JPS59126739A - Quickly liquid-cooled alloy foil strip for brazing - Google Patents

Abstract

PURPOSE:To provide a quickly liquid-cooled alloy foil strip for brazing ceramics and metals which consists of specific amt. of Ti, Zr and Hf and Cu and can adhere securely the ceramics and metals having any shape with a simple operation. CONSTITUTION:A titled alloy foil strip consists of 25-75atom% >=1 kind among Ti, Zr and Hf, and the balance Cu, and is used to adhere ceramics to each other, ceramics to metals and metals to each other. The above-described balance may be, if necessary, composed of 100atom% in total of <=30atom% in total of >=1 group within the limit of each group of a) <=20atom% >=1 kind among Co, Fe, Ni, Pd, Rh and Be, b) <=20atom% >=1 kind among Cr, Mo, W, V, Nb, Ta, and Mn, c) <=30atom% >=1 kind of Ag and Au, d) <=10atom% >=1 kind among Sc, Y and La groups, e) <=15atom% >=1 kind among B, Si, Ge, P, As and Sb, and f) <=10atom% >=1 kind among Al, Ga, In, Sn, Cd and Zn, as well as <=20atom% Cu.

Description

[Detailed Description of the Invention] Technical Field The present invention relates to a brazing material for bonding ceramics to ceramics, ceramics to metals, or metals to each other, and easily creates a foil strip suitable for bonding objects with complex shapes. Regarding the brazing filler metal obtained in

BACKGROUND ART The active metal method has been put into practical use as a technology for bonding ceramics and metals, and this method consists of active metal powders such as TL and Zr, and QL and N, which are made into alloys with relatively low melting points.
This is a method in which a mixed powder of L, Ac+ powder, etc. is made into a paste using an organic binder, the paste is inserted between ceramic and metal, and the paste is bonded by heating operations twice in vacuum or in an inert gas.

However, since this active metal method uses the above-mentioned paste-like brazing material, there are various problems in the reliability of bonding and the operability during bonding.

That is, active metal powders such as TL and ZY are very easily oxidized and oxides are formed on the powder surface, and these oxides remain in the bonded area, causing a decrease in reliability after bonding.
In addition, the paste-like brazing filler metal described above is simply mixed with an organic binder, making it impossible to obtain a uniform alloy composition after bonding, and the organic binder evaporates during heating, producing unnecessary gas. Bubbles tend to form in the parts, resulting in uneven adhesive strength and reduced reliability after adhesion. Furthermore, when applying the above-mentioned paste brazing filler metal to ceramics or metals, the amount of application tends to be uneven.
There are problems such as inefficient adhesive strength and workability such as application before heat bonding.

In order to replace the paste brazing filler metal that forms pores and residues during adhesion, Japanese Patent Application Publication No. 56-4396 describes cobalt as a brazing alloy that can be obtained as a ductile foil. Although a base alloy is disclosed, this alloy is different from the composition of the alloy foil strip of the present invention and is a brazing material for metal members such as cobalt and nickel base alloys, and is not suitable for bonding metals other than those mentioned above and ceramics. It is.

In addition, using a well-known technique, it was developed as a ductile glassy alloy that can be made into thin plates by rapidly cooling the melt.
Although a zirconium-titanium alloy is disclosed in Publication No. 2947, the invention in the publication relates to an alloy for electrical resistance, and does not disclose anything regarding a brazing material for adhesion between ceramics and ceramics, ceramics and metals, or metals. .

Purpose of the Invention The purpose of the present invention is to eliminate the drawbacks of the conventional paste brazing filler metal used in the above-mentioned active metal method, and to provide a brazing filler metal that has excellent bonding workability and is easy to bond even with complex shapes. shall be. The aim is also to provide a brazing material that has high and uniform bonding strength and is highly reliable after bonding.

Furthermore, the present invention aims at a brazing material that is easy to bond and handle, and is intended for use in moulds, such as foils, ribbons, wires, etc.
The purpose is to create a brazing filler metal that can easily form L-bands.

In addition, the present invention has wide applicability to bonding ceramics to ceramics, ceramics to metals, and metals to metals, and has reliability such as bonding strength and uniformity, corrosion resistance, oxidation resistance, aging, etc. The aim is to create a brazing material with excellent adhesive properties, such as ease of bonding operations and ease of handling of the brazing material itself.

DISCLOSURE OF THE INVENTION This invention relates to Ti, Zr, H? The gist is a liquid-quenched alloy foil strip containing at least one of these in an amount of 25 to 75 at %, and the remainder including unavoidable impurities.

Furthermore, the present invention provides at least one of TL, Zy, The liquid quenched alloy foil strip is used for brazing with a total amount of 100 atomic % and unavoidable impurities exceeding 5 atomic %.

a Co , Fe , NL , Pd , Rh , Be
20 atomic % or less of at least one of the following, b Cr , t'b , W , V , r , Ta
, 20 atomic % or less of at least one of Mn, 0 to . 30 atomic % or less of at least one of Au, 10 atomic % of at least one of dSc, Y, and Li group
Hereinafter, at least one of 8B, Si, CA, P, As, and Sb is contained at 15 atomic % or less, fM, Ca, ITl, Sn, Cd, and Zn.
At least one of these in an amount of 10 atomic % or less.

This invention consists of T., 7. r, ) Contains 25 at % to 75 at % of at least one active metal among 4F,
A liquid-quenched alloy foil strip containing at least 20 at. It is characterized by

This invention has the following advantages: Compared to the conventional paste brazing filler metal used in the above-mentioned active metal method, the foil strip is more flexible and ductile, so it is easy to handle, has excellent bonding workability, and can be used in complex shapes. Even if it is, it can be evenly interposed in the bonding part without waste, and the bonding operation becomes easy. In addition, unlike conventional paste brazing materials, it is difficult to generate active metal oxides, so it has wide applicability for bonding ceramics to ceramics, ceramics to metals, and metals to metals.
It has excellent adhesion properties such as adhesive strength and uniformity, corrosion resistance, oxidation resistance, mechanical reliability such as aging, ease of adhesion operation, and ease of handling of the brazing material itself.

The reasons for limiting the ingredients will be explained below.

25 at least one of TL, Zr, 1-)P
The minimum amount of active metal required to obtain strong adhesive strength with ceramics or metals is 25 at%, and it is actively included, but 751
i! This is because if the amount exceeds 5%, the melting point becomes too high and is not suitable for practical use. Further, the content is preferably 30 atom % to 70 atom %, and most preferably 40 atom % to 60 atom %.

The brazing material lowers the melting point of the brazing filler metal through eutectic formation with the active metal, and forms the base of the brazing filler metal according to the present invention, and serves to make it easier to become amorphous, thereby aiding the function of the active metal and the brazing filler metal. Even if the following additive element groups are added, the content must exceed at least 20 atomic %, and if the following additive element groups are not added, the remaining amount will be included.

Group a, Go, Fe, NL, Pci, Rh, B
At least one of the above elements is added to e to lower the melting point of the active metal and improve wettability during adhesion, but if it is contained in a large amount, the activity will be reduced, so the content should not exceed 20 at%. do. Preferably 0.1
The content is from atomic % to 10 atomic %.

Group b, Cr, h, W, V, Nb, Ta, l
'tn is added with at least one of the above elements in order to promote the activation of the brazing filler metal, but if too much is included, the melting point will become too high, so the content should be 20 at % or less. The content is desirably 0.1 atomic % to 10 atomic %.

Group 0, ~, Au has the function of lowering the melting point of the group and improving the toughness of the joint part, so at least one of the above elements is added. The content shall be atomic percent or less. The content is desirably 0.1 atomic % to 20 atomic %. Most preferably, the content is 0.1 atomic % to 10 atomic %.

At least one of the above elements is added to the d group, Sc, Y, and La groups in order to promote the activation of the brazing filler metal. However, if the content is too large, the brazing filler metal becomes brittle, so the content should not exceed 10 at %. do. The content is desirably 0.1 atomic % to 5 atomic %.

Group 8, B, SL, Ga, P, As, and Sb have the function of lowering the melting point of 5, so at least one of the above elements is added; The content shall be 15 atomic % or less. The content is desirably 0.1 atomic % to 10 atomic %.

Group 1, #, Ga, In, Sn, Cd, and Zn are added with a small amount (or one kind) of the above elements in order to promote amorphization, but if they are included in a large amount, the activity is reduced, so The content is 10 atom % or less, preferably 0.1 atom % to 5 atom %.
Each of the above groups works effectively when contained alone or in combination of two or more groups within each content limit, but if the total amount exceeds 30 at% due to the combination of each group, the activity will decrease. The upper limit is set to 30 atom % in order to prevent the content from becoming amorphous.

The obi brazing material according to the present invention is characterized by having sufficient fine crystallinity or amorphousness to obtain flexibility,
In order to facilitate the handling of the foil strip brazing material itself and to obtain excellent adhesion, it is preferable that the amorphous portion be 30% or more, more preferably 50% or more, and most preferably 80% or more. .

Metals and ceramics that can be bonded using the foil strip brazing material of the present invention may have a melting point higher than that of the brazing material of the present invention, such as titanium and zirconium, which are difficult to bond with conventional brazing materials.

Tungsten, molybdenum, etc., stainless steel, tool steel,
In addition to metals such as Invar and Kovar, oxide ceramics, carbide ceramics, nitride ceramics,
It can be applied to almost all ceramics such as lithium ceramics, barium titanate ceramics, and ferrite ceramics.

The method for obtaining the brazing filler metal of the foil strip according to the present invention can utilize the well-known technique of cooling a molten material of a predetermined composition at a rate of about 0.5° C./sec. A foil strip can be obtained by spraying with gas pressure (104-b).Also, a method can be used in which a pair of metal drums are rotated in opposite directions and are brought into contact with each other, rotated at 3rd speed, and the molten material is sprayed onto the opposing surfaces of the drums. In addition to spraying onto the surface of a metal drum, it is also possible to spray onto the inner surface of a cylinder rotating at high speed.

To explain the brazing method, for example, a foil strip cut and press-molded according to the shape of this joint surface is inserted between the surfaces to be joined between the ceramic base and the metal part M, and the two are held together. ,゛ Heating in a reducing atmosphere such as a vacuum of about IX10-3 mmHQ or less, an inert gas, or dry hydrogen at a temperature range above the melting point of the sandwiched foil strip brazing material and below the melting point of the adherend. and then cooled to complete the bonding.

Furthermore, higher adhesive strength can be obtained when the heating temperature is higher within the above temperature range and when the holding time is shorter, such as from about 5 minutes to 20 minutes.

Examples Example 1 An alloy having a predetermined composition is high-frequency melted in an argon gas atmosphere, and is ejected under argon gas pressure onto the outer peripheral surface of a steel roll rotating at high speed at a rate of approximately 05°C/sec. By cooling at a high speed, 37 kinds of ribbons having a thickness of 20 to 60 ρ and a width of about 15 nm+m were produced.

The composition of each ribbon-shaped foil brazing filler metal is as shown in Table 1, most of which consists essentially of an amorphous alloy, and some of which consists of a mixture of amorphous and crystalline materials (5.8° 22.30,32
, 33, 34) and microcrystalline (36, 37).

The obtained ribbon-shaped brazing material was a flexible foil strip that could be wound up into a bar with a total diameter of 30 mm.

Table 1 Sample floor Composition (atomic%) 1
Ding L 34CLL 662 TiS2
To50 3 TL60Cu40 4 L67Cu33 5 Zr25Cu75 6 Zr40Cu60 7 zr55cu45 8 7, r72Cu28 9 TL 50Zr 10Cu 4010
Ti30HP5CLL6511 Zr4
0HP 5CLL5512 Zr45Ca45
F@1013 Zr 45Cu 45Co 1
014 Zr45Cw45Ni 1015
Zr45Cu45Pd 1016 TL
43Cu47Be1017 Ti 43Cu
52Cr 518 Lower L43cu52V
519 Ti50Cu40tln102
0 TL50CA40~1021
Zr505 40α1022 Ti50
cu40La 5Ce 523 Zr40
Cu60Y 1024' Zr40Cu60
B 1025 TL55CAL40P 5
26 Ti55Cu40Si 527
Ding L55CAL4ON 528
Ti55Cu40Si 529 TL40Z
r 10Cu4ONL 5Cr 530
Ding L40Zr 10Cu30Be 10Ao 103
1 Tu5Zr15Cu30SL 5#
532 Zr 45Cu 3ONL 10tl
n 10Sn 533 Zr 40Cah
45Be 5Sn ssi 534 Zr
45H1' 5Cu3ONL 10Y 5 B 5
35 TLIOCn4ONL 15SL53
6 Ti25cAL60sL 5Sn 10
37 Zr25CLL65El 5ZTl
5 Example 2 Adhesive substrate with purity 99.8% 1.15 mm x 15 mm
, using an alumina plate with a thickness of 3 mm, and a 6 m long
Using tough pitch copper with mX 6mm and thickness of 3mm, each adhesive surface was polished to I&1000 with emery paper, and the foil strip brazing filler metal of 141.2.3 in Table 1 was inserted between the two, and sx Under vacuum of io −s mm HO,
Bonding was carried out by holding at various temperatures for 5 minutes under a temperature range of 950°C to 1050°C.

After adhesion, the adhesive substrate and the adhered member were pulled in opposite directions, and the shear fracture stress at this time was measured. The results are shown in Figure 1.
The foil strip brazing material is indicated by x, positive 2 is indicated by Δ, and lV & 13 is indicated by ○. Incidentally, the shear fracture strength of the same alumina plate subjected to the heating and cooling described above was about 1014 fJ.

As is clear from FIG. 1, it can be seen that the foil strip according to the present invention bonded with a brazing material had the same strength as the alumina plate of the base. In addition, the above three types of brazing filler metals are Th
It can be seen that the higher the lead content, the higher the adhesive strength.

Example 3 An alumina plate with a purity of 99.8%, 15 mm x 15 mm, and three thicknesses was used as the bonding substrate, and a 6 mm x 6 plate was used as the bonded member.
Using tough pitch copper with a thickness of 3 mm, each adhesive surface was polished to biooo with emery paper, and a foil strip brazing filler metal shown in Table 1, positive 2, was inserted between the two, and a 5 x 10-5 m
Bonding was carried out under mHo vacuum by holding various temperatures in the temperature range of 950° C. to 1050° C. for 5 minutes.

For comparison, a conventional brazing material was prepared in which a mixed powder of foil brazing material IVb and 2 of the present invention and a powder having the same composition and T powder (both 300 mesh powder) was made into a paste form with an organic binder. Bonding was performed using the same materials under the same conditions.

After adhesion, the adhesive substrate and the adhered member were pulled in opposite directions, and the shear fracture stress at this time was measured. The results are shown in FIG. 2, where Δ indicates the case of the foil strip brazing material of the present invention, and ・ indicates the case of the conventional paste-like brazing material.

As is clear from FIG. 2, it can be seen that the bonding strength is higher when bonding is performed using the brazing filler metal of the foil strip according to the present invention. This is thought to be because the foil strip brazing material is denser and contains significantly less impurities such as oxides than conventional paste brazing material.

Example 4 A ceramic plate shown in Table 2, measuring 15 mm x 15 mm and having a thickness of 3 cylinders, was used as the adhesive base, and the adhered member was sm
Using the ceramic plates shown in Table 2 with a size of 6 mm x 6 mm and a thickness of 3 mm, each adhesive surface was polished to 1iooo with emery paper, and a foil strip brazing filler metal shown in Table 2 was inserted between them, and a 5 x 10-5 mm HO plate was used. Under vacuum, 900℃~12
Twelve sets of adhesion tests were conducted in which adhesives were bonded by holding them at various temperatures in the temperature range of 00°C for 5 minutes.

After adhesion, the adhesive substrate and the adhered member were pulled in opposite directions, and the shear fracture stress at this time was measured. The results are shown in Table 2, along with the adhesive substrates, ceramic types of the members to be adhered, foil band thickness, and adhesion temperatures.

Table 2 shows that the foil strip brazing material according to the present invention is capable of bonding various combinations of ceramics and has high bonding strength.

Table 2 [Contact Adhesive] Example 5 Table 3 A with 15 mm x 15 mm and 3 mm thickness on the adhesive substrate.

Use the ceramic plate shown in B, and attach smm to the adhered member.
Using the metal plates shown in Table 3 A and B, each measuring 6 mm x 3 mm and 3 mm thick, each adhesive surface was covered with emery paper.

After polishing to the desired temperature, a foil strip brazing filler metal shown in Table 3 A and B is inserted between the two, and heated in dry hydrogen or 5 x 10-5 mm.
42 sets of adhesion tests were carried out in which bonding was carried out by holding each sample at various temperatures in the temperature range of 900° C. to 1150° C. for 10 minutes under a vacuum of H (J).

After adhesion, the adhesive substrate and the adhered member were pulled in opposite directions, and the shear fracture stress at this time was measured. The results are shown in Table 3 A for the case where the atmosphere is in dry hydrogen, and Table 3 B for the case in vacuum.
It is shown together with the foil band ratio and adhesion temperature.

From Tables A and B, it can be seen that the foil strip brazing material according to the present invention is capable of adhering various combinations of ceramics and metals and has high adhesion strength.

The porosity of each ceramic plate used in the examples is
Alumina 0%, Zirconia approx. 20%, Silicon Carbide 0
．． 5%, titanium carbide (cermet) 0%, silicon nitride approximately 23%, titanium nitride 0%, barium titanate approximately 1%
, Calcium titanate approx. 1%, Graphite approx. 19%
Met.

Margins below Table 3 A Table 3 B Note *: Cracks occurred in the ceramic bonded substrate after bonding.

[Brief explanation of the drawing]

FIGS. 1 and 2 are graphs showing the relationship between temperature and shear fracture stress, and show the cases of Example 2 and Example 3, respectively. Applicants: Ikuo Okamoto, Masaaki Naga, Yoshiaki Aram, Kawaso Electric Materials Co., Ltd., Sumitomo Special Metals Co., Ltd., Agent 1) Yoshihisa, “l!
50 Figure 2 Sumitomo Special Metals Co., Ltd. Suita Works, 2-19-1 Minami Suita, Suita City 0 Applicant Masaaki Naga 30-6 Maruyama-cho, Suita City Applicant Yoshiaki Arata 3-13-11 Mukosho, Amagasaki City 0Applicant Kawaso Electric Materials Co., Ltd. 1-7-10 Nishihonmachi, Nishi-ku, Osaka ■Applicant Sumitomo Special Metals Co., Ltd. 5-22 Kitahama, Higashi-ku, Osaka

Claims (1)

[Claims] 25 atomic % of at least one of ITL, Zy, and HP
A liquid quenched alloy foil strip containing up to 75 atomic percent, with the remainder consisting of oxidation and unavoidable impurities. 2 At least one of Tj, Zr, and Hr is 2
5 atomic % to 75 atomic %, selected from at least one group within the limits of each group from the following groups, 31% or less, exceeding 20 atomic %, and unavoidable impurities in a total amount of 10
Liquid quenched alloy foil strip for brazing G with 0 atomic %. a At least one of Co, Fe, Ni, Pd, Rh, - at 20 atomic % or less, b Cr, Mo, W, V, Nb, Ta,
At least one of Mn is 20 atomic % or less, at least one of CAg and Au is 30 atomic % or less, and at least one of dsc, Y, and La group is 10 atomic %
Below, 8 B, SL, Ge, P, As, Sb
At least one of the following at 15 atomic % or less, f M , Ga, In, Si, Cd, Zn
At least one of these in an amount of 10 atomic % or less.