JPH03184693A - Brazing powder for joining ceramics - Google Patents
Brazing powder for joining ceramicsInfo
- Publication number
- JPH03184693A JPH03184693A JP32305289A JP32305289A JPH03184693A JP H03184693 A JPH03184693 A JP H03184693A JP 32305289 A JP32305289 A JP 32305289A JP 32305289 A JP32305289 A JP 32305289A JP H03184693 A JPH03184693 A JP H03184693A
- Authority
- JP
- Japan
- Prior art keywords
- brazing
- ceramics
- powder
- nickel
- added
- 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.)
- Granted
Links
- 238000005219 brazing Methods 0.000 title claims abstract description 45
- 239000000919 ceramic Substances 0.000 title claims abstract description 36
- 239000000843 powder Substances 0.000 title claims abstract description 30
- 238000005304 joining Methods 0.000 title abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 229910000679 solder Inorganic materials 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 claims description 3
- 229910001000 nickel titanium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 9
- 150000002739 metals Chemical class 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 229910000833 kovar Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005496 eutectics Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Ceramic Products (AREA)
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とセラミックス、セラミックスと
金属を接合するための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 for joining ceramics and ceramics and ceramics and metals.
セラミックス同志又は、セラくツクスと金属との接合に
用いられるろう材として、銀ろうをベースにし、これに
少量のＴｉ等を添加したろう材が知られている。しかし
ながら、これら銀ろうをベースにしたろう材は４００°
Ｃ以上での耐酸化性、高温強度や室温近くでの耐食性に
劣るため、これらろう材で接合された部品は、接合部に
耐酸化性、高温強度及び耐食性に弱点を持っている。従
って高温下や腐食環境下での使用に制限があり、セラミ
ックス本来の特徴である、耐酸化性、高温強度、耐食性
といった特性を十分に発揮させることができない。As a brazing material used for joining ceramics or ceramics to a metal, a brazing material based on silver solder and to which a small amount of Ti or the like is added is known. However, these silver solder-based brazing materials have an angle of 40°
Because they are inferior in oxidation resistance at temperatures above C, high-temperature strength, and corrosion resistance near room temperature, parts joined with these brazing filler metals have weaknesses in oxidation resistance, high-temperature strength, and corrosion resistance at the joints. Therefore, it is limited in its use in high temperature or corrosive environments, and cannot fully exhibit the characteristics inherent to ceramics, such as oxidation resistance, high temperature strength, and corrosion resistance.
重量％（以下同じ）でＣｒ１８〜３０χ、Ｓｔ ９〜１
２Ｘ、ＣＯ。Cr18-30χ, St 9-1 in weight% (same below)
2X, CO.
１５Ｘ以下、残部Ｎｉのニッケルろうは、Ｎｉ−Ｃｒ−
３ｉ ３元系ろう材として知られており、なかでも、Ｃ
ｒ ｔ８．０〜２０．０Ｘ、Ｓｉ ９．７５〜１０．５
％、Ｃ０．１５Ｘ以下、残部Ｎ１（７）ニッケルろうは
ＪＩＳ規格にも規定されたろう材として、各種の耐熱性
、耐食性の金属部品同志をろう付するのに広く用いられ
ている。しかしながら、このろう材を用いてセラミック
スをろう付しようとした場合、このろう材はセラミック
スとの濡れ性が全くないため、セラミックスとろう材と
の界面で剥がれてしまい、セラミックスの接合には全く
用いることができなかった。15X or less, nickel solder with balance Ni is Ni-Cr-
3i Known as a ternary brazing filler metal, especially C
r t8.0~20.0X, Si 9.75~10.5
%, C0.15X or less, balance N1 (7) Nickel brazing material is a brazing material specified in JIS standards and is widely used for brazing various heat-resistant and corrosion-resistant metal parts together. However, when trying to braze ceramics using this brazing filler metal, this brazing filler metal has no wettability with ceramics, so it peels off at the interface between the ceramic and the brazing filler metal, so it is not used at all for joining ceramics. I couldn't.
〔発明が解決しようとする課題］
本発明者等は、耐熱性、耐食性に優れる従来公知のニッ
ケルろうをセラミックスのろう付に用いる方法について
種々検討した結果、Ｔｉを１〜１０χ添加すると、セラ
ミックスに対する濡れ性が付加されることを見出し、本
発明を完成したものである。[Problems to be Solved by the Invention] The present inventors have conducted various studies on methods for using conventionally known nickel solder, which has excellent heat resistance and corrosion resistance, for brazing ceramics. It was discovered that wettability was added, and the present invention was completed.
本発明ノロう材はＣｒ １８〜３０Ｘ、Ｓｉ ９〜Ｉ２
％、Ｃ０．１５２以下、残部Ｎｉのニッケルろうに対し
、Ｔｉを１〜１０２添加したことを特徴とするセラミッ
クス接合用ろろ粉末である。The slag material of the present invention has Cr 18-30X, Si 9-I2
%, C0.152 or less, and the balance is Ni, which is a nickel solder powder with 1 to 102 Ti added thereto.
上記のニッケルろうはＮｉ−Ｃｒ−３ｉ ３元系合金の
３元共晶組成（Ｃｒ ２０．５Ｘ、Ｓｉ １１．６Ｚ、
Ｎｉ残部）をヘースニしたものである。The above nickel solder has a ternary eutectic composition of a Ni-Cr-3i ternary alloy (Cr 20.5X, Si 11.6Z,
(remaining Ni) is reduced.
ＣｒはＮｉ中に固溶してＮｉ−Ｃｒ固溶体（以後、Ｎ１
（Ｃｒ）と表す）となり合金の耐酸化性、耐熱性及び耐
食性を向上させるが、Ｃｒが１８Ｘ以下では、その効果
が少なく、十分ではない。一方、Ｃｒを３０Ｘ以上にし
ても、前記特性の改善効果はみられないばかりか、合金
の液相温度が上昇して、ろう付作業性を阻害するので好
ましくない、従って、ＣｒはＩ８〜３０２とする必要が
ある。Cr is dissolved in Ni to form a Ni-Cr solid solution (hereinafter referred to as N1
(Cr)) improves the oxidation resistance, heat resistance, and corrosion resistance of the alloy, but if Cr is 18X or less, the effect is small and not sufficient. On the other hand, even if the Cr content is 30 It is necessary to do so.
ＳｉはＮｉ （Ｃｒ）と見掛上、擬２元系の共晶反応を
示し、合金の融点を低下させる。 Ｎ１（Ｃｒ）−Ｓｉ
の共晶域は概ね１１〜１２χであり、共晶組成に近い合
金がろう付性に優れる。Ｓｔが９％以下では亜共晶とな
り、初晶Ｎ１（Ｃｒ）の晶出温度、即ち液相温度が高く
なり、ろう付温度の上昇やろう付時の固液相分離（溶は
別れ）などが起こり、ろう付性を阻害する。一方、Ｓｉ
が１２％を超えると、過共晶となり、初晶に硬質なＮ
ｉ （Ｃｒ）珪化物を晶出し、合金の靭性を著しく低下
させる。従って、Ｓｉは９〜１２％とする必要がある。Si appears to exhibit a pseudo-binary eutectic reaction with Ni (Cr), lowering the melting point of the alloy. N1(Cr)-Si
The eutectic region of is approximately 11 to 12χ, and alloys with a composition close to the eutectic composition have excellent brazing properties. When St is 9% or less, it becomes hypoeutectic, and the crystallization temperature of primary N1 (Cr), that is, the liquid phase temperature, increases, resulting in an increase in brazing temperature and solid-liquid phase separation (solution separates) during brazing. occurs, impairing brazing properties. On the other hand, Si
When it exceeds 12%, it becomes hypereutectic and hard N
i (Cr) Crystallizes silicides and significantly reduces the toughness of the alloy. Therefore, Si needs to be 9 to 12%.
ＣはＮ ｉ （Ｃｒ）中に固溶され、基質を強化するの
に役立つが、Ｃが０．１５′１以上になると固溶限度を
超え、Ｃｒ炭化物を形成して合金中に晶出又は析出し合
金の耐食性を劣化させると同時に、ろう付時のろう材の
流動性を阻害させるため、Ｃは０．１５％以下にする必
要がある。C is dissolved in N i (Cr) and serves to strengthen the matrix, but when C exceeds 0.15'1, the solid solubility limit is exceeded and Cr carbide is formed and crystallized in the alloy. C needs to be 0.15% or less because it deteriorates the corrosion resistance of the precipitated alloy and at the same time inhibits the fluidity of the brazing filler metal during brazing.
Ｔｉの添加は、Ｔｉをニッケルろう合金中に溶解、配合
する方法、又は粉末としてニッケルろう合金粉末と混合
する方法のいずれも適用可能であるが、粉末として混合
する場合には、Ｔｉ粉末単独よりもＮｉ−Ｔｉ合金粉末
、もしくはＴｉＨｚ粉末として混合する方が好ましい。Ti can be added by melting and blending Ti into a nickel braze alloy, or by mixing it as a powder with a nickel braze alloy powder, but when it is mixed as a powder, it is more difficult to add Ti than Ti powder alone. It is also preferable to mix Ni--Ti alloy powder or TiHz powder.
特にＴｉｔｈ粉末として混合すると、ろう付時の雰囲気
が多少酸化性であっても、Ｔｉの酸化が防止され、良好
なろう付が行なえる特徴がある。In particular, when mixed as Ti powder, Ti is prevented from oxidizing even if the atmosphere during brazing is somewhat oxidizing, and good brazing can be achieved.
Ｔｉの添加量は１−１０χであり、１ｚ以下では、セラ
ミックスに対するニッケルろうの濡れ性は改善されず、
ろう材界面よりセラミックスが剥がれてしまう。一方１
０Ｘ以上添加すると、ろう材の流動性が悪くなり、隙間
浸透性を阻害して、良好なろう付ができなくなる。The amount of Ti added is 1-10χ, and if it is less than 1z, the wettability of nickel solder to ceramics will not be improved.
Ceramic peels off from the brazing metal interface. On the other hand 1
If more than 0X is added, the fluidity of the brazing material will deteriorate, impeding the gap permeability and making it impossible to perform good brazing.
ニッケルろうにＴｉを添加したことにより、セラミック
スとの濡れ性が改善される作用を有する。このことによ
り、従来、ニッケルろうでは不可能であったセラミック
スとセラ名ンクス、セラミックスと金属の接合が可能と
なる。Adding Ti to nickel solder has the effect of improving wettability with ceramics. This makes it possible to join ceramics and ceramics, and ceramics and metals, which was previously impossible with nickel solder.
以下、本発明の代表的な実施例と比較例を示す。 Below, typical examples and comparative examples of the present invention will be shown.
実施例（１）
Ｃｒ １０Ｘ、Ｓｉ １０Ｘ、Ｔｉ ３Ｘ、残部Ｎｉを
配合した溶湯を、アトマイズ法により粉末となし、Ｔｆ
３Ｘを添加したセラミックス接合用ろう粉末を得た。Example (1) A molten metal containing Cr 10X, Si 10X, Ti 3X, and the balance Ni was made into powder by an atomization method, and Tf
A brazing powder for ceramic bonding to which 3X was added was obtained.
得られた粉末０．５ｇを第１図に示すように、アルミナ
板とコバール板の間に載置し、Ｉ Ｘ １０−’ｔｏｒ
ｒ。As shown in Fig. 1, 0.5 g of the obtained powder was placed between an alumina plate and a Kovar plate, and
r.
の真空中１２００ ’Ｃ，３０分加熱してろう付を行っ
た。Brazing was performed by heating at 1200'C in vacuum for 30 minutes.
この結果、アルミナ板のコバール板に接合した面、全体
にろう材が付着し、完全にろう付された状態であった。As a result, the brazing material adhered to the entire surface of the alumina plate that was joined to the Kovar plate, resulting in a completely brazed state.
実施例（２）
実施例（１）と同一ろう材を用い、アルミナ板の代わり
に窒化アル稟（＾ＩＮ）板とし、実施例（１）と同一条
件でろう付した結果、窒化アルξ板のコバール仮に接し
た面全体にろう材が付着し、完全にろう付された状態で
あった。Example (2) Using the same brazing material as in Example (1), using an aluminum nitride (^IN) plate instead of the alumina plate, and brazing under the same conditions as in Example (1), an aluminum nitride ξ plate was obtained. The brazing metal was adhered to the entire surface of the Kovar that had been in contact with it, and it was completely brazed.
実施例（３）
市販ノニッケルろうＦＰ−６０５（Ｃｒ １９Ｘ、Ｓｉ
１０％、 ＣＯ，１５Ｘ以下、残部Ｎｉ）粉末に対し
、Ｎｉ−Ｔｉ （５０Ｘ）粉末を５χ混合して、Ｔｉ
２．５χを添加させたセラミックス接合用ろう粉末を得
た。Example (3) Commercially available non-nickel brazing FP-605 (Cr 19X, Si
10% CO, 15X or less, balance Ni) powder and 5χ of Ni-Ti (50X) powder were mixed to make Ti.
A brazing powder for ceramic bonding to which 2.5χ was added was obtained.
得られた粉末を実施例（１）と同じ方法でろう付した結
果、アルミナ板のコバール板に接した面全体にニッケル
ろうが付着し、完全にろう付された状態であった。As a result of brazing the obtained powder in the same manner as in Example (1), nickel solder adhered to the entire surface of the alumina plate in contact with the Kovar plate, resulting in a completely brazed state.
実施例（４）〜（６）
アトマイズ法で得られた、Ｃｒ ２７Ｚ、Ｓｉ １１．
５Ｘ、Ｎｉ残部の粉末に対しＴｉＨｚ粉末を１．１χ（
実施例（４）） 、 ５２（実施例（５）） 、ｌｏｇ
（実施例（６））それぞれ混合し３種のセラミックス
接合用ろう粉末を作成した。Examples (4) to (6) Cr 27Z, Si 11. obtained by atomization method.
5X, the TiHz powder was 1.1χ (
Example (4)), 52 (Example (5)), log
(Example (6)) Three types of solder powders for ceramic bonding were prepared by mixing them.
得られたろう粉末を実施例（１）と同じ条件でアルミナ
板とコバール板のろう付を行った。ろう付状態の結果を
第１表に示す。The obtained brazing powder was used to braze an alumina plate and a Kovar plate under the same conditions as in Example (1). The results of the brazed state are shown in Table 1.
比較例（１）〜（２）
市販のニッケルろうＦＰ−６０５（Ｃｒ １９χ、Ｓｉ
１０χ、ＣＯ，１５Ｘ以下、残部Ｎｉ）粉末に対し、
ＴｉＯｘ粉を添加しないでそのまま用いる場合（比較例
（１））と、１５％混合した場合（比較例（２））の２
種の粉末を用いて、実施例（１）と同じ条件でアルミナ
板とコバール板のろう付を行った。ろう付状態の結果を
第１表に示す。Comparative Examples (1) to (2) Commercially available nickel solder FP-605 (Cr 19χ, Si
10χ, CO, 15X or less, balance Ni) for powder,
Two cases are used: one is used as it is without adding TiOx powder (Comparative Example (1)), and the other is when it is mixed at 15% (Comparative Example (2)).
Using the seed powder, an alumina plate and a Kovar plate were brazed under the same conditions as in Example (1). The results of the brazed state are shown in Table 1.
第１表
〔効果〕
以上に示したように、通常のニッケルろうに対しＴｉを
１〜ＩＯＸ添加することによりセラミックスとの濡れ性
が改善され、従来不可能であったセラミックスとセラミ
ックス又はセラミックスと金属のろう付が可能となり、
また、耐熱性、耐食性のあるニッケルろうが用いられる
ことから、従来にない複合材料を製造することができ、
産業上有用な発明である。Table 1 [Effects] As shown above, by adding 1 to IOX of Ti to ordinary nickel solder, the wettability with ceramics is improved, which was previously impossible to achieve between ceramics and ceramics or between ceramics and metals. It is now possible to braze
In addition, since heat-resistant and corrosion-resistant nickel solder is used, it is possible to manufacture unprecedented composite materials.
This is an industrially useful invention.
第１図はろう付性の試験に用いたアルミナ板とろう材及
びコバール板の配置及び寸法を示す。Figure 1 shows the arrangement and dimensions of the alumina plate, brazing filler metal, and Kovar plate used in the brazeability test.
Claims (4)
０．１５％以下、残部Ｎｉのニッケルろうに対し、Ｔｉ
を１〜１０％添加したことを特徴とするセラミックス接
合用ろう粉末。(1) Cr18-30%, Si9-12%, C in weight%
0.15% or less, for nickel solder with the balance Ni, Ti
A brazing powder for ceramic bonding, characterized in that 1 to 10% of is added.
請求項第１項記載のセラミックス接合用ろう粉末。(2) The brazing powder for ceramic bonding according to claim 1, wherein Ti is added by mixing Ti powder.
を添加した請求項第１項記載のセラミックス接合用ろう
粉末。(3) By mixing Ni-Ti alloy powder, Ti
The brazing powder for ceramic bonding according to claim 1, further comprising the following: 1.
加した請求項第１項記載のセラミックス接合用ろう粉末
。(4) The brazing powder for ceramic bonding according to claim 1, wherein Ti is added by mixing TiH_2 powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32305289A JP2755455B2 (en) | 1989-12-12 | 1989-12-12 | Brazing powder for ceramic bonding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32305289A JP2755455B2 (en) | 1989-12-12 | 1989-12-12 | Brazing powder for ceramic bonding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03184693A true JPH03184693A (en) | 1991-08-12 |
| JP2755455B2 JP2755455B2 (en) | 1998-05-20 |
Family
ID=18150565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32305289A Expired - Fee Related JP2755455B2 (en) | 1989-12-12 | 1989-12-12 | Brazing powder for ceramic bonding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2755455B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04157089A (en) * | 1990-10-18 | 1992-05-29 | Nippon Steel Corp | Ni base heat resisting brazing filler metal excellent in wettability and oxidation resistance |
| JP2012521951A (en) * | 2009-03-31 | 2012-09-20 | アルストム テクノロジー リミテッド | Double brazing member comprising at least one first layer of Ni-based brazing and at least one second layer containing an active element, method of manufacturing the double brazing member and use of the double brazing member |
| JP2018004105A (en) * | 2016-06-28 | 2018-01-11 | 株式会社ディ・ビー・シー・システム研究所 | Molten metal treatment device and manufacturing method of the same |
-
1989
- 1989-12-12 JP JP32305289A patent/JP2755455B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04157089A (en) * | 1990-10-18 | 1992-05-29 | Nippon Steel Corp | Ni base heat resisting brazing filler metal excellent in wettability and oxidation resistance |
| JP2012521951A (en) * | 2009-03-31 | 2012-09-20 | アルストム テクノロジー リミテッド | Double brazing member comprising at least one first layer of Ni-based brazing and at least one second layer containing an active element, method of manufacturing the double brazing member and use of the double brazing member |
| JP2018004105A (en) * | 2016-06-28 | 2018-01-11 | 株式会社ディ・ビー・シー・システム研究所 | Molten metal treatment device and manufacturing method of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2755455B2 (en) | 1998-05-20 |
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