CN113798731A - Amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy, and preparation method and application thereof - Google Patents
Amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy, and preparation method and application thereof Download PDFInfo
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- 229910002482 Cu–Ni Inorganic materials 0.000 title claims abstract description 118
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 109
- 239000000956 alloy Substances 0.000 title claims abstract description 109
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 94
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000005219 brazing Methods 0.000 claims abstract description 273
- 239000000945 filler Substances 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 75
- 229910052751 metal Inorganic materials 0.000 claims abstract description 68
- 239000002184 metal Substances 0.000 claims abstract description 66
- 239000010936 titanium Substances 0.000 claims abstract description 66
- 238000002844 melting Methods 0.000 claims abstract description 60
- 230000008018 melting Effects 0.000 claims abstract description 60
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 49
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 46
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
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- 239000002994 raw material Substances 0.000 claims abstract description 9
- 230000007704 transition Effects 0.000 claims abstract description 8
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
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- 238000004364 calculation method Methods 0.000 claims description 17
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003723 Smelting Methods 0.000 claims description 4
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/32—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
- B23K35/325—Ti as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Pressure Welding/Diffusion-Bonding (AREA)
Abstract
The invention discloses an amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy, a preparation method and application thereof. The weight percentages of the raw materials are as follows: 30-70% of Zr, 3-14% of Cu, 13-35% of Ni and the balance of Ti. The melting point of the brazing filler metal is 761-821 ℃, the beta transition temperature of the brazing filler metal is 79-139 ℃ lower than that of the SP700 titanium alloy, and the phase of the brazing reaction layer formed by combining the Ti-Zr-Cu-Ni brazing filler metal alloy with the SP700 titanium alloy in the brazing reaction process is as follows: a NiTiZr phase with the length-diameter ratio of 3.1 and the mass fraction of 17-47 percent; cu (Ti, Zr) with aspect ratio of 1.9 and mass fraction of 35-59%2Phase (1); a Bcc phase with the mass fraction not more than 35 percent and NiZr with the mass fraction not more than 13 percent2Phase (1); does not contain brittle phase (Cu, Ni) (Ti, Zr) phase. Preparing the brazing filler metal into an amorphous brazing foil strip with the thickness of 0.01-0.1 mm by adopting an amorphous strip throwing method, lapping with SP700 titanium alloy, brazing at the temperature of 850-890 ℃, and preserving heatAnd (5) obtaining a soldered joint in 60 min. The average weld thickness of the brazing joint is 50-100 microns, the highest room temperature shear strength is 450-576 MPa, and the use requirements of SP700 titanium alloy brazing are met.
Description
Technical Field
The invention relates to a Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy and a brazing method, belonging to the field of titanium alloy smelting.
Background
The brazing base material SP700 titanium alloy is an important alloy applied to the field of aerospace, and in recent years, the SP700 titanium alloy has attracted much attention due to the superplasticity exhibited at 900 ℃. However, the titanium alloy is expensive in manufacturing cost and limits further popularization and application of the titanium alloy, so that the titanium alloy is an effective way for producing composite materials, welding the titanium alloy and other materials to form a composite structure and fully exerting excellent performance of the titanium alloy and popularizing the application of the titanium alloy. The SP700 titanium alloy is an (alpha + beta) type titanium alloy rich in beta phase by adding beta phase stabilizing elements Mo and Fe on the basis of the composition of an aeronautical titanium alloy-Ti-6 Al-4V (TC 4). After the addition of these two elements, the SP700 titanium alloy has a beta phase transition temperature of 900 ℃. The brazing temperature of the existing titanium-based brazing filler metal is between 900 and 940 ℃, so that the alpha phase of a matrix close-packed hexagonal structure is converted into the beta phase of a body-centered cubic structure, and the shearing performance of a joint is reduced. Therefore, aiming at the brazing characteristics of the SP700 titanium alloy, the design of a novel brazing filler metal composition is urgent.
The components of the titanium alloy solder are mainly divided into two parts of a solder matrix element and an additive element. Different matrix elements can cause the change of brazing conditions such as brazing temperature, brazing heat preservation time and the like; different added elements can generate different intermetallic compounds at the brazing joint, and influence the shearing performance at the joint. In the brazing temperature range of the current brazing filler metal, only two types of brazing filler metals, namely Ag-based brazing filler metal and Ti-Zr-based brazing filler metal, meet the requirement in the expected temperature range (800-900 ℃). Prior document 1 discloses "novel amorphous solder for brazing titanium and titanium alloys" to Ningxing Longman et al, and uses Ag-based and Ti — Zr-based solders for brazing SP700 titanium alloys. However, because the difference between the components of the Ag-based brazing filler metal and the base metal is large, the ductility of the Ag-based brazing filler metal at a brazing interface is poor, and the Ag-based brazing filler metal cannot be completely wetted with the base metal, so that the strength of a brazed joint is far lower than that of the brazing base metal; the Ti and Zr elements are completely solid-dissolved in the brazing temperature range and are relatively close to the components of the brazing base metal, so that the brazed joint with the shear strength of 280MPa can be obtained. For the reasons, the most practical brazing connection method at present is to adopt Ti-Zr-based brazing filler metal to perform SP700 titanium alloy brazing connection.
By using Ti-Zr based brazing filler metalWhen the SP700 titanium alloy is brazed, in selecting the additive elements, Al, V and other elements similar to those of the base metal attract considerable attention in view of rationality and joining efficiency. Prior document 2 discloses Increasing Ti-6 Al-4V brazedjointingstrongth equivalent to the base metal Ti and Zr Amorphous filealloys by Ganjeh et Al, and a welded structure is formed by using Ti-42 Al-24V brazing filler metal and Ti-6 Al-4V titanium alloy. However, from the brazing results, Al is formed at the interface between the two brazes3Ti2And Al-Ti intermediate brittle phase is equal, so that a fracture path is formed in the shearing process, and the shearing strength of the brazed joint can only reach 196 MPa.
In order to avoid the formation of an Al-Ti intermediate brittle phase, a method of adding Cu and Ni elements can be adopted, so that the generation of the Al-Ti intermediate phase is effectively reduced; in addition, the addition of Cu and Ni elements can also realize the technical effects of keeping the layered structure of a brazing reaction zone to be minimum at low temperature in the brazing process, delaying the growth of crystal grains and preventing the generation of a coarse Widmannstatten structure due to the growth of the crystal grains in the solidification process after the brazing is finished. Further, in conventional document 3, ("Infrared vacuum brazing of Ti-6 Al-4V and Using the Ti-15 Cu-15 Ni foil") Liaw et Al, Ti-6 Al-4V and Nb were brazed by the Infrared brazing method, and at 3600s of Infrared brazing at 970 ℃, it was realized that an intermediate alloy phase formed between Cu, Ni and Ti elements hardly existed in the brazing sample. However, according to the shear test results, cracks all propagate along the Nb matrix and have a typical ductile pitting appearance, and the Ti-6 Al-4V side shear strength can only reach 230 MPa.
As can be seen from the above analysis of the prior art, the following technical problems still exist:
1. the existing Ti-Zr-Cu-Ni brazing filler metal designed in the prior art has higher brazing temperature, can only meet the brazing connection of Ti-6 Al-4V, and cannot be suitable for SP700 titanium alloy with the beta transition temperature of 900 ℃. Specifically, the prior document 4 is a chinese patent with patent application number 201611094879.6, and discloses a solder alloy: the Ti-Zr-Cu-Ni-Co-Fe brazing filler metal has the melting point value of 858-; prior document 5 is a chinese patent with patent application number 201911003215.8, and discloses a solder alloy, the melting point value is 850-. When the brazing filler metal is used for brazing SP700 titanium alloy at 900 ℃ or higher, phase transformation of a brazing base material can be caused, and when the brazing temperature is reduced to be below 900 ℃, the brazing filler metal can not be completely melted in the brazing process, a large brittle phase is formed in the solidification process, and the shear strength of a brazed joint is reduced.
2. In the prior art, after Cu and Ni elements are introduced, the phase transformation can occur at the brazing joint to generate (Cu, Ni) (Ti, Zr) brittle phases. Specifically, prior document 6 discloses Infrered brazing Ti-6 Al-4V and SP700 alloys using the Ti-20 Zr-20 Cu-20 Ni brazing alloy of Chang et Al, and a brazing experiment is performed on the Ti-20 Zr-20 Cu-20 Ni brazing alloy. When a (Cu, Ni) (Ti, Zr) phase appears at the brazing joint, a thin-walled structure is formed at the brazing joint interface, the structure is cracked due to insufficient brazing temperature, and the shear strength is only 391 MPa.
In summary, for the brazing process of the SP700 titanium alloy, the problems to be solved by the existing Ti-Zr-Cu-Ni system brazing filler metal are as follows:
1. the brazing temperature of the melting point of the existing brazing filler metal is higher than the brazing requirement temperature of SP700 titanium alloy, the melting point of the brazing filler metal needs to be further reduced, and the optimal melting point of the brazing filler metal is lower than 800 ℃;
2. brittle phases (Cu, Ni) (Ti, Zr) need to be avoided in the brazing process so as to avoid forming a thin-wall structure at the interface of a brazed joint and reduce the performance of the joint;
3. the technological parameters including the brazing temperature and the brazing heat preservation time are not matched with the components of the brazing filler metal in the brazing process, so that the strength of a brazing joint cannot reach more than 400MPa, and the brazing joint with the brazing layer thickness of less than 100 micrometers cannot be obtained;
4. the cost is too high, which hinders the practical application of the product.
Therefore, according to the common requirements of both the brazing melting point value and the brittle phase, a Ti-Zr-Cu-Ni brazing alloy with the melting point value of 761-821 ℃ and the brazing temperature of 850-890 ℃ is developed, the brittle phase (Cu, Ni) (Ti, Zr) is avoided, the strength of a brazing joint can reach more than 400MPa, and the thickness of a brazing layer is less than 100 microns, so that the Ti-Zr-Cu-Ni brazing alloy has obvious application value and economic value and becomes a technical problem to be solved urgently.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art, and provides a Ti-Zr-Cu-Ni brazing filler metal component and a brazing method. The brazing filler metal is suitable for brazing of SP700 titanium alloy, and has the advantages of melting temperature lower than 800 ℃ and good performance of avoiding harmful phases (Cu, Ni) (Ti, Zr) in the brazing process.
In order to realize the purpose of the invention, the invention adopts the following sub-concepts:
and (3) obtaining the target Ti-Zr-Cu-Ni solder component by using a computer system, adopting a CALPHAD method and adopting a method combining experimental test and phase diagram analysis. According to the common requirements of both brazing melting point value and brittle phase, a melting point value is 761-821 ℃, the brazing temperature is 850-890 ℃, the strength of the brazing joint can reach more than 400MPa by avoiding the brittle phase (Cu, Ni) (Ti, Zr).
According to the inventive concept, the invention adopts the following technical scheme:
an amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy comprises the following components in percentage by mass: 30-70% of Zr, 3-14% of Cu, 13-35% of Ni and the balance of Ti; the obtained amorphous Ti-Zr-Cu-Ni solder alloy is in a foil strip shape, and the thickness is 0.01-0.1 mm; in the process of brazing reaction, the phase contained in a brazing reaction layer formed by combining the Ti-Zr-Cu-Ni brazing filler metal alloy and the SP700 titanium alloy is NiTiZr phase and Cu (Ti, Zr)2Phase, Bcc phase and NiZr2The phase does not contain a brittle phase (Cu, Ni) (Ti, Zr).
Preferably, the aspect ratio of the NiTiZr phase in the amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy is 3.1, and the quality of the NiTiZr phaseThe weight fraction is 17-47%; cu (Ti, Zr)2Aspect ratio of phase 1.9, Cu (Ti, Zr)2The mass fraction of the phase is 35-59%; bcc phase mass fraction not more than 35%, NiZr2The mass fraction of phases is not more than 13%.
Preferably, the melting point of the amorphous Ti-Zr-Cu-Ni solder alloy is 761-821 ℃ which is lower than the beta transition temperature of the SP700 titanium alloy by 79-139 ℃, and the amorphous Ti-Zr-Cu-Ni solder alloy is contacted with the SP700 titanium alloy as a base material in a liquid phase to increase the brazing surface area; the amorphous Ti-Zr-Cu-Ni brazing alloy is used as the brazing filler metal, and the SP700 base metal titanium alloy is welded to obtain the brazing joint with the strength not lower than 400 MPa.
The invention discloses a preparation method of an amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy, which comprises the following steps:
according to the mass fraction of the Ti-Zr-Cu-Ni solder alloy: the Ti-Zr-Cu-Ni solder alloy comprises the following components in percentage by mass: 30-70% of Zr, 3-14% of Cu, 13-35% of Ni and the balance of Ti; weighing pure Ti, pure Zr, pure Cu and pure Ni as raw materials; wherein the addition amount of pure Cu is 105% of the mass fraction of the Cu content; then, carrying out vacuum melting on the raw materials to obtain a Ti-Zr-Cu-Ni solder alloy ingot; and preparing the Ti-Zr-Cu-Ni brazing alloy ingot into a Ti-Zr-Cu-Ni brazing alloy foil strip.
Preferably, the mass fraction of the Ti-Zr-Cu-Ni solder alloy is obtained by designing the Ti-Zr-Cu-Ni alloy solder by the following method:
calculating a phase diagram of the Ti-Zr-Cu-Ni solder alloy by using a computer system and adopting a CALPHAD method, and screening a melting point contour map according to a phase diagram database of the Ti-Zr-Cu-Ni alloy to determine the Zr content meeting the requirement of a melting point value; and calculating the phase type and phase fraction in the solidification process through a solidification path, and obtaining the component proportion of the Ti-Zr-Cu-Ni solder alloy without brittle phases (Cu, Ni) (Ti, Zr) in the phase according to the calculation result.
Preferably, the solidification path of the Ti-Zr-Cu-Ni alloy under different Zr element addition amounts is calculated through a Ti-Zr-Cu-Ni alloy phase map database, the phase types and phase fractions in the solidification processes of different solders are counted, and whether brittle phases (Cu, Ni) (Ti, Zr) are contained in the phase is judged according to the calculation result; if the precipitated phase contains brittle phases (Cu, Ni) (Ti, Zr), adjusting the content proportion of elements in the alloy components, returning and recalculating; if the precipitated phase does not contain brittle phases (Cu, Ni) (Ti, Zr), the specific solder alloy components are recorded, and preparation and soldering experiments are carried out for verification.
Preferably, the method for establishing the Ti-Zr-Cu-Ni alloy phase map database comprises the following steps: a CALPHOD method is adopted, a ternary phase diagram of Ti-Cu-Zr, Ti-Ni-Zr and Ti-Cu-Ni is obtained through experiments, a titanium-rich angle phase-related system of a Ti-Zr-Cu-Ni quaternary system is obtained through extrapolation calculation of the ternary system, thermodynamic information of the melting point, the beta transition temperature and the phase content of the brazing filler metal of the Ti-Zr-Cu-Ni system is obtained, and the relation between the components, the melting point, the phase composition and the phase content is obtained.
Preferably, the method for determining the Zr content meeting the melting point value requirement by screening the melting point contour map is a secondary screening method, which comprises the following steps:
firstly, calculating a Ti-Zr-Cu-Ni alloy liquid phase projection diagram under different Zr element adding amounts through a Ti-Zr-Cu-Ni alloy phase diagram database, and calculating a corresponding melting point contour diagram according to the projection diagram; then, carrying out first screening, wherein the specific method comprises the following steps:
carrying out first screening according to the requirement that the melting point value is lower than 800 ℃ by using the gradient that the addition amount of Zr element is 10%; and then carrying out secondary screening, wherein the specific method comprises the following steps:
and (4) carrying out secondary screening according to the requirement that the melting point value is lower than 800 ℃ by a gradient that the addition amount of the Zr element is 1%.
Preferably, the vacuum melting method comprises the following steps:
vacuum arc melting furnace is adopted, and the vacuum is pumped to not less than 5 multiplied by 10-3And (3) introducing argon after the vacuum degree of the Pa value is reached, repeatedly smelting for 3-5 times in an arc heating mode to ensure that the alloy components are uniform, and then cooling along with the furnace to obtain a Ti-Zr-Cu-Ni solder alloy ingot.
Preferably, the preparation method of the Ti-Zr-Cu-Ni brazing alloy foil strip comprises the following steps:
crushing a Ti-Zr-Cu-Ni brazing alloy ingot, heating the Ti-Zr-Cu-Ni brazing alloy ingot in an induction heating mode, and then performing spray casting by adopting an amorphous strip casting method under the conditions that the rotating speed of a copper wheel is 2000-2500 r/s and the spray pressure is 0.02-0.05 MPa to obtain a continuous Ti-Zr-Cu-Ni brazing alloy foil strip.
The application of the amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy adopts the amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy as a solder to weld the SP700 titanium alloy as a base material, and comprises the following steps:
(1) brazing material preparation and pretreatment:
placing the amorphous Ti-Zr-Cu-Ni solder alloy in acetone with the temperature of not less than 50 ℃ for ultrasonic cleaning; simultaneously, grinding and polishing the surface of the brazing parent metal and ultrasonically cleaning in acetone;
(2) the brazing treatment process comprises the following steps:
lapping the amorphous Ti-Zr-Cu-Ni brazing alloy and a brazing base metal together by using a clamp, and adhering the amorphous Ti-Zr-Cu-Ni brazing alloy to the surface of the brazing base metal; then, at not higher than 5 × 10-3The vacuum degree of the Pa value, the heating rate of 10-15 ℃/min, the brazing temperature of 850-; the average weld thickness of the obtained brazing joint is 50-100 microns, and the shear strength is 450-576 MPa.
Preferably, in the step (1), cutting the amorphous Ti-Zr-Cu-Ni solder alloy foil strip for the SP700 titanium alloy into an amorphous Ti-Zr-Cu-Ni solder alloy sample with the thickness of 10 multiplied by 1mm, and cleaning the cut solder alloy sample in acetone at the temperature of 50 ℃ for 20 min; 2 samples of 50 x 10 mm are cut from the brazing base material, and surface grinding, polishing and ultrasonic cleaning in acetone are carried out.
Preferably, the amorphous Ti-Zr-Cu-Ni solder alloy has a melting point value of 761-821 ℃ lower than the beta transus temperature of the SP700 titanium alloy of 79-139 ℃. In the brazing reaction process, the amorphous Ti-Zr-Cu-Ni brazing filler metal alloy is combined with the SP700 titanium alloy to form the brazing reactionThe phase included in the layer is: NiTiZr, Cu (Ti, Zr)2Bcc and NiZr2The (Cu, Ni) (Ti, Zr) harmful phase is avoided, and the method is superior to the prior art.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the amorphous Ti-Zr-Cu-Ni brazing filler metal alloy for the SP700 titanium alloy does not contain a brittle phase (Cu, Ni) (Ti, Zr), the amorphous brazing foil strip with the thickness of 0.01-0.1 mm is prepared from the brazing filler metal by an amorphous strip throwing method, and is lapped with the SP700 titanium alloy, and then brazed at 850-890 ℃ and the temperature is kept for 60min to obtain a brazed joint; the average weld thickness of the brazing joint is 50-100 microns, the highest room temperature shear strength is 450-576 MPa, and the use requirements of SP700 titanium alloy brazing are met; the invention utilizes a computer system and adopts a CALPHAD method to improve the efficiency of designing and developing the amorphous Ti-Zr-Cu-Ni solder alloy;
2. the brazing temperature of the melting point of the amorphous Ti-Zr-Cu-Ni brazing filler metal alloy for the SP700 titanium alloy is lower than the brazing requirement temperature of the SP700 titanium alloy, the phase transformation of a brazing base metal cannot be induced, a large brittle phase cannot be formed, the higher shearing strength of a brazing joint can be ensured, and the welding quality and the joint performance can be ensured;
3. the technological parameters including the brazing temperature and the brazing heat preservation time in the brazing process are well matched with the components of the brazing filler metal, the strength of a brazing joint reaches more than 400MPa, the brazing joint with the brazing layer thickness of less than 100 micrometers can be obtained, and the welding technological level is improved;
4. the invention does not adopt precious metal raw materials, has low cost and is beneficial to the practical popularization and application of solder products.
Drawings
FIG. 1 shows the results of calculation of the melting point and solidification path of the brazing filler metal in example 1 of the present invention.
FIG. 2 shows the results of calculation of the melting point and solidification path of the brazing filler metal in example 2 of the present invention.
FIG. 3 shows the calculation results of the melting point and solidification path of the brazing filler metal in example 3 of the present invention.
FIG. 4 is a calculation result of melting point and solidification path of the brazing filler metal of comparative example 5 of the present invention.
FIG. 5 is an SEM photograph of the shear fracture morphology of the brazed joint in example 1 of the present invention.
FIG. 6 shows DSC test results of the solder of examples 1 to 3 of the present invention.
FIG. 7 is a microstructure photomicrograph of a braze joint in accordance with example 1 of the present invention.
FIG. 8 is a graph showing a comparison of shear strengths of brazed joints according to examples 1 to 3, comparative example 5 and comparative example 6 of the present invention.
FIG. 9 is a graph showing the square root fit of the braze soak time to the diffusion layer thickness for inventive example 1 and comparative examples 1-4.
FIG. 10 is an SEM photograph of the composition of the brazing reaction layer in example 1 of the present invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example 1:
a preparation method of an amorphous Ti-Zr-Cu-Ni solder alloy with the chemical element composition and the mass percentage that Zr content is 60%, Cu content is 10%, Ni content is 14%, and the balance is Ti comprises the following steps:
firstly, thermodynamic parameters of Ti-Zr-Cu-Ni system phases are measured through experiments to serve as calculation bases, and then corresponding thermodynamic models are established according to crystal structures of the phases;
then, establishing thermodynamic data of four ternary systems of Ti-Cu-Zr, Ti-Ni-Zr, Ti-Cu-Ni and Cu-Ni-Zr by using a computer system and a CALPHAD method according to a thermodynamic principle, a phase equilibrium law and phase diagram calculation software; establishing a high-element system through a low-element system to obtain a Ti-Zr-Cu-Ni alloy phase map database of a quaternary system;
then according to a Ti-Zr-Cu-Ni alloy phase map database, screening through a melting point contour map to determine that the Zr content meeting the requirement of the melting point value is 60 percent; calculating the phase type and phase fraction in the solidification process through a solidification path, wherein the calculation result is shown in figure 1, and the element composition and the mass percentage of the Ti-Zr-Cu-Ni solder alloy which does not contain brittle phases (Cu, Ni) (Ti, Zr) in the phase are obtained according to the calculation result, namely the Zr content is 60%, the Cu content is 10%, the Ni content is 14%, and the balance is Ti;
step 2, preparing the Ti-Zr-Cu-Ni solder alloy:
pure Ti, pure Zr, pure Cu and pure Ni are used as raw materials, and the raw materials are weighed according to the component proportion of the Ti-Zr-Cu-Ni solder alloy obtained in the step 1, wherein the addition amount of the pure Cu is 105% of the mass fraction of the Cu content; the weighed raw materials are put into a vacuum arc melting furnace, and the vacuum degree in the furnace reaches 5 multiplied by 10-3When the pressure is lower than Pa, argon is filled; repeatedly smelting for 5 times in an arc heating mode to ensure that the alloy components are uniform, then cooling along with the furnace, and taking out a brazing alloy ingot; crushing the obtained brazing alloy ingot, and heating the Ti-Zr-Cu-Ni brazing alloy in an induction heating mode;
and then after the alloy is completely melted and the liquid level fluctuates, spraying the molten alloy onto the copper wheel rotating at high speed by using an amorphous strip spinning method under the conditions that the rotating speed of the copper wheel is 2500r/s and the spraying pressure is 0.05MPa by using the air pressure difference to obtain a continuous Ti-Zr-Cu-Ni brazing alloy foil strip with the thickness of 0.1 mm.
The brazing method of the Ti-Zr-Cu-Ni brazing alloy prepared by the embodiment comprises the following steps:
firstly, cutting a 10 x 1mm sample from an amorphous solder foil, and cleaning the cut sample in acetone at 50 ℃ for 20 min; simultaneously, 2 samples of 50 mm by 10 mm are cut from the brazing base material, and surface grinding, polishing and ultrasonic cleaning in acetone are carried out;
lapping the amorphous sample and the brazing base metal together by using a clamp, and attaching the brazing filler metal sample to the surface of the brazing base metal; subsequently, the vacuum degree is reduced to less than 5X 10-3Pa, heating the sample in a brazing reaction furnace at the heating rate of 10 ℃/min until the sample is molten; after the brazing filler metal is completely melted, brazing and heat preservation time is 60min according to the brazing temperature of 890 ℃, and the brazing filler metal is fed along with furnace cooling conditions after brazingAnd (5) performing brazing to obtain a brazed joint.
Experimental test analysis:
in order to test the actual melting point values of the solder, the designed solder was subjected to DSC testing, the results of which are shown in fig. 6. Compared with the calculation result, the actual melting point of the brazing filler metal is 775 ℃, and the brazing filler metal can be completely melted by selecting 890 ℃ for a brazing experiment. The shear performance of the obtained brazing joint is evaluated, the average value of the room-temperature shear strength of the brazing joint is 576MPa, and the fracture morphology is shown in figure 5. In order to observe the microstructure and the phase composition of the brazed joint, the microstructure and the morphology of the brazed joint obtained in the embodiment are analyzed by a scanning electron microscope, and the main phase composition of the microstructure and the phase composition are as follows: NiTiZr and Cu (Ti, Zr)2The phase comprises NiTiZr with the length-diameter ratio of 3.1 and the mass percent of 47 percent, Cu (Ti, Zr) with the length-diameter ratio of 1.9 and the mass percent of 53 percent2The composition of the brazing reaction layer phases is shown in fig. 10. Fine needle-shaped widmannstatten structures are generated in the solder solidification process, the thickness of a brazing layer reaches 66 micrometers, and the appearance of a joint is shown in figure 7.
The Ti-Zr-Cu-Ni brazing filler metal foil strip prepared by the embodiment has the advantages of bright surface, neat edge and good toughness, and the melting temperature of the brazing filler metal is 775 ℃. The solder prepared by the embodiment is used for carrying out vacuum brazing connection on the SP700 titanium alloy at the brazing temperature of 890 ℃ and under the condition of keeping the temperature for 60min, and the average value of the room-temperature shear strength of a brazed joint is 576 MPa.
In the brazing process, the change of the brazing heat preservation time can influence the diffusion degree of elements, and is mainly reflected in the change of the diffusion rate. Since the diffusion rate of the element cannot be directly measured, the method for characterizing the thickness of the diffusion layer is adopted for analysis. The relation between the thickness of the diffusion layer and the brazing heat preservation time is calculated by adopting a kinetic model, and the selected model is a solid-phase reaction kinetic model. According to the model, under the diffusion-controlled interface solid-liquid phase reaction condition, the square of the thickness (x) of the reaction layer is in direct proportion to the brazing heat preservation time (t) within 30-180 min. Thus, comparative examples 1, 2, 3, 4 are provided below, comparing experiments of the effect of different holding times on the braze layer thickness to find the corresponding braze reaction layer thickness at different holding times:
comparative example 1
A Ti-Zr-Cu-Ni amorphous solder alloy for SP700 titanium alloy, the steps not specifically described being the same as those of example 1 except that:
the brazing holding time was 30min, and the composition of the brazing filler metal alloy was the same as in example 1.
Analysis of experimental tests
In order to obtain the thickness of the brazing layer of comparative example 1, the phase composition of the brazed joint obtained in this example was analyzed by a scanning electron microscope, and the (Ti, Zr) phase was not completely melted in the brazing filler metal, the interface position between the brazing filler metal and the base metal was not completely reacted, and no intermediate structure was formed during the solidification process. The brazing layer of comparative example 1 was 167 μm thick. The average value of the room-temperature shear strength of the soldered joint is 261 MPa.
Comparative example 2
A Ti-Zr-Cu-Ni amorphous solder alloy for SP700 titanium alloy, the steps not specifically described being the same as those of example 1 except that:
the brazing holding time was 120min, and the composition of the brazing filler metal alloy was the same as in example 1.
Analysis of experimental tests
In order to obtain the brazing layer thickness of comparative example 2, the brazed joint obtained in this example was analyzed by a scanning electron microscope, and the phase composition thereof was mainly NiTiZr and Cu (Ti, Zr)2And the solidification structure is needle-shaped Widmannstatten structure. The brazing layer of comparative example 2 has a thickness of 357 μm. The average value of the room-temperature shear strength of the soldered joint is 191 MPa.
Comparative example 3
A Ti-Zr-Cu-Ni amorphous solder alloy for SP700 titanium alloy, the steps not specifically described being the same as those of example 1 except that:
the brazing holding time was 150min, and the composition of the brazing filler metal alloy was the same as in example 1.
Analysis of experimental tests
In order to obtain the brazing layer thickness of comparative example 3, the brazing joint obtained in this example was analyzed by scanning electron microscopy, and its phase composition was mainly Cu (Ti, Z)r)2And the coagulation tissue is widmannstatten tissue. The braze layer thickness of comparative example 3 was 667 microns. The average value of the room-temperature shear strength of the soldered joint is 147 MPa.
Comparative example 4
A Ti-Zr-Cu-Ni amorphous solder alloy for SP700 titanium alloy, the steps not specifically described being the same as those of example 1 except that:
the brazing holding time was 180min, and the composition of the brazing filler metal alloy was the same as in example 1.
Analysis of experimental tests
In order to obtain the brazing layer thickness of comparative example 4, the brazing joint obtained in this example was analyzed by a scanning electron microscope, and its phase composition was mainly Cu (Ti, Zr)2The coagulated structure was a coarse basket structure. The brazing layer of comparative example 4 has a thickness of 714 μm. The average value of the room-temperature shear strength of the soldered joint is 144 MPa.
According to a solid-phase reaction kinetic model, a Fick first law and experimental results are combined, under the diffusion-controlled interface solid-liquid phase reaction condition, a proportional relation between the thickness x of a reaction layer and the 1/2 th power of brazing heat preservation time t can be fitted, a fitting schematic diagram is shown in FIG. 9, and the fitting result is as follows:
x＝120t1/2-884.7
the brazing layer thickness of comparative example 1 was increased to 167 μm, but the shear strength of the braze joint was decreased to 261MPa, compared to example 1; the heat preservation time of the comparative example 1 is short, the elements of the brazing reaction layer are not completely diffused, and the obvious layering phenomenon can occur at the brazing joint, so that the brazing filler metal cannot be completely combined with the base metal; while the brazing reaction layer of the comparative examples 2, 3 and 4 shows a gradual increase in thickness with the extension of the brazing holding time from 60min to 180min, and the phase of the brazing reaction layer gradually changes into Cu (Ti, Zr)2And the brazing reaction layer is changed from a fine needle-shaped widmannstatten structure into a coarse basket structure, and the shearing strength of the brazing joint is gradually reduced to 144 MPa.
Therefore, the preferred braze reaction layer thickness ranges are set as: 1/2 the thickness of the brazing filler metal is more than the thickness of the brazing reaction layer and more than the thickness of the brazing filler metal, namely more than 50 microns and more than 100 microns. In the interval, the brazing filler metal elements can be fully diffused into the brazing base metal, the generation of an intermediate phase of a brazing reaction layer can be reduced, and the negative influence on the structure of a brazed joint is reduced.
The following conclusions can be drawn from example 1, comparative example 2, comparative example 3 and comparative example 4:
under diffusion-controlled interfacial solid-liquid phase reaction conditions:
1. the brazing heat preservation time is reduced, so that the reaction of a brazing interface is incomplete, and an intermediate structure cannot be generated between the brazing filler metal and a base metal;
2. the brazing heat preservation time is prolonged, so that the thickness of a brazing layer can be effectively increased, and the diffusion degree of brazing filler metal elements is increased;
3. increasing the soldering heat preservation time and increasing Cu (Ti, Zr)2Phase content, change the structure and appearance of the soldered joint.
To demonstrate the effect of the different element contents of the Ti-Zr-Cu-Ni solder alloys, the cases of example 2, example 3, comparative example 5 and comparative example 6 are provided.
Example 2:
this embodiment is substantially the same as embodiment 1, and is characterized in that:
the Ti-Zr-Cu-Ni amorphous solder alloy for the SP700 titanium alloy has the same steps as the example 1, except that the chemical element composition and the mass percent are as follows:
Experimental test analysis:
in order to test the actual melting point values of the solder, the designed solder was subjected to DSC testing, the results of which are shown in fig. 6. Compared with the calculated result, the actual melting point of the brazing filler metal is 761 ℃, so that the brazing filler metal can be completely melted by selecting the brazing experiment at 850 ℃. The main composition of the composition is as follows: NiTiZr and Cu (Ti, Zr)2Phase, solder solidification processFine needle-shaped widmannstatten tissues are generated in the process. The shear performance of the obtained brazed joint is evaluated, and the average value of the room-temperature shear strength of the brazed joint is 488 MPa.
Example 3:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
the Ti-Zr-Cu-Ni amorphous solder alloy for the SP700 titanium alloy has the same steps as the example 1, except that the chemical element composition and the mass percent are as follows:
30% of Zr, 4% of Cu, 35% of Ni and the balance of Ti. The mass percentages of the phases are as follows: bcc phase content of 35%, NiZr2Phase content 13%, NiTiZr phase content 17%, Cu (Ti, Zr)2The phase content was 35%, and the calculation results are shown in fig. 3.
Experimental test analysis:
in order to test the actual melting point values of the solder, the designed solder was subjected to DSC testing, the results of which are shown in fig. 6. Compared with the calculation result, the actual melting point of the brazing filler metal is 821 ℃, and the brazing filler metal can be completely melted by selecting 890 ℃ for a brazing experiment. The morphology of the brazed joint structure obtained in the embodiment is analyzed by a scanning electron microscope, and the main component phase composition of the brazing joint structure is as follows: bcc phase, NiTiZr and Cu (Ti, Zr)2And needle-shaped widmannstatten structures are generated in the solidification process of the brazing filler metal. The shear properties of the obtained brazed joints were evaluated, and the average value of the room-temperature shear strength of the brazed joints was 450 MPa.
Comparative example 5:
a Ti-Zr-Cu-Ni amorphous solder alloy for SP700 titanium alloy, the steps not specifically described being the same as those of example 1 except that: the chemical element composition and mass percentage of the alloy is that Zr content is 40%, Cu content is 4%, Ni content is 29%, and the balance is Ti, and the calculation result is shown in figure 4.
Analysis of experimental tests
In order to test the actual melting point value of the solder, the designed solder is subjected to DSC test, and compared with the calculated result, the actual melting point of the solder is 958 ℃, so that the solder can not be completely melted by selecting the braze experiment at 890 ℃. The phase mainly comprises (Ti, Zr) phase which is not completely melted in the brazing filler metal, the brazing filler metal and the base metal do not have interface reaction, and intermediate structure is not formed in the solidification process. The shear properties of the resulting brazed joints were evaluated, and the average value of the room-temperature shear strength of the brazed joints was 163 MPa.
Comparative example 6:
a Ti-Zr-Cu-Ni amorphous solder alloy for SP700 titanium alloy, the steps not specifically described being the same as in comparative example 5 except that: since the braze test was chosen at 890 ℃ and did not completely melt the braze, the braze test was chosen at 970 ℃. The main composition of the composition is as follows: the (Cu, Ni) (Ti, Zr) phase, widmannstatten structure is generated in the solidification process of the solder. The shear properties of the obtained brazed joints were evaluated, and the average value of the room-temperature shear strength of the brazed joints was 342 MPa.
By comparative analysis of the data obtained in examples 1 to 3, comparative example 5 and comparative example 6, as shown in FIG. 8, the following conclusions can be drawn:
(1) along with the increase of the brazing heat preservation time, the thickness of a brazing joint reaction layer shows a trend of decreasing firstly and then increasing, wherein when the heat preservation time is 60min, the thickness of the brazing reaction layer reaches a minimum value of 66 microns; the structure at the soldered joint shows the trend of refining first and then coarsening, wherein the structure at the soldered joint is a fine acicular Widmannstatten structure when the temperature is kept for 60 min.
(2) Along with the increase of Zr element in the brazing filler metal, the melting point of the brazing filler metal shows a gradually-reduced change trend, wherein when the Zr content reaches 60-70%, the melting point of the brazing filler metal can reach below 800 ℃, and when the Zr content reaches 30-50%, the melting point of the brazing filler metal can reach below 850 ℃.
(3) When the chemical element composition and the mass percentage of the brazing filler metal are that the Zr content is 60%, the Cu content is 10%, the Ni content is 14%, and the balance is Ti, the actual melting point of the brazing filler metal is 775 ℃, the brazing experiment is carried out at 890 ℃, and after the heat preservation is carried out for 60min, the main composition of the brazing joint is as follows: NiTiZr and Cu (Ti, Zr)2The average value of the room-temperature shear strength of the soldered joint can reach 576 MPa.
In summary, the above implementationExample SP700 amorphous Ti-Zr-Cu-Ni solder alloy for titanium alloys and methods of making and using the same. The mass percentage of each raw material is that Zr content is 30-60%, Cu content is 3-14%, Ni content is 14-35%, and the rest is Ti. The melting point value of the brazing filler metal is 761-821 ℃, the beta transition temperature of the brazing filler metal is 79-139 ℃ lower than that of the SP700 titanium alloy, and the phase of a brazing reaction layer formed by combining the Ti-Zr-Cu-Ni brazing filler metal alloy and the SP700 titanium alloy in the brazing reaction process is a NiTiZr phase with the length-diameter ratio of 3.1 and the mass fraction of 17-47%; cu (Ti, Zr) with aspect ratio of 1.9 and mass fraction of 35-59%2Phase (1); a Bcc phase with the mass fraction of not more than 35 percent and NiZr with the mass fraction of not more than 13 percent2Phase (1); does not contain brittle phase (Cu, Ni) (Ti, Zr) phase. The brazing filler metal is prepared into an amorphous brazing foil strip with the thickness of 0.01-0.1 mm by an amorphous strip throwing method, and the amorphous brazing foil strip is lapped with SP700 titanium alloy, then is brazed at 850-890 ℃ and is subjected to heat preservation for 60min to obtain a brazed joint. The average weld thickness of the brazing joint in the embodiment of the invention is 50-100 microns, the highest room temperature shear strength is 450-576 MPa, and the use requirement of the SP700 titanium alloy brazing is met.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitution patterns, as long as the purpose of the present invention is met, and the technical principle and the inventive concept of the Ti-Zr-Cu-Ni solder for SP700 titanium alloy and the brazing method of the present invention shall not depart from the scope of the present invention.
Claims (10)
1. An amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy is characterized in that the mass fraction of the Ti-Zr-Cu-Ni solder alloy is as follows: 30-70% of Zr, 3-14% of Cu, 13-35% of Ni and the balance of Ti; the obtained amorphous Ti-Zr-Cu-Ni solder alloy is in a foil strip shape, and the thickness is 0.01-0.1 mm; the Ti-Zr-Cu-Ni solder alloy is formed by combining with SP700 titanium alloy in the process of brazing reactionThe phase contained in the brazing reaction layer is NiTiZr phase and Cu (Ti, Zr)2Phase, Bcc phase and NiZr2The phase does not contain a brittle phase (Cu, Ni) (Ti, Zr).
2. The amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy according to claim 1, characterized in that: wherein the length-diameter ratio of the NiTiZr phase is 3.1, and the mass fraction of the NiTiZr phase is 17-47%; cu (Ti, Zr)2Aspect ratio of phase 1.9, Cu (Ti, Zr)2The mass fraction of the phase is 35-59%; bcc phase mass fraction not more than 35%, NiZr2The mass fraction of phases is not more than 13%.
3. The amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy according to claim 1, characterized in that: the melting point of the amorphous Ti-Zr-Cu-Ni brazing filler metal alloy is 761-821 ℃, the beta transition temperature of the amorphous Ti-Zr-Cu-Ni brazing filler metal alloy is 79-139 ℃ lower than that of the SP700 titanium alloy, and the amorphous Ti-Zr-Cu-Ni brazing filler metal alloy is in contact with the SP700 titanium alloy serving as a base material in a liquid phase, so that the brazing surface area is increased; the amorphous Ti-Zr-Cu-Ni brazing alloy is used as the brazing filler metal, and the SP700 base metal titanium alloy is welded to obtain the brazing joint with the strength not lower than 400 MPa.
4. A method for preparing an amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy as claimed in claim 1, characterized by comprising the steps of:
according to the mass fraction of the Ti-Zr-Cu-Ni solder alloy: the Ti-Zr-Cu-Ni solder alloy comprises the following components in percentage by mass: 30-70% of Zr, 3-14% of Cu, 13-35% of Ni and the balance of Ti; weighing pure Ti, pure Zr, pure Cu and pure Ni as raw materials; wherein the addition amount of pure Cu is 105% of the mass fraction of the Cu content; then, carrying out vacuum melting on the raw materials to obtain a Ti-Zr-Cu-Ni solder alloy ingot; and preparing the Ti-Zr-Cu-Ni brazing alloy ingot into a Ti-Zr-Cu-Ni brazing alloy foil strip.
5. The method for preparing the amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy according to claim 4, wherein the method comprises the following steps: the mass fraction of the Ti-Zr-Cu-Ni solder alloy is obtained by designing the Ti-Zr-Cu-Ni alloy solder by the following method:
calculating a phase diagram of the Ti-Zr-Cu-Ni solder alloy by using a computer system and adopting a CALPHAD method, and screening a melting point contour map according to a phase diagram database of the Ti-Zr-Cu-Ni alloy to determine the Zr content meeting the requirement of a melting point value; and calculating the phase type and phase fraction in the solidification process through a solidification path, and obtaining the component proportion of the Ti-Zr-Cu-Ni solder alloy without brittle phases (Cu, Ni) (Ti, Zr) in the phase according to the calculation result.
6. The method for preparing the amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy according to claim 5, wherein the method comprises the following steps: the method for establishing the Ti-Zr-Cu-Ni alloy phase map database comprises the following steps: a CALPHOD method is adopted, a ternary phase diagram of Ti-Cu-Zr, Ti-Ni-Zr and Ti-Cu-Ni is obtained through experiments, a titanium-rich angle phase-related system of a Ti-Zr-Cu-Ni quaternary system is obtained through extrapolation calculation of the ternary system, thermodynamic information of the melting point, the beta transition temperature and the phase content of the brazing filler metal of the Ti-Zr-Cu-Ni system is obtained, and the relation between the components, the melting point, the phase composition and the phase content is obtained.
7. The method for preparing the amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy according to claim 5, wherein the method comprises the following steps: the method for determining Zr content meeting the requirement of the melting point value by screening the melting point contour map is a secondary screening method, and comprises the following steps:
firstly, calculating a Ti-Zr-Cu-Ni alloy liquid phase projection diagram under different Zr element adding amounts through a Ti-Zr-Cu-Ni alloy phase diagram database, and calculating a corresponding melting point contour diagram according to the projection diagram; then, carrying out first screening, wherein the specific method comprises the following steps:
carrying out first screening according to the requirement that the melting point value is lower than 800 ℃ by using the gradient that the addition amount of Zr element is 10%; and then carrying out secondary screening, wherein the specific method comprises the following steps:
and (4) carrying out secondary screening according to the requirement that the melting point value is lower than 800 ℃ by a gradient that the addition amount of the Zr element is 1%.
8. The method for preparing the amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy according to claim 4, is characterized in that the vacuum melting method comprises the following steps:
vacuum arc melting furnace is adopted, and the vacuum is pumped to not less than 5 multiplied by 10-3And (3) introducing argon after the vacuum degree of the Pa value is reached, repeatedly smelting for 3-5 times in an arc heating mode to ensure that the alloy components are uniform, and then cooling along with the furnace to obtain a Ti-Zr-Cu-Ni solder alloy ingot.
9. The method for preparing the amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy according to claim 4, wherein the method for preparing the Ti-Zr-Cu-Ni solder alloy foil strip comprises the following steps:
crushing a Ti-Zr-Cu-Ni brazing alloy ingot, heating the Ti-Zr-Cu-Ni brazing alloy ingot in an induction heating mode, and then performing spray casting by adopting an amorphous strip casting method under the conditions that the rotating speed of a copper wheel is 2000-2500 r/s and the spray pressure is 0.02-0.05 MPa to obtain a continuous Ti-Zr-Cu-Ni brazing alloy foil strip.
10. The application of the amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy is characterized in that: the method for welding the SP700 titanium alloy as the base material by using the amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy as the solder in claim 1 comprises the following steps:
(1) brazing material preparation and pretreatment:
placing the amorphous Ti-Zr-Cu-Ni solder alloy in acetone with the temperature of not less than 50 ℃ for ultrasonic cleaning; simultaneously, grinding and polishing the surface of the brazing parent metal and ultrasonically cleaning in acetone;
(2) the brazing treatment process comprises the following steps:
lapping the amorphous Ti-Zr-Cu-Ni brazing alloy and a brazing base metal together by using a clamp, and adhering the amorphous Ti-Zr-Cu-Ni brazing alloy to the surface of the brazing base metal; then, at not higher than 5 × 10-3The vacuum degree of Pa value, the heating rate is 10-15 ℃/min,the brazing temperature is 850-; the average weld thickness of the obtained brazing joint is 50-100 microns, and the shear strength is 450-576 MPa.
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