CN104772578B - A kind of solder for including titanium zirconium cupro-nickel - Google Patents

Abstract

The present invention relates to a kind of solder that can reduce brazing filler metal melts temperature, and it includes 10 20wt% zirconium, 10 20wt% copper, 10 20wt% nickel, and the titanium of surplus.The invention further relates to a kind of solder for improving wetability, and it includes titanium, zirconium, copper, nickel and lanthanum.

Description

A kind of solder including titanium-zirconium-copper-nickel

technical field

The invention relates to a brazing filler metal comprising titanium-zirconium-copper-nickel, in particular to a brazing filler metal comprising titanium-zirconium-copper-nickel-lanthanum.

Background technique

Titanium is an important structural metal developed in the 1950s. Titanium and titanium alloys have been widely used in aviation, aerospace, rockets, and artificial It is widely used in industrial sectors such as satellite and shipbuilding.

As an excellent structural material, titanium and titanium alloys have developed rapidly although they have been used for a short time, which is inseparable from the rapid development of aviation and aerospace technology and their excellent performance. Therefore, it has also been highly valued as a brazing filler metal for titanium and titanium alloy brazing.

There are many kinds of solder used for brazing titanium and titanium alloys, which can be divided into four categories: silver-based, palladium-based, aluminum-based, and titanium-based. Among them, aluminum-based solder brazing titanium alloy will form brittle and hard intermetallic compounds at the brazing joint, and the joint performance is poor; both silver and palladium are precious metals, and the cost of silver-based solder and palladium-based solder is relatively high. It is not suitable for large-scale production, and the performance of the joint is also poor; and the titanium-based solder has the best wetting performance and fluidity like the titanium alloy matrix, and can achieve brazed welds with performance similar to that of the base metal. Among all titanium-based solders, Ti-Cu-Ni alloys are widely used. However, the melting temperature of Ti-Cu-Ni solder is relatively high in the brazing process, and the titanium alloy will undergo phase transformation during brazing at high temperatures, which will cause damage to the titanium alloy base material and affect the performance of the brazed joint.

Contents of the invention

In order to overcome the shortcomings in the prior art, zirconium (Zr) can be added to the titanium-based solder, the most widely used Ti-Cu-Ni alloy, Zr can be infinitely solid-soluble with Ti, and Zr can not be added to Ti. A brittle phase is produced, therefore, a larger amount of Zr is allowed to be added. In addition, Zr is one of the main strengthening elements of titanium alloys, which can increase the alloy strength without significantly reducing the plasticity of titanium alloys. Therefore, one of the present inventions provides a solder composition capable of lowering the melting temperature of the solder, which includes zirconium, copper, nickel and titanium.

After a lot of research by the inventors, it has been found that the content of each component of the solder is controlled within a certain range, which can achieve better performance of the solder, that is, the solder includes 10-20wt% zirconium, 10-20wt% copper, 10-20wt% nickel, and the rest titanium. Preferably, the solder includes 10-15 wt% zirconium, 10-15 wt% copper, 10-15 wt% nickel, and the balance titanium. The melting temperature range of the solder is 830-880°C.

During the research process, the inventors found that the wettability of the solder was greatly improved when adding lanthanum to the above-mentioned solder, especially when the above-mentioned solder included 0.5-2.5wt% lanthanum , The wettability of the solder has reached an excellent state. Therefore, in a specific embodiment, the solder also includes lanthanum, especially 0.5-2.5 wt% of lanthanum, preferably the solder includes 1.0-1.5 wt% of lanthanum, the improvement of solder wettability can Greatly improve the spreading performance and filling ability of solder.

In a preferred embodiment, the solder includes 15 wt% zirconium, 15 wt% copper, 15 wt% nickel, 1.5 wt% lanthanum, and 53.5 wt% titanium. At this time, the brazing filler metal has better wettability, the joint structure brazed with the brazing filler metal is more dense and continuous, and the weld seam and the master material achieve better metallurgical bonding; at the same time, the joint brazed with the brazing filler metal also has The higher shear strength reaches 269.4MPa. In short, considering the brazing temperature, the wettability of the solder and the structure and performance of the brazed joint, it is determined that the most preferred solder is Ti-15Zr-15Cu-15Ni-1.5La solder.

The second invention also provides a brazing product, which includes the above-mentioned brazing filler metal for welding.

The third aspect of the present invention also provides the application of the above solder in welding.

Description of drawings

Fig. 1 is a diagram showing the wettability test (spreading area) results of some solders in Example 1 of the present invention. It adopts a digital camera to take pictures, and after importing the obtained pictures into CAD software, the wetted area is measured to be 26.04mm ² .

Fig. 2 is a diagram showing the wettability test (spreading area) results of some solders in Example 3 of the present invention. It adopts a digital camera to take pictures, and after importing the obtained pictures into CAD software, the wetted area is measured to be 29.37mm ² .

Fig. 3 is a graph showing the wettability test (spreading area) results of some solders in Example 6 of the present invention. It adopts a digital camera to take pictures, and after importing the obtained pictures into CAD software, the wetted area is measured to be 50.24mm ² .

Fig. 4 is a graph showing the wettability test (spreading area) results of some solders in Example 8 of the present invention. It adopts a digital camera to take pictures, and after importing the obtained pictures into CAD software, the wetted area is measured to be 33.05mm ² .

Fig. 5 is a photograph of the joint structure of titanium alloy brazed with the brazing material (a) of Example 3 of the technical solution of the present invention and the brazing material (b) of Example 8 taken by a scanning electron microscope CS3400.

Figure 6 Schematic diagram of the assembly of the brazed joint.

detailed description

The present invention will be described in detail below in conjunction with the embodiments and accompanying drawings.

Example 1

Weighing 70.0 parts by mass of titanium sponge with a purity greater than 99.95%, 10 parts by mass of electrolytic pure copper with a purity greater than 99.99%, 10 parts by mass of electrolytic pure nickel with a purity greater than 99.99%, and 10 parts by mass of zirconium with a purity greater than 99.99%.

The weighed brazing material was placed in a water-cooled copper crucible in an argon-protected non-consumable electric arc furnace. Before smelting, vacuumize the furnace to 5×10 ^-1 Pa, and then protect it with argon. When melting the sample, in order to ensure the uniformity of the chemical composition of the solder, the sample in the water-cooled copper crucible was repeatedly smelted 3-4 times. Titanium alloy bulk solder was obtained after arc melting, and the bulk solder was processed into thin sheet solder with a size of 15mm×2mm×0.8mm by wire electric discharge cutting. Then, use 400# SiC water sandpaper to polish the solder, finally make each surface of the solder bright, and use acetone reagent to perform ultrasonic cleaning, so as to obtain the Ti-Zr-Cu-Ni solder of the present invention.

Example 2

Weigh 62.0 parts by mass of titanium sponge with a purity greater than 99.95%, 15 parts by mass of electrolytic pure copper with a purity greater than 99.99%, 10 parts by mass of electrolytic pure nickel with a purity greater than 99.99%, and 13 parts by mass of zirconium with a purity greater than 99.99%.

The preparation method of brazing filler metal is the same as embodiment 1.

Example 3

Weighing 55.0 parts by mass of titanium sponge with a purity greater than 99.95%, 15 parts by mass of electrolytic pure copper with a purity greater than 99.99%, 15 parts by mass of electrolytic pure nickel with a purity greater than 99.99%, and 15 parts by mass of zirconium with a purity greater than 99.99%.

The preparation method of brazing filler metal is the same as embodiment 1.

Example 4

Weighing 47.0 parts by mass of titanium sponge with a purity greater than 99.95%, 15 parts by mass of electrolytic pure copper with a purity greater than 99.99%, 20 parts by mass of electrolytic pure nickel with a purity greater than 99.99%, and 18 parts by mass of zirconium with a purity greater than 99.99%.

The preparation method of brazing filler metal is the same as embodiment 1.

Example 5

Weighing 40.0 parts by mass of titanium sponge with a purity greater than 99.95%, 20 parts by mass of electrolytic pure copper with a purity greater than 99.99%, 20 parts by mass of electrolytic pure nickel with a purity greater than 99.99%, and 20 parts by mass of zirconium with a purity greater than 99.99%.

The preparation method of brazing filler metal is the same as embodiment 1.

Example 6

Weigh 69.5 parts by mass of titanium sponge with a purity greater than 99.95%, 10 parts by mass of electrolytic pure copper with a purity greater than 99.99%, 10 parts by mass of electrolytic pure nickel with a purity greater than 99.99%, 10 parts by mass of zirconium with a purity greater than 99.99%, and The purity of 0.5 parts by mass is greater than 99.95% block lanthanum.

The preparation method of brazing filler metal is the same as embodiment 1.

Example 7

Weigh 62.0 parts by mass of titanium sponge with a purity greater than 99.95%, 15 parts by mass of electrolytic pure copper with a purity greater than 99.99%, 10 parts by mass of electrolytic pure nickel with a purity greater than 99.99%, 12 parts by mass of zirconium with a purity greater than 99.99%, and The purity of 1.0 parts by mass is greater than 99.95% block lanthanum.

The preparation method of brazing filler metal is the same as embodiment 1.

Example 8

Weighing 53.5 parts by mass of titanium sponge with a purity greater than 99.95%, 15 parts by mass of electrolytic pure copper with a purity greater than 99.99%, 15 parts by mass of electrolytic pure nickel with a purity greater than 99.99%, 15 parts by mass of zirconium with a purity greater than 99.99%, and The purity of 1.5 parts by mass is greater than 99.95% block lanthanum.

The preparation method of brazing filler metal is the same as embodiment 1.

Example 9

Weighing 45.5 parts by mass of titanium sponge with a purity greater than 99.95%, 15 parts by mass of electrolytic pure copper with a purity greater than 99.99%, 20 parts by mass of electrolytic pure nickel with a purity greater than 99.99%, 18 parts by mass of zirconium with a purity greater than 99.99%, and The purity of 1.5 parts by mass is greater than 99.95% block lanthanum.

The preparation method of brazing filler metal is the same as embodiment 1.

Example 10

Weighing 38 parts by mass of titanium sponge with a purity greater than 99.95%, 20 parts by mass of electrolytic pure copper with a purity greater than 99.99%, 20 parts by mass of electrolytic pure nickel with a purity greater than 99.99%, 20 parts by mass of zirconium with a purity greater than 99.99%, and The purity of 2.5 parts by mass is greater than 99.95% block lanthanum.

The preparation method of brazing filler metal is the same as embodiment 1.

Example 11

Through the DSC test of the brazing filler metal, it is found that the melting temperature range of the brazing filler metal is 830-880°C. It can be seen that the melting point of the brazing filler metal of the present invention is greatly lowered compared with the Ti-Cu-Ni based solder filler metal. The wetting angle of the solder was tested by a wetting angle meter. Then, the brazing process is determined according to the wetting behavior of the solder, and the brazing experiment is carried out.

Example 12

The method of brazing using the above solder is:

(1) Assembling, use the fixture to realize the lap joint between the titanium alloy specimens, select the assembly gap of 0.1mm, place the thin sheet brazing filler metal at the position where the brazing filler metal and the base metal are heated more evenly, and cling to the base metal, Try to make the molten solder fill the gap in the brazing seam by gravity, and its assembly diagram is shown in Figure 6;

(2) Heating, put the assembled test piece into the vacuum brazing furnace to evacuate, and at the same time heat up the resistance furnace, heat it to the brazing temperature of 930-950°C, keep it warm for 5 minutes to connect the titanium alloy/titanium alloy joint, keep it warm , and then cooled to room temperature with the furnace.

According to the national standard GB/T 2651—2008/ISO 4136:2001 of the People's Republic of China, each brazing sample is processed into a standard tensile sample, and then the mechanical properties of the joint of the brazing sample are tested using a micro-controlled electronic universal testing machine .

Table 1 shows the mechanical properties of the brazed titanium alloy/titanium alloy joint according to the embodiment of the technical solution of the present invention. It can be seen that the brazed sample joint is obtained by vacuum brazing at 930-950 °C using thin-sheet solder, and the room temperature shear strength of the corresponding brazed joint reaches 250-295 MPa, and it can be seen from Fig. The joint structure of -15Cu-15Ni-1.5La solder brazing is dense and continuous, and the weld and the base metal have achieved good metallurgical bonding.

Table 1

Table 2

Table 2 shows the wetting angles corresponding to various solder components. The smaller the wetting angle, the better the wettability. From the results, it can be seen that the addition of La element greatly improves the wettability of the solder. At the same time, the brazing joint using the brazing material of Example 8 also has a relatively high shear strength, reaching 269.4 MPa.

Based on the brazing temperature, the wettability of the solder, and the structure and performance of the brazed joint, the optimal solder is determined to be the Ti-15Zr-15Cu-15Ni-1.5La solder in Example 8.

Claims (4)

1. A brazing material, which comprises 10-15wt% of zirconium, 10-15wt% of copper, 10-15wt% of nickel and the balance of titanium, and further comprises 1.0-1.5wt% of lanthanum. 2. The solder according to claim 1, characterized in that the solder comprises 15 wt% zirconium, 15 wt% copper, 15 wt% nickel, 1.5 wt% lanthanum, and 53.5 wt% titanium. 3. A brazing product comprising the brazing filler metal according to claim 1 or 2 for soldering. 4. The application of the brazing filler metal as claimed in claim 1 or 2 in welding.