a: Ni plating layer 5: Metal
Claims (3)
るメタライズ処理を施し、メタライズ層を形成した後、
前記メタライズ層にＮｉ金属を接触せしめ、真空、或い
は不活性ガス雰囲気中、６５０〜９００℃の温度で加熱
処理し、前記メタライズ層内にＮｉを拡散させることを
特徴とするセラミックスのメタライズ方法。(1) After metallizing the ceramic surface with Ag-Cu-Ti metal and forming a metallized layer,
A method for metallizing ceramics, characterized in that Ni metal is brought into contact with the metallized layer and heat treated at a temperature of 650 to 900° C. in a vacuum or an inert gas atmosphere to diffuse Ni into the metallized layer.
キであることを特徴とする請求項第１項記載のメタライ
ズ方法。(2) The metallizing method according to claim 1, wherein the Ni metal is Ni plating applied to the surface of the metallized layer.
るメタライズ処理を施しメタライズ層を形成した後、該
セラミックスを金属に接合するにあたり、前記メタライ
ズ層と金属間に、上下にろう材が貼着され、さらに前記
メタライズ層と接する表面にＮｉメッキ層を有する熱応
力緩衝材を介在せしめ、しかる後真空、或いは不活性ガ
ス雰囲気中、８５０〜９００℃の温度で、１０分以上加
熱し接合することを特徴とするセラミックスと金属の接
合方法。(3) After metallizing the ceramic surface with an Ag-Cu-Ti metal to form a metallized layer, when joining the ceramic to the metal, a brazing material is pasted above and below between the metallized layer and the metal. Further, a thermal stress buffering material having a Ni plating layer is interposed on the surface in contact with the metallized layer, and then the bonding is performed by heating at a temperature of 850 to 900° C. for 10 minutes or more in a vacuum or an inert gas atmosphere. A distinctive method of joining ceramics and metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24026389A JPH03103385A (en) | 1989-09-18 | 1989-09-18 | Metallization of ceramic and bonding of ceramic to metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24026389A JPH03103385A (en) | 1989-09-18 | 1989-09-18 | Metallization of ceramic and bonding of ceramic to metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03103385A true JPH03103385A (en) | 1991-04-30 |
Family
ID=17056896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24026389A Pending JPH03103385A (en) | 1989-09-18 | 1989-09-18 | Metallization of ceramic and bonding of ceramic to metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03103385A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04238875A (en) * | 1990-04-12 | 1992-08-26 | E I Du Pont De Nemours & Co | Method for brazing metalized constitutional element on ceramic base sheet |
| WO2004092785A2 (en) | 2003-03-31 | 2004-10-28 | Litton Systems, Inc. | Bonding method for microchannel plates |
| US8994482B2 (en) | 2011-05-19 | 2015-03-31 | Fuji Electric Co., Ltd. | Electromagnetic contactor |
| CN105057919A (en) * | 2015-09-16 | 2015-11-18 | 江苏科技大学 | Metalized materials for Si3N4 ceramic surface and preparation method as well as brazing technique |
-
1989
- 1989-09-18 JP JP24026389A patent/JPH03103385A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04238875A (en) * | 1990-04-12 | 1992-08-26 | E I Du Pont De Nemours & Co | Method for brazing metalized constitutional element on ceramic base sheet |
| JP2602372B2 (en) * | 1990-04-12 | 1997-04-23 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Method of brazing metallized components to ceramic substrate |
| WO2004092785A2 (en) | 2003-03-31 | 2004-10-28 | Litton Systems, Inc. | Bonding method for microchannel plates |
| EP1613448A2 (en) * | 2003-03-31 | 2006-01-11 | Litton Systems, Inc. | Bonding method for microchannel plates |
| EP1613448A4 (en) * | 2003-03-31 | 2008-09-10 | Litton Systems Inc | Bonding method for microchannel plates |
| US8994482B2 (en) | 2011-05-19 | 2015-03-31 | Fuji Electric Co., Ltd. | Electromagnetic contactor |
| CN105057919A (en) * | 2015-09-16 | 2015-11-18 | 江苏科技大学 | Metalized materials for Si3N4 ceramic surface and preparation method as well as brazing technique |
| CN105057919B (en) * | 2015-09-16 | 2017-04-05 | 江苏科技大学 | For Si3N4The material and preparation method of ceramic surface metallization and soldering processes |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5023147A (en) | Ceramics-metal jointed body | |
| JPH0367985B2 (en) | ||
| JPH03103385A (en) | Metallization of ceramic and bonding of ceramic to metal | |
| JPH05148053A (en) | Ceramics-metal joined material | |
| JPS62289396A (en) | Joining method for ceramics | |
| JPH0520392B2 (en) | ||
| JPH02217372A (en) | Method for jointing silicon nitride and metal | |
| JP3302714B2 (en) | Ceramic-metal joint | |
| JP2651847B2 (en) | Aluminum alloy for ceramic joining | |
| JP3505212B2 (en) | Joint and method of manufacturing joint | |
| JPS6338244A (en) | Manufacture of ceramic substrate for semiconductor device and clad material used for the same | |
| JPH07110795B2 (en) | Ceramic-metal bonded body with excellent bonding strength | |
| JPS63169348A (en) | Amorphous alloy foil for jointing ceramics | |
| JPS63170279A (en) | Ceramic joining method | |
| JPH02199075A (en) | Joined product of ceramic and metal | |
| JP2729751B2 (en) | Joining method of alumina ceramics and aluminum | |
| JP2001048670A (en) | Ceramics-metal joined body | |
| JPH04235246A (en) | Alloy for metalizing for ceramics and metalizing method | |
| JPH0240028B2 (en) | SERAMITSUKUSUTOKINZOKU * DOSHUSERAMITSUKUSUDOSHIMATAHAISHUSERAMITSUKUSUKANNOSETSUGOHOHO | |
| JP3153872B2 (en) | Metal-nitride ceramic bonding structure | |
| JPH07187839A (en) | Nitride ceramics-metal joined body and its production | |
| JPH0362674B2 (en) | ||
| JPH07172944A (en) | Adhesive composition, bonded product, and bonding process | |
| JP2001114575A (en) | Joining material of ceramics to ceramics and method for joining the same | |
| JPS62166087A (en) | Joining method for ceramics and metal |