JPS59116350A - Alloy foil strip formed by quick liquid cooling for brazing - Google Patents

Abstract

PURPOSE:To provide a titled light-gage alloy strip which has excellent adhesive workability and permits an easy adhering operation with an intricate shape as well by contg. >=1 kind among Ti, Zr, Hf at a prescribed ratio and consisting of the balance >=1 kind among Cu, Ni, Fe, Be and unavoidable impurities. CONSTITUTION:An alloy foil strip formed by quick liquid cooling contains 25- 80atom% active metal of >=1 kind among Ti, Tr, Hf, and >=10atom% >=1 kind among Co, Ni, Fe, Be. Such light-gage alloy strip has higher resilience and ductility than a conventional pasty brazing material used in an active metal method and is therefore easy to handle and has excellent adhesive workability. The light-gage alloy strip can be efficiently and uniformly interposed in the parts to be adhered having an intricate shape, thus permitting easy adhering operation. Since the light-gage alloy strip hardly forms oxide, it has wide adaptability to adhering between metals and between metals and ceramics and provides excellent adhesiveness such as adhesive strength and uniformity thereof.

Description

[Detailed Description of the Invention] Technical Field This invention relates to a brazing material for bonding metals to metals, metals and ceramics, and ceramics to ceramics.
This invention relates to a brazing material that can easily produce a foil strip suitable for bonding objects with complicated shapes.

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

However, since this active metal method uses the above-mentioned PACE 1-type solder, there are various problems in the reliability of bonding and the operability during bonding.

However, active metal powders such as Tj and Zr 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 above-mentioned pehesto-shaped brazing filler metal is mixed with an organic binder (), so it is not possible to obtain a uniform alloy composition after bonding, and the organic binder evaporates during heating, producing unnecessary scum. As the bonding occurs, bubbles form in that area and the bonding strength becomes uneven, reducing reliability after bonding. Furthermore, when applying the above-mentioned PACE 1 to ceramic wax to ceramics or metals, there are problems such as non-uniformity of the application layer and poor adhesive strength and inefficient workability such as application prior to heat bonding.

JP-A-5G-4396 discloses a brazing alloy obtained in the form of a ductile foil as an alloy for brazing G in place of the Pace 1 to brazing filler metal, which forms pores and residues during adhesion. Although a Copal 1-based alloy for Attachment 1 is disclosed, this alloy differs from the composition of the alloy foil strip of the present invention and is a brazing material for metal members such as Cobal 1- and Nitrogen-based alloys, and other than the above. It is unsuitable for bonding metals and ceramics.

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.
No. 52947 discloses a zirconium-titanium alloy, but the invention of the above publication relates to an electrical resistance alloy.
Regarding brazing fillers for bonding metals to metals, metals to ceramics, and ceramics to ceramics, C is not shown in all <11.

Purpose of the Invention The purpose of the present invention is to solve the drawbacks of the conventional paste brazing filler metal used in the above-mentioned active metal method, and to provide a soldering filler metal that has excellent bonding workability and is easy to bond even when the shape is complex. 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 from which foil strips such as foils, ribbons, and wires can be easily obtained.

In addition, this invention is applicable to metals and metals, metals and ceramics,
It has wide applicability for adhesion of ceramics and ceramics, and has uniformity of adhesive strength, corrosion resistance, oxidation resistance, reliability in terms of aging, ease of adhesion operation, and ease of handling of the brazing material itself. It is intended to be a brazing material with excellent adhesive properties such as adhesive properties.

DISCLOSURE OF THE INVENTION The present invention is directed to a method containing at least one of Tt, Zr, and f (251 Di) to 80 atomic %, and the balance being Co.
, NL, Fe, 13e and unavoidable impurities.

Further, the present invention includes at least one of Tj, Zr, and He selected from 25 at% to 80 at%, and at least one group selected from the following groups within the limits of each group to a total of 30 at%.
Below, Co, NL, Fe, at least -b1
This is a liquid quenched alloy foil strip for brazing 1) in which the total amount of seeds and unavoidable impurities is 100 atomic % or more.

20 at% of at least one of aPd, Rh, and Cu
Hereinafter, b Cr , I'lo , W , V , Nb ,
20 atomic % or less of at least one of Ta and Mn, 30 atomic % or less of at least one of CAo and Au, 10 atomic % of at least one of dSc, Y, and La group.
Hereinafter, at least one of e B, SL, Cue, P, As, and Sb is contained at 75 atomic % or less, f M, Ca, In, STI, Cd, and Zn.
At least one of these in an amount of 10 atomic % or less.

This invention contains 25 at% to 80 at% of at least one active metal among Ti, Zr, and Hr, and
A liquid quenched alloy foil strip containing 10 atomic % or more of at least one of Fe, Be, and Be, and is a foil, ribbon, soybean, etc. made of microcrystalline or amorphous material necessary to have flexibility. It is characterized by being a waxed foil strip.

Compared to the conventional paste-like wax used in the above-mentioned active metal method, this invention uses a foil strip that is highly flexible and ductile, so it is easy to handle, has excellent bonding workability, and can be used in complex shapes. Even if there is such a material, it can be uniformly interposed in the bonding part without waste, and the bonding operation becomes easy. In addition, unlike conventional PACE 1-shaped brazing materials, it is difficult to form oxides with active metals, so it has wide applicability for bonding metals to metals, metals to ceramics, and ceramics to ceramics.
Uniformity of adhesive strength, corrosion resistance, and oxidation resistance.

It has excellent adhesive properties such as mechanical reliability against aging, ease of adhesion operations, and ease of handling the brazing filler metal itself.

The reasons for limiting the ingredients will be explained below.

The reason why at least one of TL, Zy, and f4F is contained from 25% to 80% is because the minimum amount of active metal necessary to obtain strong adhesive strength with ceramics or metals is 25%. However, if it exceeds 80 atom%, the melting point becomes high (and becomes unsuitable for practical use).In addition, it is preferably 30 atom% to 70 atom%, and more preferably 40 atom% to 60 atom%. % content.

Co, NL, Fe, - lower the melting point of the active metal, and form the base of the foil brazing filler metal according to the present invention. Even if the following additive element groups that assist the functions of =, Fe, and Be are added, at least 10 atomic % is required, and if the following additive element groups are not added, the remainder will be occupied.

At least one of the above elements is added to group a, Pd, Rh, and Cu in order to lower the melting point of the active metal and improve wettability during bonding, but if it is contained in a large amount, it will actually reduce the activity. The content is 20 atomic % or less. The content is desirably 0.1 atomic % to 10 atomic %.

Group b, Cr, Mo, W, V, Nb, Ta,
At least one of the above elements is added to Mn in order to promote the activation of the brazing filler metal, but if it is included in a large amount, the melting point will become too high, so the content is limited to 20 atomic % or less. The content is desirably 0.1 atomic % to 10 atomic %.

c BI′, ~, Au has the function of lowering the electrical resistance of the brazing filler metal and improving the toughness of the joint part, so at least one of the above elements is added, but if it is contained in a large amount, the foil strip brazing filler metal Since non-uniformity becomes significant, the content should be 30 atomic % or less. The content is preferably 0.1 atomic % to 20 atomic %, most preferably 0.1 atomic % to 10 atomic %.
Ru.

At least one of the above elements is added to the D, Y, and La groups to promote initial activation of the solder, but if too much J is added, the foil strip brazing material becomes brittle, so The content shall be atomic percent or less. The content is preferably 0.1 atomic % to 5 atomic %.

For group e, B, SL, Qe, P, As, and Sb, at least one of the above elements is added in order to promote amorphization and lower the melting point. 1.
The content is 5 at% or less. Desirably 0.1 atomic%~
The content is 10 atom%.

Group 1, M, Ga, In, Sn, Cd, and Zn have the function of lowering the melting point of the brazing filler metal, so at least one of the above elements is added. In order to reduce the amount, the content is set to be 10 atomic % or more. The content is desirably 0.1 atomic % to 5 atomic %.

In addition, each of the above groups works on IrWJ even when contained alone or in combination of two or more groups within the respective content limits, but if the total amount exceeds 30 at% in the combination of each group, the activity will be reduced. In order to reduce the quality or prevent S = quality improvement,
The upper limit is set to 30 atom%.

The foil strip brazing material according to the present invention is characterized by having sufficient microcrystalline or amorphous material to obtain flexibility,
In order to facilitate the handling of the foil strip brazing material itself and to obtain excellent adhesion, the amorphous portion should preferably be 30% or more, more preferably 50% or more, and most preferably 80% or more. It's good to have.

In particular, when containing TL as an active metal, in order to obtain a cyto-quality portion of 50% or more, in the case of TL NL system, ■
, is less than 60 atomic % of the total, and in the case of TL-Co system, Ti
I is less than 50 atomic % of the total, in the case of Ti Fe system, T
LI, less than 25 atom% of the total, T, - in the case of the intestinal system, TL
must be 68 atomic percent or less of the total.

The metals and ceramics that can be bonded using the foil strip braze according to the present invention need only have a melting point higher than the melting point of the wax coat according to the present invention, and bonding is difficult with conventional brazing materials. !
Metals such as cum, tungsden, molybdenum, stainless steel, tool steel, invar, kovar, oxide ceramics, carbide ceramics, nitride ceramics, real ceramics,
Barium titanate-based ceramics, Ferrai 1-based Relamix, and the like can be applied to almost all types of ceramics.

The method for obtaining the brazing filler metal of the foil strip according to the present invention is to use the well-known technique of cooling a molten material of a predetermined composition with a heat sink at a rate of about 05°C/sec. The molten material is blown off with gas pressure to obtain a foil strip.A pair of metal drums are rotated in opposite directions and are brought into contact with each other at high speed, and the molten material is blown onto the opposite surfaces of the drums. In addition to squealing on the surface of a metal drum, a method of squirting on the inner surface of a cylinder rotating at high speed can also be used.

To explain the brazing method, for example, a foil strip cut and press-formed according to the shape of the joint surface is sandwiched between the surfaces to be joined between a ceramic substrate and a metal member, and the two are held together. In a reducing atmosphere such as a vacuum, an inert gas, or dry hydrogen at a temperature of about 1xlO-3111m t ('J or less), the melting point of the sandwiched foil strip brazing material or more and the melting point of the non-adhesive material or less. Cover by heating in a temperature range and then cooling to complete the bonding.

Further, the higher the heating temperature within the above temperature range, the shorter the holding time of about 5 minutes to 20 minutes, the better the adhesive strength can be obtained.

Examples Examples 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. 37 kinds of ribbon-shaped foil brazing materials having a thickness of 20 to 6011 m and a width of about 15 mm were produced.

The composition of each ribbon-shaped brazing filler metal foil strip is as shown in Table 1. Most of the brazing filler metals are made of an amorphous alloy, and some are a mixture of amorphous and crystalline materials (5,15 ,17,19,22
, 27, 32, 33, 35, 37), and the rest are microcrystalline (2, 20, 21, 23, 24, 25, 34, 3
6).

The ribbon-shaped brazing material obtained was a flexible foil strip C' that could be wound up into a rod having a total diameter of 30++vn.

Table 1 Sample M Composition (atomic %) I
TL77Co23 2 Ti25Co75 3 TL 7ONj 30 4 Ti6ONi40 5 T*38N12 6Zr78Fe22 7Zr78Co22 8 2r65Co35 9 Zr76NL24 10 Zr63NL37 11 Zr 36NL64 12 TL 60Zr 108e 3013
Ti 50Zy 25NL 5Co 2
016 ZrS2))F 1ONi3515
TL55Zr 10Be 1ONj251
6 -' Tj50Zr 1ONL20QL2
017 TL4ONL40α20+8
Zr 35Nt 55Pd +.

19 Zr65Ni25Cr 1020
Zy 70Be2ONb 1021
Zy 6ONi 201')n 2022
Ti65NL20Cr 511n1023
Ti6ONL 10Fe 1 (lco 10Cr
5Mp 524 ZY 65NL25Cd
1025 TL7ONL15CulOAa
526 Zr60Co35Y 527
Zr 58NL 32Li 5C@528
Zr57NL33B1029 T
i7ONi20SilO30n 6ONi 25Cr
10 P531, T't55NL2
0Cu20M532 TL b5NL 20
Qi20Sn 533 TL50Zr 1
0E3e 20Cu? 5 P 534
TL50Zγ7ONi20 intestine 10V 58 535
TL50Be20Cu20i%+5SL
536 Zr50Mn2ONL20Co1
037 TL6ONL20Ta 10B 70 Example 2 Adhesive substrate, purity 99.8%, t5mm x 45mm
, using an alumina plate with a thickness of 3 m1n, and using 5t JS-304 with a thickness of 6 nm +
After polishing to 950°C to 1050°C in dry hydrogen, insert the foil brazing filler metal No. 3 in Table 1 between the two.
Bonding was carried out by holding at various temperatures for 5 minutes in the temperature range of .

For comparison, TL powder and NL powder (both 300 mesh powder) with the same composition as the tropical brazing filler metal of positive 3 according to the present invention are also shown.
Bonding was carried out under the same conditions using a conventional brazing filler metal made of a mixed powder of 1- and 2-3% with an organic binder as paste 1-.

After the bonded board was bisected at the center by a plane C perpendicular to the bonding surface, the bonded substrate and other adhered members were pulled in the opposite direction, and the shear fracture stress at this time was measured. The results are shown in FIG. 1, where the case of the foil strip brazing material of the present invention is shown by a circle, and the case of a conventional paste brazing material is shown by a mark.

As is clear from FIG. 1, 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 3 A poly-metal plate with a size of 15 mm x 15 mm and a thickness of 3 cylinders was used as the adhesive substrate, and a 6+um x
6mm.

Using a metal plate shown in Table 2 with a thickness of 3 ml, rub the contact surface of each W by 100 mm, and then apply a foil band brazing filler metal not shown in Table 2 between the two. insert,
980℃-1 under vacuum of 5 x 16-5 mmt-10
Thirteen sets of adhesion tests were conducted in which adhesives were bonded by holding them at various temperatures within a temperature range of 300° C. for 5 minutes.

After bonding, the board was divided into two by a plane perpendicular to the center C' bonding surface, and the bonding substrate and the adhered member were pulled in the opposite direction, and the shear fracture stress at this time was measured. The results are shown in Table 2 along with each bonding substrate, metal type of the bonded member, foil strip M, and bonding temperature.

From Table 2, it can be seen that the foil strip wax according to the present invention can bond metals together, which is difficult to bond with conventional wax wires, and has high adhesive strength using IW.

Margin below Table 2 Margin below Example 4 A ceramic grade shown in Table 3 with 15 books x 15 mm and a thickness of 3 mm was used as the bonding substrate, and the bonded member was 6 mm x
Using the metal plates shown in Table 3 with a thickness of 6 mm and a thickness of 3 mm, each adhesive surface was polished to b i ooo with emery paper, then a foil band wax not shown in Table 3 was inserted between the two, and dried. Thirty-four sets of adhesion tests were carried out in hydrogen, in which adhesion was performed by holding at various temperatures in the temperature range of 980° C. to 1300° C. for 10 minutes.

After bonding, the board was placed on three sides with the center perpendicular to the joint surface, and the bonding base and the bonded member were pulled in opposite directions, and the shear fracture stress at this time was measured. The results are based on each bonding substrate, ceramic and metal types of the bonded parts, foil strip layer, bonding temperature,
and are shown in Table 3.

Table 3 shows that the foil strip wax shrine according to the present invention is capable of adhering ceramics and metals in various combinations and has high adhesion strength.

Margins below Table 3 Example 5 A ceramic plate with dimensions shown in Table 4 of 15 mm x 15 mm and a width of 3 mm was used as the bonding substrate, and a 6 m
Using the 1 ceramic plate shown in Table 4, m x 6 mm, thickness 3 mm, each adhesive surface was 14.100 mm with F1-no paper.
After polishing to 0, the foil shown in Table 4 was inserted between the two, and under a vacuum of 5 x 10-5 mmH (110
Seven sets of adhesion tests were conducted at various temperatures (from 0°C to 1300°C) and were held for 5 minutes before bonding.

After bonding, the board was divided into three sides at the center in a plane perpendicular to the bonding surface (this), and the bonding substrate and the bonded BB material were pulled in opposite directions, and the shear fracture stress at this time was determined as 1Il11.The results are for each bonding substrate , the ceramic type of the adhered member, the foil banding temperature, and the contact temperature are shown in Table 4.

From Table 4, it can be seen that the bonding of the foil 4x1 wax U-ceramics of the various combinations U according to the present invention can easily achieve a high adhesive strength.

Table 4 Margin below

[Brief explanation of drawings]

FIG. 1 is a graph showing the relationship between bonding temperature and shear fracture stress.

Claims (1)

[Claims] At least one of 1 Ti, Zr, and Hf is 2
Contains 5 at% to 80 at%, the remainder Go, NL,
Liquid quenched alloy foil strip for J (J) consisting of at least one of Fe, Be and unavoidable impurities.
5 atomic %・~8080 atoms Select at least 1:) 1 group within the limits of each group from the following groups and combine l F 30 atomic %
Below, G. A liquid quenched alloy foil strip for use in brazing pipes containing at least 10 atomic % of at least one of Nj, Fe, and Be, and 100 atomic % in total including unavoidable impurities. 20 at% of at least one of aPd, Rh, and Cu
Hereinafter, t) Cr, 1%, W, V, Nb, T
20 atomic % or less of at least one of a, Ma+, 30 atomic % or less of at least one of CAg and Au, 10 atomic % of at least one of dSc, Y, and La group.
Hereinafter, at least one of e B , SL, Ca , P , As , and Sb is contained at 15 atomic % or less, f /V , Ca , In , STl , Cd , and Z
10 atomic % or less of at least one of n.