JPS6317267A - Solder material for joining ceramics each other or ceramic and metal - Google Patents
Solder material for joining ceramics each other or ceramic and metalInfo
- Publication number
- JPS6317267A JPS6317267A JP15879686A JP15879686A JPS6317267A JP S6317267 A JPS6317267 A JP S6317267A JP 15879686 A JP15879686 A JP 15879686A JP 15879686 A JP15879686 A JP 15879686A JP S6317267 A JPS6317267 A JP S6317267A
- Authority
- JP
- Japan
- Prior art keywords
- ceramics
- bonding
- metal
- brazing
- brazing filler
- 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
- 229910052751 metal Inorganic materials 0.000 title claims description 140
- 239000002184 metal Substances 0.000 title claims description 137
- 239000000919 ceramic Substances 0.000 title claims description 117
- 239000000463 material Substances 0.000 title claims description 93
- 238000005304 joining Methods 0.000 title claims description 28
- 229910000679 solder Inorganic materials 0.000 title description 3
- 238000005219 brazing Methods 0.000 claims description 120
- 239000002245 particle Substances 0.000 claims description 76
- 239000000945 filler Substances 0.000 claims description 75
- 229910052719 titanium Inorganic materials 0.000 claims description 48
- 239000000843 powder Substances 0.000 claims description 33
- 150000002739 metals Chemical class 0.000 claims description 23
- 230000008018 melting Effects 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 19
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000011888 foil Substances 0.000 claims description 7
- 150000004767 nitrides Chemical class 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 58
- 239000010936 titanium Substances 0.000 description 46
- 238000010438 heat treatment Methods 0.000 description 34
- 238000000034 method Methods 0.000 description 27
- 239000011572 manganese Substances 0.000 description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 15
- 229910052748 manganese Inorganic materials 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052581 Si3N4 Inorganic materials 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- -1 SiO2 and Si3N4 Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 208000018459 dissociative disease Diseases 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 229910017309 Mo—Mn Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、セラミックス同志またはセラミックスと金
属との接合に使用するろう材に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a brazing material used for joining ceramics together or joining ceramics and metals.
一般に、セラミックスは金属に較べて耐摩耗性。 In general, ceramics are more wear resistant than metals.
耐熱性、耐腐食性、絶縁性などにすぐれた特性を有する
材料であるが、機械的な衝撃に脆い、導電性に劣る。加
工性に劣るなどの欠点がある。一方、金属はこのような
セラミックスの欠点とされる面には逆にすぐれているこ
とが多い。Although it is a material with excellent properties such as heat resistance, corrosion resistance, and insulation, it is brittle against mechanical shock and has poor electrical conductivity. It has drawbacks such as poor workability. On the other hand, metals often have advantages over the disadvantages of ceramics.
そこで、セラミックスを金属との接合体として使用した
場合には、それぞれの持つ欠点を相互に補うことが可能
となり、セラミックスと金属との有用性を共に生かして
利用することができ、セラミツクス−金属接合体として
の用途範囲が広いものとなる。Therefore, when ceramics are used as a bonded body with metal, it becomes possible to mutually compensate for the shortcomings of each, and the usefulness of ceramics and metal can be utilized together. It has a wide range of uses as a body.
また、セラミックス同志の接合による場合はセラミック
スの成形方法を簡略化でき、小型に成形できることから
価格が安くなり、セラミックスの用途範囲が極めて広い
ものとなる。In addition, when ceramics are bonded together, the method of molding the ceramics can be simplified, and since the ceramics can be molded into a smaller size, the price is lower, and the range of uses for the ceramics is extremely wide.
さらに、異種セラミックス間の接合による場合、それぞ
れのセラミックスのもつ特性、たとえば電気絶縁性、熱
伝導性、耐摩耗性などの特性を相互に補うことができ、
セラミックスの用途範囲は極めて広いものとなる。Furthermore, when bonding different types of ceramics, the properties of each ceramic, such as electrical insulation, thermal conductivity, and abrasion resistance, can be mutually complemented.
The range of applications for ceramics is extremely wide.
しかるに、このようなセラミックスと金属との接合体は
、通常過酷な条件下で使用されることが多く、特にセラ
ミックスと金属との熱膨張率の差に起因して両者の接合
部では高い熱応力が発生しやすいという問題がある。ま
た、同種セラミックス同志の接合においては、セラミッ
クスの特性を生かす必要があるところから、耐熱性ある
いは気密性のある接合を必要とする課題がある。さらに
、異種セラミックス間の接合においても同様の技術的な
課題がある。However, such joined bodies of ceramics and metals are often used under harsh conditions, and in particular, the joints between ceramics and metals are subject to high thermal stress due to the difference in coefficient of thermal expansion between the two. There is a problem that this is likely to occur. Furthermore, in bonding similar ceramics together, there is a problem in that heat-resistant or airtight bonding is required because it is necessary to take advantage of the characteristics of the ceramics. Furthermore, there are similar technical issues in joining different types of ceramics.
このため、セラミックスと金属、セラミックス同志は強
力に接合されていることが要求されるが、このような接
合を金属ろう材を用いて一回の加熱により行う接合技術
が確立されれば極めて利用価値の高いものとなる。For this reason, it is required that ceramics and metals, as well as ceramics, be strongly bonded to each other, but if a bonding technology that performs such bonding using a metal brazing filler metal and heating once is established, it would be extremely useful. The value will be high.
従来、セラミックスと金属との接合方法として、酸化物
型セラミックスと銅とを酸化性雰囲気中で加熱して両者
を接合させる技術（以下、酸下銅法という）が知られて
いる（特公昭５８−３９９９号公報、特開昭３９−２１
７６８９号公報）。Conventionally, as a method for bonding ceramics and metals, a technique is known in which oxide type ceramics and copper are heated in an oxidizing atmosphere to bond them together (hereinafter referred to as the oxidized copper method) (Japanese Patent Publication No. 58 -3999 Publication, JP-A-39-21
Publication No. 7689).
この方法は一回の加熱により良好な接合強度を得るすぐ
れた方法ではあるが、酸化性雰囲気による加熱によって
銅表面にこの表面性状を著しく阻害する酸化銅被膜が形
成され、かつ高温による加熱のため銅自体が変形し、こ
のため後加工が必要となるなどの雛点がある。Although this method is an excellent method for obtaining good bonding strength with one heating, heating in an oxidizing atmosphere forms a copper oxide film on the copper surface that significantly impairs the surface quality, and because of heating at high temperatures, There are some issues, such as the copper itself deforming and therefore requiring post-processing.
また、焼結セラミックスの金属化法として、マンガンの
融点より低い温度でマンガンと珪素との反応を起こし得
る珪素化合物を含有する焼結セラミックス表面に、マン
ガン含有金属層を形成し、この金属層をマンガンの融点
より低い温度に加熱してマンガンと珪素との結合反応を
行わせる方法であって、上記マンガン含有金属層を上記
結合反応に先立って上記セラミックス表面に緊密に密着
させ、上記珪素化合物とマンガンとをマンガンの融点よ
り低い温度で反応させる方法（以下、マンガン含有金属
による接合法という）が提案されている（特開昭５８−
２０４８８５号公報）。In addition, as a metallization method for sintered ceramics, a manganese-containing metal layer is formed on the surface of sintered ceramics that contains a silicon compound that can cause a reaction between manganese and silicon at a temperature lower than the melting point of manganese. This is a method of heating to a temperature lower than the melting point of manganese to perform a bonding reaction between manganese and silicon, in which the manganese-containing metal layer is brought into close contact with the ceramic surface prior to the bonding reaction, and the metal layer is heated to a temperature lower than the melting point of manganese. A method of reacting manganese with manganese at a temperature lower than the melting point of manganese (hereinafter referred to as a joining method using manganese-containing metals) has been proposed (Japanese Patent Application Laid-Open No. 1983-1999).
204885).
しかし乍ら、この方法はマンガン含有金属層とセラミッ
クスとを加熱中に緊密に密着させる必要があり、また被
接合セラミックスにはマンガン含有金属層と反応を起こ
し得る珪素化合物、即ちＳｉＯ２およびＳｉ３Ｎ４を必
ず含有させておかねばならないため、被接合セラミック
スの種類が限定されるという難点がある。However, this method requires that the manganese-containing metal layer and the ceramic be brought into close contact with each other during heating, and the ceramic to be joined must contain silicon compounds, such as SiO2 and Si3N4, which can react with the manganese-containing metal layer. Since it must be contained, there is a drawback that the types of ceramics to be joined are limited.
また、特に酸化物型のセラミックスの金属化法として、
たとえばＭ ｏ −Ｍ ｎ粉末を主体にＳｉＯ２、Ｃａ
Ｏなどを添加してなるメタライズペーストを塗布し、加
湿還元雰囲気中で焼結して金属化層を形成し、しかるの
ちＮｉメッキを施してろう付けする方法（以下、Ｍ ｏ
−Ｍ ｎ法という）が一般的に行われている。In addition, especially as a metallization method for oxide type ceramics,
For example, SiO2, Ca mainly based on Mo-Mn powder
A method of applying a metallizing paste made by adding O, etc., sintering it in a humidified reducing atmosphere to form a metallized layer, and then applying Ni plating and brazing (hereinafter referred to as M o
-Mn method) is commonly used.
この方法は焼結とろう付けの温度の加熱を必要とし、ま
たその間にＮｉメッキを行わねばならないので、生産性
が悪く、煩雑な工程管理を必要とするなどの難点がある
。This method requires heating to sintering and brazing temperatures, and Ni plating must be performed during that time, resulting in poor productivity and the need for complicated process control.
一方、酸素に対して活性な金属Ｔｉ、Ｚｒ、Ｎｂなどと
セラミックスとの界面における反応を利用して接合する
方法（以下、活性金属法という）が知られている。たと
えばアルミナに対してはＴｉ−２５％ｖ−２５％Ｃｒ合
金を用い、その接合温度を１，５５０〜１，６５０℃と
して真空、 Ａ ｒなどの不活性雰囲気中で行われてい
る。しかし、この方法は接合温度が高く、設備面から制
約を受は生産性の低いものであった。On the other hand, a method of bonding using a reaction at the interface between a metal such as Ti, Zr, or Nb that is active toward oxygen and a ceramic is known (hereinafter referred to as an active metal method). For example, for alumina, Ti-25%v-25%Cr alloy is used, and the bonding temperature is 1,550 to 1,650°C in an inert atmosphere such as vacuum or Ar. However, this method requires a high bonding temperature and is limited by equipment, resulting in low productivity.
さらに、従来、酸化物型セラミックス、窒化物型セラミ
ックス、炭化物型セラミックスにおいてセラミックス同
志を接合する接着剤として、フッ化ナトリウムおよびフ
ッ化カルシウムの少なくとも１種、またはこれとカオリ
ンとの混合物を有効成分とする接着剤が提案されている
（特開昭５８−９５６６８号公報）、。Furthermore, in oxide type ceramics, nitride type ceramics, and carbide type ceramics, at least one of sodium fluoride and calcium fluoride, or a mixture of these and kaolin has been used as an active ingredient as an adhesive for bonding ceramics together. An adhesive has been proposed (Japanese Unexamined Patent Publication No. 58-95668).
しかるに、この接着剤による接合は、接着後の接合強度
は大きいが、接合加熱中に接合面は半溶融状態となり、
接合後のセラミックスの相互寸法精度の維持が難しいと
いう難点がある。However, although the bonding using this adhesive has a high bonding strength after bonding, the bonding surface becomes semi-molten during bonding heating.
There is a drawback in that it is difficult to maintain the mutual dimensional accuracy of the ceramics after joining.
このように、セラミックスと金属あるいはセラミックス
同志の接合方法としては、今日まで種々の方法が提案さ
れているが、それぞれ固有の問題点がある。この問題点
の一部はすでに記述したとおりであるが、この点も含め
てさらに検討整理すれば以下の通りである。As described above, various methods have been proposed to date for joining ceramics and metals or ceramics together, but each method has its own problems. Some of these problems have already been described, but if we consider them further, they will be as follows.
まず、上記従来の酸化銅法では、前述の問題点のほか、
この方法で得られた金属化面を利用して引き続き金属構
造体に接合しようとすると、約８００℃付近の硬ろう付
の場合には、セラミックスと銅層との熱膨張率の差に起
因し、セラミックス側にクラックが生じる。このため強
度の低い約３Ｏｏ℃以下で施工する軟ろう付により金属
構造体に接合せざるを得ない。その結果、最終的な接合
強度は総合して弱いものとなり、また折角のセラミック
スの耐熱性も軟ろう付の耐熱性が低いことにより、その
性能を充分に発揮できないという重大な問題がある。First of all, in addition to the problems mentioned above, the conventional copper oxide method described above has
If you try to use the metallized surface obtained by this method to continue bonding to a metal structure, in the case of hard brazing at around 800°C, the difference in thermal expansion coefficient between the ceramic and the copper layer will cause problems. , cracks occur on the ceramic side. For this reason, it has no choice but to join to the metal structure by soft brazing, which is performed at a temperature of about 30° C. or lower, which has low strength. As a result, the final joint strength is weak overall, and there is a serious problem in that the heat resistance of ceramics and the low heat resistance of soft brazing cannot fully demonstrate their performance.
次に、上記従来のマンガン含有金属による接合法は、加
熱と同時に加圧する必要があるため、それだけ複雑な治
具あるいは装置を必要とするという問題があり、またマ
ンガン含有金属層と反応を起こし得る珪素化合物をセラ
ミックス側に含有させておく必要があるので、セラミッ
クスの特性を劣化させる場合があると同時に、そのセラ
ミックスの種類が限定されるという問題がある。Next, the above-mentioned conventional bonding method using manganese-containing metal requires heating and pressurization at the same time, so there is a problem in that it requires complicated jigs or equipment, and it can also cause reactions with the manganese-containing metal layer. Since it is necessary to contain a silicon compound in the ceramic side, there is a problem that the characteristics of the ceramic may be deteriorated and at the same time, the types of the ceramic are limited.
また、上記従来のＭｏ−Ｍｎ法は焼結−メツキーろう付
という複雑な工程が必要であると同時に。Further, the conventional Mo-Mn method requires complicated steps of sintering and Metsky brazing.
Ｓｉｎ、とＣａＯなどの比較的融点の低い脆弱なガラス
質の中にＭｏ、Ｗなどの粉末が混在した異質層が残ると
いう問題がある。There is a problem in that a heterogeneous layer in which powders such as Mo and W are mixed remains in a brittle glass material with a relatively low melting point such as Sin and CaO.
更に、上記従来の活性金属法は接合に用いるろう材の融
点が高いため、設備面からの制約が大きく、生産性の低
いものであると同時に接合温度が高いことにより、セラ
ミックスと金属化面の熱膨張差が大きく影響し、総合的
な接合強度は低いものとならざるをえなかった。Furthermore, the conventional active metal method described above has a high melting point of the brazing filler metal used for bonding, which imposes large restrictions on equipment, resulting in low productivity and high bonding temperatures, making it difficult to bond ceramics and metallized surfaces. Due to the large difference in thermal expansion, the overall bonding strength had to be low.
一方、上記従来のフッ化ナトリウムおよびフッ化カルシ
ウムの少なくとも１種またはこれとカリオンとの混合物
を用いるセラミックス用接着剤は、被接着セラミックス
へはげしく拡散し、半溶融ガラス層がセラミックス接合
境面に生じ、セラミックス相互の寸法精度の維持が殖し
くなると同時に接合面全体にわたり均一な境界層を得る
ことが固壁であるという問題がある。On the other hand, the conventional adhesive for ceramics using at least one of sodium fluoride and calcium fluoride, or a mixture of these and carrion, diffuses vigorously into the ceramics to be bonded, and a semi-molten glass layer forms at the ceramic bonding interface. However, there is a problem in that it becomes difficult to maintain the dimensional accuracy between the ceramics, and at the same time, it is difficult to obtain a uniform boundary layer over the entire joint surface using a solid wall.
したがって、この発明は、上記従来の諸方法の問題点を
すべて解決して、加熱接合時の温度制御が容易で、−回
の加熱により安定して大きな接合強度を得ることができ
、被接合体相互の寸法精度維持も容易に実現できるセラ
ミックス同志またはセラミックスと金属とを接合するた
めの工業的に有用なろう材を提供することを目的として
いる。Therefore, the present invention solves all of the problems of the conventional methods described above, makes it easy to control the temperature during heating bonding, stably obtains high bonding strength with - times of heating, and The object of the present invention is to provide an industrially useful brazing material for joining ceramics together or ceramics and metals, which can easily maintain mutual dimensional accuracy.
上記目的を達成するため、鋭意研究した結果、−例とし
て、ろう材母材中にチタニウムの粉末粒子をそれにより
低融点の母材中に固形状態で分散させて粉末粒子、箔状
乃至は線状に形成したろう材を、セラミックスと金属と
の接合部に当てがい、これを不活性雰囲気中、例えば真
空中で上記ろう材母材の融点より高く且つチタニウム粉
末粒子が固形状態を保つ温度に加熱すると、チタニウム
の一部がろう材母材を構成する金属又は合金中へ拡散し
上記従来の問題を悉く解消でき、且つ、接合強度の大き
なセラミックスと金属との接合体が得られることを知得
した。In order to achieve the above objective, as a result of intensive research, we have found that - for example, titanium powder particles are dispersed in a solid state in a low melting point matrix into powder particles, foils or wires. The shaped brazing filler metal is applied to the joint between ceramic and metal, and heated in an inert atmosphere, for example in vacuum, to a temperature higher than the melting point of the brazing filler metal base material and at which the titanium powder particles remain in a solid state. It was discovered that when heated, part of the titanium diffuses into the metal or alloy constituting the brazing filler metal base material, which eliminates all of the above conventional problems and provides a ceramic-metal bonded body with high bonding strength. I got it.
一般に、チタニウムはその溶融状態でセラミックスに対
して良好なぬれ性を示し、かつセラミックス中へ拡散す
る性質を有していることから、この特性を利用した金属
ろう材が種々開発されてきたが、チタニウムを多量に含
むろう材はろう付後脆く延性も低い。In general, titanium exhibits good wettability to ceramics in its molten state and has the property of diffusing into ceramics, so various metal brazing materials have been developed that take advantage of this property. Brazing filler metals containing a large amount of titanium are brittle and have low ductility after brazing.
一方、チタニウムを少量含有する銀ろう材、銅ろう材、
ニッケルろう材も考えられ、これらは比較的低融点で延
性のある特性を付与することができるが、セラミックス
へのぬれ性が悪く、充分な接合特性が得られない。On the other hand, silver brazing filler metal, copper brazing filler metal containing a small amount of titanium,
Nickel brazing fillers are also considered, and although they have a relatively low melting point and can impart ductile properties, they have poor wettability to ceramics and do not provide sufficient bonding properties.
これに対し、本発明ではセラミックス及び又は金属に対
しぬれ性を示すチタニウムのような粉末粒子を分散して
含むことができ、且つ、この粉末粒子より低融点の金属
又は合金をろう材母材とし、ろう材を粉末粒子、線状又
は箔状に形成して接合用ろう材としたので、被接合物の
接合部にこのろう材を当てがい、ろう材母材は溶融する
が及チタニウムのような粉末粒子は固形状態を保つ温度
に加熱することにより、ろう材母材とチタニウム等の粉
末粒子が一部合金化して接合用ろう材として有効に作用
する。In contrast, in the present invention, powder particles such as titanium that exhibit wettability to ceramics and/or metals can be dispersed and included, and a metal or alloy having a lower melting point than the powder particles is used as the brazing material base material. Since the brazing filler metal is formed into powder particles, wires, or foils to be used as a bonding filler metal, this brazing filler metal is applied to the joint part of the objects to be bonded, and the base material of the filler metal melts, but it is By heating the powder particles to a temperature at which they remain in a solid state, the brazing filler metal base material and the powder particles of titanium or the like become partially alloyed and effectively act as a bonding brazing filler metal.
本発明による上記ろう材は、その接合時の加熱初期にお
いて、溶融した低融点の金属ろう材母材が被接合物であ
るセラミックスあるいは金属と固形状態を保つチタニウ
ム粉末粒子との間を液密に充填し、かっこのチタニウム
粉末粒子に対してぬれ性良好に接触する。ここで、チタ
ニウム粉末粒子とろう材母材とは互いに合金化しうる性
質を有しているため、引き続き加えられる加熱温度によ
りチタニウム粉末粒子が部分的にろう材母材の中へ溶解
拡散する現象がおこり、この拡散によってろう材母材自
体がセラミックスに対し充分なぬれ性を発揮するように
なる。In the brazing filler metal according to the present invention, in the initial stage of heating during bonding, the molten low-melting-point metal brazing filler metal forms a liquid-tight gap between the ceramic or metal to be bonded and the titanium powder particles that remain in a solid state. It is filled and comes into contact with the titanium powder particles in the brackets with good wettability. Here, since the titanium powder particles and the brazing metal base material have the property of being able to alloy with each other, there is a phenomenon in which the titanium powder particles partially dissolve and diffuse into the brazing metal matrix due to the subsequently applied heating temperature. As a result of this diffusion, the brazing filler metal base material itself exhibits sufficient wettability to ceramics.
そして、上記の拡散したチタニウム粉末粒子は、これが
さらにセラミックス中に拡散していくことにより、セラ
ミックスの接合強度の増大に大きく寄与する。一方、上
記セラミックスへの拡散によりろう材母材中のチタニウ
ム粉末粒子量は減少するが、これはろう材母材の中にぬ
れ性良好に接触する固体状態のチタニウム粉末粒子から
逐次的に補給されるため、溶融状態のろう材母材中のチ
タニウム含有量は一定量に保たれ、この量は加熱温度と
加熱時間を制御することによって必要最小限に設定でき
る。The diffused titanium powder particles further diffuse into the ceramic, thereby greatly contributing to increasing the bonding strength of the ceramic. On the other hand, the amount of titanium powder particles in the brazing material base material decreases due to the diffusion into the ceramic, but this is successively replenished from solid titanium powder particles that come into contact with the brazing material material with good wettability. Therefore, the titanium content in the molten brazing filler metal base material is kept constant, and this amount can be set to the minimum necessary by controlling the heating temperature and heating time.
このため、加熱処理後のろう材母材中にチタニウムが過
剰に存在するという弊害もなく、ろう材母材自体は延性
を保ち、またチタニウム自体比較的熱膨張率が低いうえ
に加熱温度も低いため、残留応力からくる接合特性の低
下への影響は少ない。For this reason, there is no negative effect of excessive titanium existing in the brazing material after heat treatment, the brazing material itself remains ductile, titanium itself has a relatively low coefficient of thermal expansion, and the heating temperature is low. Therefore, there is little influence on deterioration of bonding properties due to residual stress.
さらに、固体状態のチタニウム粉末粒子は加熱処理中ろ
う材母材中へ溶解拡散していくことによって減少するた
め、その初期の量と加熱処理の温度。Furthermore, since the solid titanium powder particles are reduced by dissolving and diffusing into the brazing filler metal matrix during heat treatment, the initial amount and the heat treatment temperature will be affected.
時間を適当に定めることによって、加熱処理後にこれが
ろう材母材中に残存しない状態とすることも可能である
。しかし、これが残存していてもセラミックスの接合特
性には特に悪影響をおよぼさないものであり、この残存
をあえてさける必要はない。By setting the time appropriately, it is also possible to ensure that the brazing material does not remain in the brazing material base material after the heat treatment. However, even if this remains, it does not particularly adversely affect the bonding properties of ceramics, and there is no need to intentionally avoid this remaining.
また、上記の接合用ろう材の加熱接合は不活性雰囲気あ
るいは、真空中で行われることにより、加熱初期におけ
るろう材母材中のチタニウム粉末粒子に対するぬれ性を
良好にでき、またろう材母材中へのチタニウム粉末粒子
の溶解拡散によるろう材母材自体のセラミックスへのぬ
れ性を一層良好とすることができる。In addition, by performing the heating bonding of the above-mentioned brazing filler metal in an inert atmosphere or vacuum, it is possible to improve the wettability of the titanium powder particles in the brazing filler metal base material at the initial stage of heating, and The wettability of the brazing material base material itself to the ceramic can be further improved by dissolving and diffusing the titanium powder particles therein.
このように、この発明の上記接合用ろう材は、チタニウ
ムのような粉末粒子の有するセラミックスへの良好なぬ
れ性と拡散性を充分に利用できるうえに、接合時の加熱
温度を低く設定できるから、セラミックスと金属などと
の接合強度を大幅に向上できるとともに接合作業性の改
善をも図りうる。As described above, the above-mentioned brazing filler metal for bonding of the present invention can fully utilize the good wettability and diffusivity to ceramics that powder particles such as titanium have, and can also set the heating temperature at a low temperature during bonding. , it is possible to significantly improve the bonding strength between ceramics and metals, and also to improve bonding workability.
この発明は以上の知見をもとになされたもであり、その
要旨とすることろは、Ｔｉ含有粒子と合金を形成しかつ
該粒子より低融点の金属又は合金をろう材母材とし、該
母材と前記粒子とを用いて当該ろう材母材中に少なくと
もＴｉ粒子を含有させて粉末粒子、箔又は線状に形成し
たろう材をセラミックスと金属又はセラミックス同志の
接合用ろう材とする点にある。This invention was made based on the above knowledge, and its gist is that a metal or alloy that forms an alloy with Ti-containing particles and has a lower melting point than the particles is used as a brazing material base material, A brazing filler metal formed into powder particles, foil, or wire by using a base material and the particles and containing at least Ti particles in the brazing filler metal base material is used as a brazing filler metal for bonding ceramics and metals or ceramics together. It is in.
この発明の接合用ろう材は、セラミックスと金属、同種
セラミックス同志および異種セラミックス間の接合に用
いるろう材が包含される。上記のセラミックスには、酸
化物型セラミックス、窒化物型セラミックス炭化物型セ
ラミックスなどの従来公知のセラミックスがいずれも含
まれ、また、これと接合させる金属としてはろう材母材
の融点より高い金属であれば特に制限はなく、たとえば
Ｔｉ、Ｃｕ、Ｆｅ、Ｎｉなどの金属ないし合金あるいは
これら金属と他種金属との合金などが挙げられる。The brazing filler metal for bonding of the present invention includes brazing filler metals used for bonding ceramics and metals, ceramics of the same type, and ceramics of different types. The above-mentioned ceramics include all conventionally known ceramics such as oxide-type ceramics, nitride-type ceramics, and carbide-type ceramics, and the metal to be bonded to them may be any metal whose melting point is higher than that of the brazing material. There are no particular limitations, and examples include metals or alloys such as Ti, Cu, Fe, and Ni, and alloys of these metals and other metals.
同種セラミックス同志の接合としては、たとえば酸化型
セラミックス同志の接合、窒化物型セラミックス同志の
接合、炭化物型セラミックス同志の接合などがあり、ま
た異種セラミックス間の接合には、たとえば酸化物型セ
ラミックスと窒化物型セラミックスとの接合、酸化物セ
ラミックスと炭化物型セラミックスとの接合などがある
。Bonding of similar ceramics includes, for example, bonding of oxide type ceramics, bonding of nitride type ceramics, bonding of carbide type ceramics, and bonding of different types of ceramics, such as bonding of oxide type ceramics and nitride type ceramics. Examples include bonding with solid-type ceramics, and bonding between oxide ceramics and carbide-type ceramics.
この発明において接合用ろう材の製造に用いるろう材母
材は、チタニウム含有粒子と合金化が可能でかつこのチ
タニウム含有粒子より低融点のものであればよく、この
ものは一般に不活性ガス中あるいは真空中での加熱にお
いてチタニウム含有粒子と良好なぬれ性を示す、具体的
には、Ａ ｇ ｒＣｕ、ＮｉまたはＡｇとＣｕの合金、
ＡｕとＣｕの合金、ＮｊとＣｒ、 Ｂの合金などのろう
材母材から適宜選択できる。The brazing material base material used in the production of the joining brazing material in this invention may be one that can be alloyed with the titanium-containing particles and has a lower melting point than the titanium-containing particles, and is generally prepared in an inert gas or Specifically, Ag rCu, Ni or an alloy of Ag and Cu, which exhibits good wettability with titanium-containing particles when heated in vacuum;
The brazing material base material can be appropriately selected from alloys of Au and Cu, alloys of Nj, Cr, and B.
而して、これらの合金においては、ろう材母材の組成と
して、たとえば、Ａｇ７２％−Ｃｕ ２８％、Ａｕ３８
％−Ｃｕ６２％、Ｎｉ８１％−Ｃｒ１５．３％−８３，
７％の組成が考えられる。In these alloys, the composition of the brazing material base material is, for example, Ag72%-Cu28%, Au38
%-Cu62%, Ni81%-Cr15.3%-83,
A composition of 7% is possible.
なお、ろう材母材中の成分におけるチタニウム含有粒子
としては、チタニウム粉末粒子に加えてカルシウムおよ
びモリブデン粉末粒子を含ませたもの、あるいは、アル
ミニウムおよびモリブデン粉末粒子を含ませたものを用
いて接合用ろう材を形成すると、これらが接合時ろう材
として加熱されるときセラミックス表面の解離反応を促
進する機能を有しているので、セラミックス界面から極
く微量解離した諸々の元素（たとえばＡｌ、Ｏ。In addition, as the titanium-containing particles in the components of the brazing metal base material, those containing calcium and molybdenum powder particles in addition to titanium powder particles, or those containing aluminum and molybdenum powder particles are used for bonding. When a brazing filler metal is formed, it has the function of promoting a dissociation reaction on the ceramic surface when heated as a brazing filler metal during bonding, so various elements (for example, Al, O, etc.) dissociated in very small amounts from the ceramic interface.
Ｓｉ、Ｎ）との相互溶解あるいは結合力が強いことによ
って接合特性に好結果を与える。したがって、このよう
なろう材組成の配合は、この発明において、特に好まし
いものである。Mutual dissolution or strong bonding force with Si, N) gives good results in bonding properties. Therefore, such a brazing filler metal composition is particularly preferred in the present invention.
また、ろう材母材中の成分におけるチタニウムを含む粉
末粒子としては、チタニウム粉末粒子に加えてカルシウ
ムおよびモリブデン粉末粒子を含ませたもの、あるいは
アルミニウムおよびモリブデン粉末粒子を含ませたもの
を用いて接合用ろう材を形成する場合、カルシウムおよ
びアルミニウムの含有量と同量かあるいはそれ以上のモ
リブデンを含有さすことにより、前述のセラミックス表
面の解離反応をより効果的に促進することができると同
時に、モリブデンの熱膨張係数が小さいところから接合
界面の残留応力を低減し、接合特性をより向上させるこ
とができる。In addition, as the titanium-containing powder particles in the brazing metal base material, powder particles containing calcium and molybdenum powder particles in addition to titanium powder particles, or particles containing aluminum and molybdenum powder particles are used for bonding. When forming a brazing filler metal, by containing molybdenum in an amount equal to or greater than the calcium and aluminum content, it is possible to more effectively promote the above-mentioned dissociation reaction on the ceramic surface, and at the same time, the amount of molybdenum Since the coefficient of thermal expansion is small, the residual stress at the bonding interface can be reduced and the bonding characteristics can be further improved.
更に、ろう材母材中の成分におけるチタニウム含有粒子
として、チタニウム、カルシウム、モリブデン粉末粒子
を含んで組合せ配合したもの、あるいはチタニウム、ア
ルミニウム、モリブデン粉末粒子を含んで組合せ配合し
たものに加えて、ニッケル、コバルト、鉄の中から選ば
れた少なくとも一種または二種以上の粉末粒子を配合し
たものを用いることによって、炭化物型セラミックス界
面から極く微量解離した諸々の元素と（たとえばＳｉ、
Ｃ）との相互溶解あるいは結合力を強化でき、従って、
炭化物型セラミックスの接合特性に特に好ましい結果を
与える。Furthermore, as titanium-containing particles in the components of the brazing material base material, in addition to those containing titanium, calcium, and molybdenum powder particles, or those containing titanium, aluminum, and molybdenum powder particles, nickel By using a blend of at least one or two or more kinds of powder particles selected from among , cobalt, and iron, various elements dissociated in extremely small amounts from the carbide-type ceramic interface (for example, Si,
It is possible to strengthen the mutual dissolution or bonding force with C), and therefore,
It gives particularly favorable results to the bonding properties of carbide type ceramics.
加えて、前記の各ろう材母材において含有させる粉末粒
子は上記の各組合せ配合のものに、更にチタニウムもし
くはジルコニウムの窒化物、炭化物またはほう物の中か
ら選ばれた少なくとも一種または二種以上の粉末粒子を
加えたものをろう材母材中に含有させて接合用ろう材を
形成することによって、この接合用ろう材のセラミック
スへのぬれ性を一層向上させることができ、また、接合
用ろう材に凝固後の延性と同時に高強度を発揮させるこ
とができる。さらにこれらの化合物はいずれも高融点で
あるところから接合用ろう材の加熱溶融時において形状
保持機能を発揮させることができる。In addition, the powder particles to be contained in each of the above-mentioned brazing filler metal base materials are those of the above-mentioned combinations, and at least one or two or more selected from the group consisting of titanium or zirconium nitrides, carbides, and borons. By incorporating powder particles into the brazing filler metal base material to form a bonding brazing filler metal, the wettability of this bonding brazing filler metal to ceramics can be further improved. It is possible to make the material exhibit both ductility and high strength after solidification. Furthermore, since all of these compounds have high melting points, they can exhibit a shape-retaining function when the joining brazing filler metal is heated and melted.
これらの化合物の物理特性とその主要特性は、次の第１
表に示されるとおりである。この表から判るように、こ
れらの化合物はいずれもその熱膨張率が小さく、そのう
ちの一種あるいは二種以上を選定組み合わせることによ
り、接合用ろう材の熱膨張率を接合しようとするセラミ
ックスの熱膨張率へ近づけることができるから、熱応力
の緩和にも有効である。The physical properties of these compounds and their main properties are as follows:
As shown in the table. As can be seen from this table, all of these compounds have a small coefficient of thermal expansion, and by selecting one or more of them in combination, the coefficient of thermal expansion of the brazing filler metal for joining can be adjusted to the thermal expansion of the ceramics to be joined. It is also effective in alleviating thermal stress because it can approach the same temperature as the thermal stress.
この発明においてろう材母材中に含有させる粉末粒子の
形状２粒子の大きさは任意であって、接合用ろう材を形
成するろう材母材中にほぼ均一に “分散しうるも
のであればよく１通常０．５μｍから ′５０μｍ
である。In this invention, the shape and size of the powder particles contained in the brazing filler metal base material are arbitrary, as long as they can be dispersed almost uniformly into the brazing filler metal base material forming the joining brazing filler metal. Well1 Usually 0.5μm to '50μm
It is.
また、これらの接合用ろう材の中へ分散包含される金属
粉末粒子は最終的に接合用ろう材を形成するろう材母材
に相互溶解する金属元素とあらかじめ合金化された粒子
であってもよい。In addition, even if the metal powder particles dispersed and included in these brazing filler metals are particles that have been alloyed in advance with metal elements that will be mutually dissolved in the brazing filler metal base material that ultimately forms the brazing filler metal, good.
更に、接合用ろう材を形成するろう材母材中に含有され
る各々の金属粉末粒子の含有量は、各金属元素とも、接
合のための加熱処理の際の温度によりこの接合用ろう材
中への溶解拡散量が決まるものであって、その全量が接
合用ろう材となるろう材母材中へ溶解拡散してもよく、
また、一部残存してもよいところから、その含有量は任
意である。また、チタニウムおよびジルコニウムの窒化
物、炭化物およびほう化物の含有量は接合用ろう材の凝
固後の機械的性質あるいは熱膨張係数から決めればよい
ので、その含有量は適宜選定すればしく任意である。Furthermore, the content of each metal powder particle contained in the brazing filler metal base material that forms the brazing filler metal for bonding varies depending on the temperature during the heat treatment for bonding. The amount of dissolution and diffusion into the solder metal is determined, and the entire amount may be dissolved and diffused into the base material of the brazing filler metal, which becomes the brazing filler metal for joining.
Moreover, the content is arbitrary, as some of it may remain. In addition, the content of titanium and zirconium nitrides, carbides, and borides can be determined from the mechanical properties or thermal expansion coefficient after solidification of the joining brazing filler metal, so the content can be selected as appropriate. .
これらの要因を配慮して接合用ろう材を形成す５ろう材
母材中に含有される各々の粉末粒子の好ましい含有量を
第２表に示した。Taking these factors into consideration, Table 2 shows the preferred content of each powder particle contained in the five brazing filler metal base materials that form the bonding brazing filler metal.
このようにしてろう材母材により粉末粒子、箔状又は線
状に形成された本発明の接合用ろう材は、接合部間に当
てがって介在させ不活性雰囲気あるいは真空中での加熱
処理に供される。この際の加熱温度は接合用ろう材を形
成しているろう材母材の融点以上の温度でかつチタニウ
ムを含む粉末粒子が固形状態を保つ温度、一般的には使
用したろう材母材の融点、つまり液相点温度より５０℃
ないし１５０℃高い温度に保持すればよい。The brazing filler metal of the present invention, which is formed into powder particles, foil shapes, or wires from the brazing filler metal base material in this way, is applied between joints and heat-treated in an inert atmosphere or vacuum. served. The heating temperature at this time is above the melting point of the brazing material that forms the joining brazing material and at which the powder particles containing titanium remain in a solid state, generally the melting point of the brazing material used. , that is, 50℃ below the liquidus temperature
It is sufficient to maintain the temperature at a temperature between 150°C and 150°C higher.
保持時間は、溶融した接合用ろう材中へ溶解拡散させる
べきチタニウムおよび他の金属元素の量、つまり各接合
態様に応じて決められる上記チタニウムおよび他の金属
元素の量に応じて選択でき、通常は２〜３０分間で充分
である。尚、この溶解量は温度と時間の関数で定まるも
のである。The holding time can be selected depending on the amount of titanium and other metal elements to be dissolved and diffused into the molten brazing filler metal, that is, the amount of titanium and other metal elements determined according to each joining mode. 2 to 30 minutes is sufficient. Note that this amount of dissolution is determined by a function of temperature and time.
このような温度２時間は通常の金属同志のろう付作業条
件と大差ないので、本発明るう材を使用した接合は生産
性の向上に大きく寄与する。Since two hours at such a temperature is not much different from ordinary brazing work conditions for metals together, joining using the solder material of the present invention greatly contributes to improving productivity.
上記の加熱処理における真空度は、例えば含有される粒
子がチタニウムのときチタニウムの酸化を防止しかつ接
合用ろう材のぬれ性をよくするため、低露点の不活性ガ
ス雰囲気あるいは１×１１０−３ｍ１Ｈ以上の高真空度
とするのが好ましく、さらに好ましくはｌＸ１０″″４
ＩＨｇ以上とするのがよい。For example, when the particles contained in the heat treatment are titanium, the degree of vacuum is set to a low dew point inert gas atmosphere or 1 x 110 m It is preferable that the degree of vacuum is higher than 1×10″″4, more preferably 1×10″″4
It is better to set it to IHg or higher.
この加熱処理により、加熱初期において接合用ろう材の
うちまずろう材母材が溶融してチタニウム表面にぬれ性
良好になじみ、ついでこの溶融ろう材母材中へチタニウ
ムが徐々に溶解拡散することにより、ろう材母材自体が
セラミックスによくぬれ、ろう材母材中へ拡散したチタ
ニウムはさらにセラミックス中へ拡散していく。この拡
散によって消費されたチタニウムは溶融ろう材母材に接
触しているチタニウムよりさらに平衡量に達するまで適
宜補充される。Through this heat treatment, the base material of the joining brazing material first melts and becomes well-wettable to the titanium surface in the initial stage of heating, and then the titanium gradually dissolves and diffuses into the molten brazing material. , the brazing filler metal base material itself wets the ceramic well, and the titanium that has diffused into the brazing filler metal base material further diffuses into the ceramic. The titanium consumed by this diffusion is replenished from the titanium in contact with the molten brazing filler metal matrix as appropriate until an equilibrium amount is reached.
尚、上記の平衡量は加熱温度などの設定によって必要最
小限に調整できるから、加熱処理後の接合用ろう材は良
好な延性を保ち、これと上記溶融ろ−う材母材のセラミ
ックスへの良好なぬれ性およびチタニウムのセラミック
スへの拡散作用とにより、接合特性の良好な、つまりセ
ラミックスと金属などとの強度の非常に大きい接合が実
現できる。Note that the above equilibrium amount can be adjusted to the necessary minimum by setting the heating temperature, etc., so the joining brazing filler metal after heat treatment maintains good ductility, and this and the above-mentioned molten brazing filler metal base material to ceramics. Due to the good wettability and the diffusion effect of titanium into the ceramic, it is possible to realize a bond with good bonding properties, that is, a very strong bond between a ceramic and a metal.
つぎに、この発明者は、上記の接合用ろう材の製造にお
いて、予め前記ろう材母材およびチタニウム等とともに
、チタニウムもしくはジルコニウムの窒化物、炭化物ま
たはほう化物の中から選ばれた少なくとも一種または二
種以上を介在させ粉末粒子、箔状又は線状のろう材に形
成することにより、接合用ろう材のセラミックスへのぬ
れ性を一層向上させることができ、また接合用ろう材を
その凝固後の延性と同時に高強度とすることができ、さ
らにこれらの化合物はいずれも高融点であるところから
、ろう材母材の加熱溶融時において形状保持機能を発揮
させることができることを知得した。Next, in the production of the above-mentioned joining brazing material, the present inventor previously added at least one or two selected from nitrides, carbides, or borides of titanium or zirconium together with the brazing material base material and titanium. By forming the brazing filler metal in the form of powder particles, foil or wire with the presence of a seed or more, the wettability of the brazing filler metal to ceramics can be further improved, and the brazing filler metal can be used for bonding after solidification. It has been found that these compounds can provide high strength as well as ductility, and since all of these compounds have high melting points, they can exhibit a shape-retaining function when the brazing material base material is heated and melted.
これらの化合物は一般に０．５μ１１１〜５０μｍの粉
末状として用いられ、その使用量としてはＴｉを含む粉
末粒子ならびにろう材母材１００重量部に対して０．１
〜２０重量部、さらに好ましくは０．５〜１ｏ重量部程
度するのがよい。These compounds are generally used in the form of powder of 0.5 μm to 50 μm, and the amount used is 0.1 part by weight per 100 parts by weight of Ti-containing powder particles and brazing material base material.
The amount is preferably about 20 parts by weight, more preferably about 0.5 to 10 parts by weight.
尚、本発明るう材を使用する接合体金属がチタニウムあ
るいはその合金である場合には、第２表に示す各々の接
合用ろう材に包含されるチタニウム粉末粒子は必要はな
い。これはろう材母材の加熱溶融時にチタニウムあるい
はその合金の界面からチタニウム元素が接合時の加熱温
度と時間に応じた量だけろう材中の溶融液中へ溶出する
からである。したがって、このような接合態様に使用す
る接合用ろう材には、接合用ろう材中にチタニウム粉末
粒子を除いた残りの金属元素および化合物の粉末粒子を
含有させるたけて足りることとなる。Incidentally, when the joining body metal using the filler material of the present invention is titanium or its alloy, the titanium powder particles included in each of the joining brazing materials shown in Table 2 are not necessary. This is because when the brazing material base material is heated and melted, the titanium element is eluted from the interface of titanium or its alloy into the molten liquid in the brazing material in an amount that depends on the heating temperature and time during bonding. Therefore, it is sufficient for the joining brazing material used in such a joining mode to contain the remaining metal element and compound powder particles except for the titanium powder particles.
実施例１
第３表に示す各種セラミックス同志ならびにセラミック
スと金属との接合体との組合わせにおいて、各接合部に
、銅コーテイングチタニウム及び銅コーテングモリブデ
ン粉末粒子、銅マンガン母合金及びカルシウム母合金粉
末粒子、銀及びアルミニウム粉末粒子からなるチタニウ
ム粉末粒子を含むろう材母材を、第３表に示す配合成分
になるようにスクリーンオイルで混合して介在させた。Example 1 In the combinations of various ceramics and ceramic-metal bonded bodies shown in Table 3, copper-coated titanium, copper-coated molybdenum powder particles, copper-manganese mother alloy and calcium mother alloy powder particles were added to each joint. A brazing filler metal base material containing titanium powder particles consisting of silver and aluminum powder particles was mixed with screen oil so as to have the composition shown in Table 3.
上記の組合わせ体を充分乾燥させた後、１×１０−’ａ
ｎＨｇの真空度において８９０℃で１０分間加熱処理を
行ったのち、炉内で冷却し取り出して接合体を得た。After thoroughly drying the above combination, 1×10-'a
After performing a heat treatment at 890° C. for 10 minutes in a vacuum of nHg, it was cooled in a furnace and taken out to obtain a bonded body.
各接合体の接合特性は下記の第３表に示される通りであ
った。The bonding characteristics of each bonded body were as shown in Table 3 below.
第３表
注１）Ａ：９５％アルミナセラミックス板と９５％アル
ミナセラミックス円柱との組み合わせ接合体Ｂ：窒化珪
素セラミックス板と窒化珪素セラミックス円柱との組み
合わせ接合体
Ｃ：窒化珪素セラミックス板とタングステンカーバイド
超硬合金直方体との組み合わせ接合体性２）ろう材部か
らの破断はなくいずれもセラミックスの破損による破断
実施例２
第４表に示す各種セラミックス同志ならびにセラミック
スと金属との接合体との組み合わせにおいて実施例１と
同様の手順で各接合体を得た。Table 3 Note 1) A: Combination joined body of 95% alumina ceramic plate and 95% alumina ceramic cylinder B: Combination joined body of silicon nitride ceramic plate and silicon nitride ceramic cylinder C: Silicon nitride ceramic plate and tungsten carbide super Bondability in combination with a hard metal rectangular parallelepiped 2) There was no breakage from the brazing filler metal part, and all fractures were due to ceramic damage.Example 2: Conducted in combination with various ceramics and ceramic-metal bonded bodies shown in Table 4. Each zygote was obtained in the same manner as in Example 1.
このチタニウムを含むろう材の配合成分はカルシウムな
らびにアルミニウムの成分量に対し、それぞれの成分量
より多くモリブデン量を配合しである。The components of this titanium-containing brazing material are such that the amount of molybdenum is greater than the amount of calcium and aluminum.
各接合体の接合特性は下記の第４表に示される通りであ
った。The bonding characteristics of each bonded body were as shown in Table 4 below.
第４表
注１）Ａ：９５％アルミナセラミックス板と９５％アル
ミナセラミックス円柱との組み合わせ接合体Ｂ：窒化珪
素セラミックス板と窒化珪素セラミックス円柱との組み
合わせ接合体
Ｃ：窒化珪素セラミックス板とタングステンカーバイド
超硬合金直方体との組み合わせ接合体性２） ろう材部
からの破断はなくいずれもセラミックスの破損による破
断
実施例３
第５表に示す各種セラミックス同志ならびにセラミック
スと金属との接合体との組み合わせにおいて実施例１と
同様の手順で各接合体を得た。Table 4 Note 1) A: Combination joined body of 95% alumina ceramic plate and 95% alumina ceramic cylinder B: Combination joined body of silicon nitride ceramic plate and silicon nitride ceramic cylinder C: Silicon nitride ceramic plate and tungsten carbide super Bondability in combination with a hard metal rectangular parallelepiped 2) There was no fracture from the brazing filler metal part, and all fractures were due to ceramic failure Example 3 Conducted in combination with various ceramics and ceramic-metal bonded bodies shown in Table 5 Each zygote was obtained in the same manner as in Example 1.
各接合体の接合特性は下記の第５表に示される通りであ
った。The bonding characteristics of each bonded body were as shown in Table 5 below.
第５表
注１）Ａ：９５％アルミナセラミックス板と９５％アル
ミナセラミックス円柱との組み合わせ接合体Ｃ：窒化珪
素セラミックス板とタングステンカーバイド超硬合金直
方体との組み合わせ接合体Ｄ＝９５％アルミナセラミッ
クス板ど純銅円柱との組み合わせ接合体
注２）ろう材部からの破断はなくいずれもセラミックス
の破損による破断
注３）ろう材母材１００部としての重量部を示す。Table 5 Note 1) A: Combination joint of 95% alumina ceramic plate and 95% alumina ceramic cylinder C: Combination joint of silicon nitride ceramic plate and tungsten carbide cemented carbide rectangular parallelepiped D = 95% alumina ceramic plate Combined joined body with pure copper cylinder Note 2) There was no breakage from the brazing filler metal part, and all of the fractures were due to damage to the ceramic Note 3) Parts by weight are shown based on 100 parts of the brazing filler metal base material.
以上のように、この発明は接合用ろう材を、チタニウム
を含む金属粉末粒子およびこのチタニウム含有粉末粒子
にぬれ性を有する低融点でかつチタニウム含有粒子と合
金化しうるろう材母材を用いて粉末粒子、箔状又は線状
の接合用ろう材を形成したから、このろう材を接合面に
介在させ例えば真空中において上記ろう材を形成してい
る母材が融液となる温度に加熱することによって、この
母材中へチタニウムを含む粉末粒子の一部分の拡散をは
かり、ついで溶融母材を介してセラミックス中へのチタ
ニウムを含む粉末粒子の拡散を行わせ、必要に応じこの
拡散と同時に、所要の金属元素と化合物との粉末粒子を
添加することにより接合部界面におけるセラミックスの
解離反応を促進し、これら解離元素との結合力を向上さ
せることができ、従って、このろう材はセラミックスと
金属またはセラミックス同志を接合するための接合用ろ
う材としてきわめて有用であり、しかも、従来の接合法
における問題点を悉く解消できるものである。As described above, the present invention uses metal powder particles containing titanium and a brazing material base material that has a low melting point that has wettability to the titanium-containing powder particles and can be alloyed with the titanium-containing particles to form a bonding brazing filler metal. Having formed a particle, foil-shaped, or linear brazing filler metal, this brazing filler metal is interposed on the bonding surface and heated, for example, in a vacuum to a temperature at which the base material forming the brazing filler metal becomes a melt. A portion of the titanium-containing powder particles are diffused into this base material, and then the titanium-containing powder particles are diffused into the ceramic through the molten base material, and if necessary, at the same time as this diffusion, the required By adding powder particles of a metal element and a compound, it is possible to promote the dissociation reaction of the ceramic at the joint interface and improve the bonding strength with these dissociated elements. It is extremely useful as a joining brazing material for joining ceramics together, and moreover, it can solve all the problems in conventional joining methods.
特に、本発明るう材は従来より手法が確立されている粉
末粒子又は箔若しくは線の形成方法を利用するので、製
造技術上の困難性が少ないのみならず、安定した品質の
ろう材を比較的容易に得ることができ、また、このよう
にして得られる本発明るう材は、セラミックスや金属の
種類、形状にかかわりなく一回の加熱により安定した大
きな接合強度を得ることができるとともに、接合にあた
って接合体相互の寸法精度をよく確保でき、また加熱接
合時の温度制御が容易で大量生産が可能となるなど、工
業的に有利な接合態様を実現することができる。In particular, since the soldering material of the present invention uses a method of forming powder particles, foil, or wire, which has been established in the past, it not only has less difficulty in manufacturing technology, but also has stable quality compared to soldering materials. The material of the present invention obtained in this way can obtain stable and large bonding strength by one heating regardless of the type and shape of ceramics or metals, and It is possible to achieve an industrially advantageous bonding mode, such as ensuring good dimensional accuracy between the bonded bodies during bonding, and facilitating temperature control during heat bonding to enable mass production.
Claims (1)
の金属又は合金をろう材母材とし、該母材と前記粒子と
を用いて母材中に少なくともＴｉ粒子が分散する粉末粒
子、箔又は線状に形成したことを特徴とするセラミック
ス同志またはセラミックスと金属との接合用ろう材。 ２ Ｔｉ含有粒子は、Ｔｉ、Ｍｏ及びＣａ、又は、Ｔｉ
、Ｍｏ及びＡｌからなる特許請求の範囲第１項記載の接
合用ろう材。 ３ Ｔｉ、Ｍｏ及びＣａ、又は、Ｔｉ、Ｍｏ及びＡｌか
らなるＴｉ含有粒子は、ＭｏとＣａ、又は、ＭｏとＡｌ
のそれぞれの含有量が同量であるか若しくは、Ｃａ又は
Ａｌの含有量より多いＭｏを含む特許請求の範囲第１項
記載の接合用ろう材。 ４ Ｔｉ含有粒子は、Ｔｉ、Ｍｏ及びＣａ、又は、Ｔｉ
、Ｍｏ及びＡｌを含有させたもののいずれかに、Ｔｉ又
はＺｒの窒化物、炭化物又はほう化物を添加したもので
ある特許請求の範囲第１項記載の接合用ろう材。[Scope of Claims] 1 A metal or alloy that forms an alloy with Ti-containing particles and has a lower melting point than the particles is used as a brazing material base material, and the base material and the particles are used to form at least Ti particles in the base material. A brazing material for joining ceramics or ceramics to metal, characterized by being formed into dispersed powder particles, foil, or linear. 2 Ti-containing particles are Ti, Mo and Ca, or Ti
, Mo, and Al. 3 Ti-containing particles consisting of Ti, Mo and Ca, or Ti, Mo and Al are composed of Mo and Ca or Mo and Al.
The brazing filler metal for bonding according to claim 1, which contains Mo in the same amount or in a larger amount than the content of Ca or Al. 4 Ti-containing particles are Ti, Mo and Ca, or Ti
2. The brazing filler metal for bonding according to claim 1, wherein a nitride, carbide, or boride of Ti or Zr is added to any one of the brazing filler metals containing , Mo, and Al.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15879686A JPS6317267A (en) | 1986-07-08 | 1986-07-08 | Solder material for joining ceramics each other or ceramic and metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15879686A JPS6317267A (en) | 1986-07-08 | 1986-07-08 | Solder material for joining ceramics each other or ceramic and metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6317267A true JPS6317267A (en) | 1988-01-25 |
Family
ID=15679534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15879686A Pending JPS6317267A (en) | 1986-07-08 | 1986-07-08 | Solder material for joining ceramics each other or ceramic and metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6317267A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7047635B2 (en) * | 2000-03-15 | 2006-05-23 | Matsushita Electric Industrial Co., Ltd. | Connecting material and connecting method |
| JP2008031748A (en) * | 2006-07-30 | 2008-02-14 | Nobuyuki Tsuboi | Automatic door device |
-
1986
- 1986-07-08 JP JP15879686A patent/JPS6317267A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7047635B2 (en) * | 2000-03-15 | 2006-05-23 | Matsushita Electric Industrial Co., Ltd. | Connecting material and connecting method |
| JP2008031748A (en) * | 2006-07-30 | 2008-02-14 | Nobuyuki Tsuboi | Automatic door device |
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