JPS6272472A - Joining method for ceramics and metal or the like - Google Patents
Joining method for ceramics and metal or the likeInfo
- Publication number
- JPS6272472A JPS6272472A JP21247885A JP21247885A JPS6272472A JP S6272472 A JPS6272472 A JP S6272472A JP 21247885 A JP21247885 A JP 21247885A JP 21247885 A JP21247885 A JP 21247885A JP S6272472 A JPS6272472 A JP S6272472A
- Authority
- JP
- Japan
- Prior art keywords
- ceramics
- joint
- silver solder
- heating
- joining
- 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
【発明の詳細な説明】
〔発明の利用分野〕
本発明はセラミックス同士およびセラミックスと金属を
加熱により溶解する中間材を介して接合する方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a method for joining ceramics to each other and to joining ceramics to a metal via an intermediate material that is melted by heating.
従来セラミックスと金属等との接合法は高融点金属法に
よるアルミナセラミックスとコバールの接合や酸化物ソ
ルダー法によるアルミナセラミックスとニオブとの接合
等が知られている。Conventionally known methods for joining ceramics and metals include joining alumina ceramics and Kovar using a high melting point metal method, and joining alumina ceramics and niobium using an oxide solder method.
前者の高融点金属法は例えば焼結アルミナセラミックス
にM o −M nメタライズペーストを塗布し、水素
炉にて1300〜1700℃で加熱焼付した後、ニッケ
ルめっきを施して水素炉中で約800℃で熱処理しメタ
ライズし、A g −Cu共晶ろうにてコバールと結合
する方法である。The former high-melting point metal method involves, for example, coating sintered alumina ceramics with Mo-Mn metallizing paste, baking it at 1300 to 1700°C in a hydrogen furnace, and then applying nickel plating and heating it at about 800°C in a hydrogen furnace. In this method, the metal is heat-treated and metalized, and then bonded to Kovar using an Ag-Cu eutectic solder.
また、後者の酸化物ソルダー法はCu0−MgO−AQ
20s B2O3の混合物を焼結アルミナセラミック
スに塗布し、金属ニオブを配置した後、10−’Tor
rの真空中にて約1500℃で加熱する接合方法である
。前者の方法は工程が複雑であり、後者の方法も真空を
利用するために接合品の量産化には難のある方法である
。In addition, the latter oxide solder method uses Cu0-MgO-AQ
After applying a mixture of 20s B2O3 to sintered alumina ceramics and placing niobium metal, 10-'Tor
This is a bonding method in which heating is performed at approximately 1500° C. in a vacuum of r. The former method involves complicated steps, and the latter method also uses vacuum, making it difficult to mass-produce bonded products.
またこれらの接合方法以外にセラミックスの接合面に直
接ろう材を介して接合する方法がある(特開昭59−2
32692号)にの方法はTi元素にCuあるいはAg
を添加した合金を予め作製し、セラミックス同士、もし
くはセラミックスと金属を接合するもので、Ti、Zr
の還元作用を利用したものである。この場合の加熱雰囲
気は真空中、Ar中等の不活性ガス中で行われる。しか
しこの接合法もAr中ではAQzOa等にはわずかなぬ
れ性を示すが、酸素センサー等に用いられる機能性Zr
0z等にはぬれ性が悪く、信頼性に欠ける欠点があり、
またぬれ性はよい真空中では量産化という点でも問題に
なる方法である。ぬれ性が悪いのは勿論接合強度も低い
ので問題になる。In addition to these bonding methods, there is also a method of bonding directly to the bonding surface of ceramics via a brazing filler metal (Japanese Unexamined Patent Publication No. 59-2
32692) is a method in which Cu or Ag is added to the Ti element.
This is a process in which an alloy containing Ti, Zr, and
This method takes advantage of the reducing effect of The heating atmosphere in this case is a vacuum or an inert gas such as Ar. However, this bonding method also shows slight wettability for AQzOa etc. in Ar, but it is not suitable for functional Zr used in oxygen sensors etc.
0z etc. have the disadvantage of poor wettability and lack of reliability.
In addition, in a vacuum with good wettability, this method poses problems in terms of mass production. This becomes a problem because not only the wettability is poor but also the bonding strength is low.
し発明の目的〕
本発明の目的は、機能性ZrO2等のセラミックスのぬ
れ性を良くシ、且つ接合強度を向上させるために、セラ
ミックスの接合面にTi膜を形成させ、N2と不活性ガ
スの混合ガス中で加熱することにより、一体間時接合が
できるセラミックスと金属の接合方法を提供することで
ある。OBJECT OF THE INVENTION] An object of the present invention is to form a Ti film on the bonding surface of ceramics and to improve the wettability of ceramics such as functional ZrO2 and to improve the bonding strength. An object of the present invention is to provide a method for joining ceramics and metal, which allows for time-intensive joining of ceramics and metals by heating in a mixed gas.
発明者らはこの目的を達成するためにTiの作用と効果
について、加熱雰囲気との相関を種々検討した。その結
果、セラミックスの還元作用をするTiはセラミックス
に近ければ近い程その作用が短時間で、しかもろう材の
ぬれ性を著しく向上し接合強度の向上に寄与することが
分った。またその作用もNz量が容量10%前後の不活
性ガス中で最も効果のあることを見い出した。In order to achieve this objective, the inventors conducted various studies on the function and effect of Ti and the correlation with the heating atmosphere. As a result, it was found that Ti, which has a reducing effect on ceramics, has a shorter time of action as it is closer to the ceramic, and moreover, it significantly improves the wettability of the brazing filler metal and contributes to improving the bonding strength. It has also been found that the effect is most effective in an inert gas with an Nz content of around 10% by volume.
本発明はこのような知見に基づいてなされたものであっ
て、セラミックス部材の接合面にTi膜を形成させ、対
面する被接合材との間に銀ろう成分の中間材を配置した
後、H2ガス30%以下混合した不活性ガス中で前記銀
ろう成分の中間材の融点以上に加熱して接合することを
特徴とするセラミックスと金属等との接合方法である。The present invention has been made based on such knowledge, and after forming a Ti film on the joint surfaces of ceramic members and placing an intermediate material of a silver solder component between the facing materials to be joined, H2 This is a method for joining ceramics and metals, etc., characterized in that the joining is performed by heating above the melting point of the intermediate material of the silver solder component in an inert gas mixed with 30% or less of the gas.
セラミックスの接合面に形成させるTi膜は、粉末とバ
インダを混合したペーストを印刷しても良いし、用途に
よってはTiターゲットを用いてスパッタする方法も良
いし、またTiを溶融してその蒸気をセラミックスの接
合面に蒸着させるのも有効である。The Ti film formed on the bonding surface of ceramics may be formed by printing a paste containing a mixture of powder and binder, or depending on the application, sputtering using a Ti target may be used, or by melting Ti and releasing its vapor. It is also effective to deposit it on the bonding surface of ceramics.
またその後続いて配置する銀ろうの成分はA g +C
u、Za、Cd、Su、Mn、Mo、W* Fe。The components of the silver solder that will be placed subsequently are A g + C
u, Za, Cd, Su, Mn, Mo, W*Fe.
co及びNiからなる群より選ばれた2種以上の元素か
ら成るものである。これらの組合せでAg。It is composed of two or more elements selected from the group consisting of co and Ni. Ag with these combinations.
Cu、Zn、Cd、Snは従来のTIS銀ろう成分であ
り、その他の元素は必要に応じて、例えば耐熱性を向上
させたいときはMn、Mo、W等の元素を、また熱膨張
緩和材を目的にする場合には銀ろう成分にFe、Ni及
びCo等を添加すればよい。この場合の添加量は銀ろう
の融点を著しく上昇させない範囲の添加が望ましく数%
以下が適量である。即ち主要元素はAg、Cuになるこ
とが多い。Cu, Zn, Cd, and Sn are conventional TIS silver solder components, and other elements are added as needed.For example, when it is desired to improve heat resistance, elements such as Mn, Mo, and W are added, and thermal expansion moderating materials are added. If this is the purpose, Fe, Ni, Co, etc. may be added to the silver solder component. In this case, the amount of addition is preferably several percent that does not significantly increase the melting point of the silver solder.
The following is the appropriate amount. That is, the main elements are often Ag and Cu.
そしてろうのぬれ性を良くする加熱雰囲気は、N2ガス
と混合するのに適するNz、Ar及びHeの1種もしく
はこれらの混合ガスであれJf十分に目的を達成できる
。量産化を考えた場合、価格が重要になるのでその点を
考慮するとHz −N z系が良いことになる。そして
ぬれ性の効果及びN2ガスの安全性を総合して考えると
N2ガスは10%位が最適と言える。The heating atmosphere that improves the wettability of the solder can be any one of Nz, Ar, and He suitable for mixing with N2 gas, or a mixed gas thereof, which can fully achieve the purpose. When mass production is considered, price becomes important, so taking that into consideration, the Hz-Nz system is better. Considering the wettability effect and the safety of N2 gas, it can be said that the optimum amount of N2 gas is about 10%.
またN2量が多くなるに従ってTiとN2の反応が生じ
脆くなる原因となるのでその点からもN2は30%以下
とすべきである。In addition, as the amount of N2 increases, a reaction between Ti and N2 occurs, causing brittleness, so from this point of view as well, N2 should be kept at 30% or less.
以下に本発明の接合方法を具体的な実施例によって説明
する。The joining method of the present invention will be explained below using specific examples.
本発明のぬれ広がり試験(a)、(a’ )、(b)、
(b’ )とセラミックスと金属の接合方法(c)を
第1図に示す。Wetting and spreading test of the present invention (a), (a'), (b),
(b') and the method of joining ceramics and metal (c) are shown in FIG.
実施例1
酸素センサー用Zr0zの板:200X1t 1の片
面にTi粉末:2、テレピネオルに5%エチルセルロー
ズを添加したバインダ:1の割合のものを良く混合して
ペースト状としたTi粉末2を印刷した。印刷されたT
i膜の上に銀ろう(72%Ag−28%Cu)の粉末3
を配置した。このぬれ広がり試験片をN2ガスの中にN
2ガスを容量パーセントで5.7.5,10,20.3
0及び50%と変化させ混合ガス中に挿入し、各々約9
00℃、30秒間加熱したときのぬれ広がり性を調査し
た。実施例2
A QxOs 板: 20’x 1 t (7)片面に
実施例1と同−ペースト状Ti粉末2を印刷した。印刷
されたTi膜の上に銀ろう、72%Ag−28%Cuの
粉末3を配置し、10%Hz−90%N2混合ガス中で
900℃、30秒間加熱した。Example 1 On one side of a Zr0z board for oxygen sensor: 200X1t 1, Ti powder 2 was printed on one side, which was made into a paste by mixing well a mixture of 2 parts Ti powder and 1 part binder made by adding 5% ethyl cellulose to terpineol. did. printed T
Silver solder (72%Ag-28%Cu) powder 3 on the i-film
was placed. This wet spread test piece was placed in N2 gas.
2 gases in volume percent 5.7.5, 10, 20.3
0 and 50% and inserted into the mixed gas, each about 9%
Wetting and spreading properties were investigated when heated at 00°C for 30 seconds. Example 2 A QxOs board: 20' x 1 t (7) The same paste-like Ti powder 2 as in Example 1 was printed on one side. Silver solder and 72%Ag-28%Cu powder 3 were placed on the printed Ti film and heated at 900°C for 30 seconds in a 10%Hz-90%N2 mixed gas.
実施例3
実施例2(7)AQzOa板の代すニS i C板:2
0゜Xltを用い、その他の条件は全〈実施例2と同様
にして加熱した。Example 3 Example 2 (7) Ni S i C board instead of AQzOa board: 2
Heating was performed using 0°Xlt, and all other conditions were the same as in Example 2.
実施例4
酸素センサー用Zr0z板1の接合面に実施例1で作製
したペースト状Ti粉末2を塗布し、その上に銀ろう、
72%Ag−28%Cuの粉末3を配置し、その対面に
被接合材Fe−42%Nil&:φ2,3×3004を
設置し、10%H−90%N2.の混合ガス中で900
℃に加熱した。Example 4 The paste-like Ti powder 2 prepared in Example 1 was applied to the joint surface of the Zr0z plate 1 for oxygen sensor, and silver solder,
A powder 3 of 72%Ag-28%Cu was placed, and a material to be joined Fe-42%Nil&:φ2,3×3004 was placed on the opposite side, and 10%H-90%N2. 900 in a mixed gas of
heated to ℃.
実施例5
実施例4のZrOz板の代りにAl2208板を用い、
その他の条件は全〈実施例4と同様にして加熱接合した
。Example 5 An Al2208 plate was used instead of the ZrOz plate of Example 4,
All other conditions were the same as in Example 4 for heat bonding.
実施例6
実施例4のZrOz板の代りに、Si板を用い、その他
の条件は全〈実施例4と同様にして加熱接合した。Example 6 A Si plate was used instead of the ZrOz plate of Example 4, and heat bonding was carried out in the same manner as in Example 4 except for the other conditions.
比較例1
実施例1で用いたものと同一のZrOx仮1とTi含金
ろう(10%T i −65%Ag−25%Cu)を組
合せて、Arガス中で900℃、30秒間加熱してぬれ
広がり試験した。Comparative Example 1 The same ZrOx temporary 1 used in Example 1 and Ti-containing solder (10% Ti - 65% Ag - 25% Cu) were combined and heated at 900°C for 30 seconds in Ar gas. A wet spread test was conducted.
比較例2
AQxOs板を用い、その他の条件は全く比較例1と同
様にしてぬれ広がり試験した。Comparative Example 2 A wetting and spreading test was conducted using an AQxOs board and using the same conditions as in Comparative Example 1 except for the other conditions.
比較例3
Si体を用い、その他の条件は全く比較例1と同様にし
てぬれ広がり試験した。Comparative Example 3 A wetting and spreading test was conducted using a Si body and using the same conditions as in Comparative Example 1 except for the other conditions.
比較例4
実施例2で用いたものと同一のZr0z板1とFe−4
2%Ni 線4の間にTi 合余ろう(10%Ti−6
5%Ag−25%Cu) を配置してArガス中で9
00℃に加熱接合した。Comparative Example 4 Same Zr0z plate 1 and Fe-4 as used in Example 2
Between 2% Ni and wire 4, Ti is added (10% Ti-6
5%Ag-25%Cu) in Ar gas.
The bonding was carried out by heating at 00°C.
比較例5
比較例4において、A Q x○δ板を用い、その他の
条件は全く比較例4と同様にして加熱接合した・比較例
6
比較例4において、SiC板を用い、その他の条件は全
く比較例4と同様にして加熱接合した。Comparative Example 5 In Comparative Example 4, A Q Heat bonding was carried out in exactly the same manner as in Comparative Example 4.
前記各実施例及び比較例で得られた試絶片をぬれ広がり
性及び引張試験に供した。The specimens obtained in each of the Examples and Comparative Examples were subjected to wet-spreadability and tensile tests.
ぬれ広がり性は加熱前の径をDとし、加熱後の径D′が
何倍(D’ /D)になっているかで表示した(第2図
(a) 、 (b) )。引張試験はFe−42%Ni
1iの断面積で除した引張強さくkg/nw”)で示し
た(第3図)、第2図(b)の図中において、Ax、A
z及びA8は各々本発明方法による実施例1(ZrOz
)、実施例2(AQ2011)及び実施例3(SiC)
の場合を、Bt、 B2.は各々比較例1(ZrOz)
、比較例2(AQZOll)及び実施例3(S i C
)の場合を示す。Wetting and spreading properties were expressed by how many times (D'/D) the diameter D' after heating was, with the diameter before heating being D (Fig. 2 (a), (b)). Tensile test was conducted using Fe-42%Ni
The tensile strength divided by the cross-sectional area of
z and A8 are respectively Example 1 (ZrOz
), Example 2 (AQ2011) and Example 3 (SiC)
In the case of Bt, B2. are respectively Comparative Example 1 (ZrOz)
, Comparative Example 2 (AQZOll) and Example 3 (S i C
) is shown.
第2図(a)から明らかなようにH2添加の効果は7.
5 %から現われ始め、それ以上の添加では大幅なぬれ
広がりは示さない。すなわちHzの添加量は30%以下
、7.5%以上であれば本発明のぬれ性は達成できる。As is clear from Figure 2(a), the effect of H2 addition is 7.
It starts to appear at 5%, and no significant wetting spread occurs when added beyond that amount. That is, the wettability of the present invention can be achieved if the amount of Hz added is 30% or less and 7.5% or more.
第2図(b)からは各種セラミックスのぬれ広がり性が
分る。従来のTi合金ろうは全般的にぬれ広がりが小さ
く、本発明の方法であるTi膜を形成したものは一段と
ぬれ広がりが大きいことが明らかである。From FIG. 2(b), the wettability and spreadability of various ceramics can be seen. It is clear that conventional Ti alloy brazes generally have a small wetting spread, and those in which a Ti film is formed using the method of the present invention have an even larger wetting spread.
第3図から明らかなようにセラミックスと金属の接合部
の引張強さでも1本発明のTi膜を形成させてろう付し
た継手の方が強度が高いことが分る。これらの結果はぬ
れ性と相関があり、ぬれ広がりが大きいもの程、継手の
接合強度も強くなっている。モしてHzとの混合ガスが
有効に作用していることが明らかである。As is clear from FIG. 3, the tensile strength of the joint between ceramic and metal is also higher in the joint in which the Ti film of the present invention is formed and brazed. These results are correlated with wettability, and the larger the wetting spread, the stronger the joint strength of the joint. It is clear that the mixed gas with Hz is effective.
本発明方法を発展させると、セラミックスのメタライズ
としての成用も一分考えられる2例えば第4図に示すよ
うにICやLSIIIなどの高級半値体素子は使用環境
に影響されることなくその性能を維持するためにパッケ
ージに収めて使用される。If the method of the present invention is developed, it is conceivable that it will be used as metallization for ceramics.2For example, as shown in Figure 4, high-grade half-value elements such as IC and LSIII can maintain their performance without being affected by the environment in which they are used. Used in a package for maintenance.
その工程をパッケージングと称し、はとんどがセラミッ
クス12にメタライズ13し、その上にはんだ付、また
はろう付によって行われる。リード14は金属材が用い
られる。高級半導体のパッケージングには完全な気密性
が要求されるために、ぬれ不良、ブロホール、はく離な
どの欠陥のない健全なはんだ付を行われなければならな
い。This process is called packaging, and is mostly performed by metallizing 13 on ceramic 12 and soldering or brazing thereon. The lead 14 is made of a metal material. Since high-grade semiconductor packaging requires perfect airtightness, sound soldering must be performed without defects such as poor wetting, blowholes, or peeling.
また本発明は細かいリードのパタニングも出来るのでこ
のような半導体にも適用できる。Furthermore, the present invention can also be applied to such semiconductors since fine lead patterning can be performed.
第5図はスパッタあるいは蒸着でメタライズ膜を一体形
成させる方法で、セラミックス12の接合面にTiある
いはZr膜15をまず形成させ、続いて銀ろうの合金膜
16を形成させる方法である。またこれらの方法により
作製したセラミック構造体も本発明の範囲に入る。FIG. 5 shows a method of integrally forming a metallized film by sputtering or vapor deposition, in which a Ti or Zr film 15 is first formed on the joint surface of the ceramic 12, and then a silver solder alloy film 16 is formed. Ceramic structures produced by these methods also fall within the scope of the present invention.
以上前記各実施例においては、被接合材としてセラミッ
クス: Zr0z、AMzOa、SiCについて、金属
:Fe−42%Niを用いた場合について述べたが、そ
の他のセラミックス、例えば5i8Na、あるいはこれ
らを用いた複合セラミックス、また金属についてもSU
S鋼やその他の一般的に用いられている金属材も適用で
きる。また中間材のろう材も一般的に使用されているも
のも広く適用でき、本発明の効果が発揮できる。Zrの
膜もTiと同様な効果を発揮する。In each of the above embodiments, ceramics: ZrOz, AMzOa, SiC and metal: Fe-42%Ni were used as the materials to be joined, but other ceramics, such as 5i8Na, or a composite using these SU for ceramics and metals
S steel and other commonly used metal materials can also be used. Furthermore, commonly used brazing filler metals as intermediate materials can be widely used, and the effects of the present invention can be exhibited. A Zr film also exhibits the same effect as Ti.
その他の方法として本発明の方法と熱膨張緩衝材とを組
合せたセラミックスとの接合もより有効な接合方法であ
る。Another more effective bonding method is to bond ceramics by combining the method of the present invention and a thermal expansion buffer.
本発明の方法によれば、ぬれ性の良い信頼性の高い継手
の接合が得られ、なお且つ安価な雰囲気中で加熱するた
め量産性にも適している。According to the method of the present invention, a highly reliable joint with good wettability can be obtained, and since heating is performed in an inexpensive atmosphere, it is suitable for mass production.
第1図(a)、 (a’ )は本発明の一実施例のぬれ
性試験を示す説明図、第1図(b)、(b’ )は銀ろ
うがぬれ広がった様子を示す説明、同第1図(c)は本
発明の接合方法を示す説明図、第2図(a)はH2ガス
の有効添加範囲を説明する線図、第2図(b)は本発明
方法と従来の方法でぬれ広がりを試験したグラフ、第3
図は本発明方法と従来の方法で接合した継手試験片の引
張強さを示すグラフ、第4゜第5図は他の応用例の説明
図である。
】・・・バインダ、2・・・Ti粉末、3・・・銀ろう
粉末。
12・・・セラミックス。FIGS. 1(a) and (a') are explanatory diagrams showing a wettability test of an example of the present invention, FIGS. 1(b) and (b') are explanatory diagrams showing how silver solder spreads and spreads, FIG. 1(c) is an explanatory diagram showing the joining method of the present invention, FIG. 2(a) is a diagram explaining the effective addition range of H2 gas, and FIG. 2(b) is a diagram showing the joining method of the present invention and the conventional method. Graph testing wet spread by method, 3rd
The figure is a graph showing the tensile strength of joint test pieces joined by the method of the present invention and the conventional method, and Figures 4 and 5 are explanatory diagrams of other application examples. ]...Binder, 2...Ti powder, 3...Silver solder powder. 12...Ceramics.
Claims (1)
形成させ、対面する被接合材との間に銀ろう成分の中間
材を配置した後、H_2ガスを容量パーセントで30%
以下混合した不活性ガス中で前記銀ろう成分の中間材の
融点以上に加熱して接合することを特徴とするセラミッ
クスと金属等との接合方法。1. After forming a Ti film or Zr film on the joining surfaces of the ceramic members and placing an intermediate material of silver solder component between the facing materials to be joined, H_2 gas is added to 30% by volume.
A method of joining ceramics and metals, etc., characterized in that the joining is performed by heating above the melting point of the intermediate material of the silver solder component in an inert gas mixed with the following:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21247885A JPS6272472A (en) | 1985-09-27 | 1985-09-27 | Joining method for ceramics and metal or the like |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21247885A JPS6272472A (en) | 1985-09-27 | 1985-09-27 | Joining method for ceramics and metal or the like |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6272472A true JPS6272472A (en) | 1987-04-03 |
Family
ID=16623308
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21247885A Pending JPS6272472A (en) | 1985-09-27 | 1985-09-27 | Joining method for ceramics and metal or the like |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6272472A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6428284A (en) * | 1987-07-21 | 1989-01-30 | Toshiba Corp | Oxide superconducting joint |
JPH01224279A (en) * | 1988-03-01 | 1989-09-07 | Ngk Spark Plug Co Ltd | Bonding of ceramic to metal |
JPH0477369A (en) * | 1990-07-16 | 1992-03-11 | Showa Denko Kk | Production of metal-ceramic laminated substrate |
WO1997040209A1 (en) * | 1996-04-19 | 1997-10-30 | Koenoenen Mauno | A method for coating titanium and titanium alloys with ceramics |
-
1985
- 1985-09-27 JP JP21247885A patent/JPS6272472A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6428284A (en) * | 1987-07-21 | 1989-01-30 | Toshiba Corp | Oxide superconducting joint |
JPH01224279A (en) * | 1988-03-01 | 1989-09-07 | Ngk Spark Plug Co Ltd | Bonding of ceramic to metal |
JPH0477369A (en) * | 1990-07-16 | 1992-03-11 | Showa Denko Kk | Production of metal-ceramic laminated substrate |
WO1997040209A1 (en) * | 1996-04-19 | 1997-10-30 | Koenoenen Mauno | A method for coating titanium and titanium alloys with ceramics |
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