CN112719688A

CN112719688A - Ti-Zr-Cu-Ni amorphous solder and preparation method and application thereof

Info

Publication number: CN112719688A
Application number: CN202011507012.5A
Authority: CN
Inventors: 李小强; 万宝; 吴祖骥; 潘存良; 屈盛官; 朱德智; 杨超
Original assignee: South China University of Technology SCUT
Current assignee: South China University of Technology SCUT
Priority date: 2020-12-18
Filing date: 2020-12-18
Publication date: 2021-04-30

Abstract

The invention discloses a Ti-Zr-Cu-Ni amorphous solder and a preparation method and application thereof. The brazing filler metal comprises the following components in percentage by mass: zr: 26-29%; ni: 21-24%; cu: 21-24% and the balance Ti. The components are proportioned according to the content, then a brazing alloy ingot is prepared by adopting an electric arc melting method, the alloy ingot is heated and melted after being crushed into small particles, and the Ti-Zr-Cu-Ni amorphous brazing alloy foil strip is prepared by adopting a rapid solidification technology. The obtained brazing filler metal has the advantages of high banding performance, low cost, high connection strength of brazed gamma-TiAl and Ni-based high-temperature alloy joints and the like.

Description

Ti-Zr-Cu-Ni amorphous solder and preparation method and application thereof

Technical Field

The invention belongs to the technical field of welding materials, and particularly relates to a Ti-Zr-Cu-Ni amorphous solder and a preparation method and application thereof.

Background

Welding is an important method of material joining, and common welding methods include fusion welding, pressure welding, and brazing. Brazing, which is a welding method that after brazing filler metal lower than the melting point of a weldment and the weldment are heated to the melting temperature of the brazing filler metal at the same time, the liquid brazing filler metal is used for filling the gap of a solid workpiece so as to connect solid base metals. The brazing filler metal is melted but the base metal is not melted in the brazing process, so that the brazing has a series of advantages, such as metal and metal, metal and nonmetal and the like; the unique advantages of mass connection and mass production, such as simultaneous brazing of multiple parts, multi-layered structures, etc., determine that brazing is becoming more and more popular in industry and life.

The gamma-TiAl alloy has excellent creep resistance and good oxidation stability at high temperature, and is widely applied to aerospace vehicles and automobile industry. Compared with the nickel-based high-temperature alloy widely applied to the aviation field, the gamma-TiAl alloy has the advantages of small density (which is only half of that of the traditional nickel-based high-temperature alloy), higher specific strength and specific stiffness and the like, but the cost is much higher. Therefore, γ -TiAl alloys are often bonded with nickel-based superalloys to achieve superior overall performance and to reduce costs. However, due to the large difference in physical and chemical properties between γ -TiAl alloys and nickel-based superalloys, it is difficult to obtain high performance joints using conventional fusion welding methods. Diffusion bonding and brazing are considered to be effective methods of bonding γ -TiAl alloys and nickel-based superalloys. Brazing is used more widely than diffusion welding because it not only joins complex shaped parts, but also is simpler in process. And the brazing can be carried out in batch connection and mass production, such as brazing of a plurality of parts, multi-layer structural members and the like at the same time. After the brazing is finished, the workpiece is attractive, the size of the workpiece is accurate, and the welding stress is small.

In recent years, there has been a small amount of research on brazing of TiAl alloys and nickel-based superalloys. Ti-13Zr-21Cu-9Ni (wt%) brazing alloy for Chen et al₃Al alloy and GH 536. However, since a large amount of intermetallic compounds such as Ti-Ni and Ti-Fe are formed in the brazed joint, the shear strength of the joint is low, only 86 MPa. He Peng et al adopted BNi₂The brazing filler metal researches the vacuum brazing connection of the gamma-TiAl-based alloy and the GH99 nickel-based superalloy, and the maximum shearing strength of a joint is 205 MPa. However BNi₂The brazing filler metal is powderThe brazing filler metal in powder form is not easy to assemble, has high melting temperature and large melting temperature range, and simultaneously is due to BNi₂The brazing filler metal contains higher elements such as silicon, boron and the like, so that the brazing filler metal contains more intermetallic compound brittle phases or brittle eutectics. Nobody uses Ag-21Cu-25Pd (wt%) solder alloy to braze Ti under vacuum condition₃Al alloys and nickel-base superalloys. Pd element and Ti₃Al reacts to form TiPd and Ti₃Pd₅And intermetallic compounds such as AlPd. When the joint is brazed for 10min at 1253K, the tensile strength of the joint is the highest and reaches 404 MPa. However, the cost of palladium is too high to be applied on a large scale.

The solder is an important factor affecting the quality of soldered joints, and a solder having a low melting point and good wettability to the base material is generally preferred for soldering. In conclusion, the search for a more reasonable low-melting-point titanium-based brazing filler metal component and a preparation method thereof are crucial to the development of the braze welding connection of TiAl alloy and nickel-based superalloy.

Disclosure of Invention

In order to solve the defects and shortcomings of the prior art, the invention aims to provide the Ti-Zr-Cu-Ni amorphous solder which is suitable for soldering gamma-TiAl and Ni-based high-temperature alloy, and the room-temperature shear strength of a soldered joint obtained by soldering can reach 279 MPa. The brazing filler metal has simple components, low cost, lower melting temperature, narrower melting interval, good spreading performance and very good processing and forming performance.

The invention also aims to provide a preparation method of the Ti-Zr-Cu-Ni amorphous solder.

The invention further aims to provide application of the Ti-Zr-Cu-Ni amorphous solder, and the Ti-Zr-Cu-Ni amorphous solder is applied to braze connection of gamma-TiAl alloy and Ni-based alloy.

The purpose of the invention is realized by the following technical scheme:

the Ti-Zr-Cu-Ni amorphous solder comprises the following components in percentage by mass: 26.0-29.0% Zr, 21.0-24.0% Ni, 21.0-24.0% Cu and the balance Ti.

Preferably, the Ti-Zr-Cu-Ni amorphous solder comprises the following components in percentage by mass: 26.5-28.5% of Zr, 21.5-23.5% of Ni, 21.5-23.5% of Cu and the balance of Ti.

The preparation method of the Ti-Zr-Cu-Ni amorphous solder comprises the following steps:

(1) adding Cu, Ni, Ti and Zr raw materials into a smelting device according to the element mass percentage for smelting to obtain a brazing alloy ingot;

(2) and crushing the brazing alloy ingot, heating and melting, and preparing the Ti-Zr-Cu-Ni amorphous foil strip brazing filler metal by a rapid solidification technology.

Preferably, the raw materials of Cu, Ni, Ti and Zr in the step (1) are all single pure metal bulk particles, and the purity of the raw materials is higher than 99.99%.

Preferably, the raw materials of Cu, Ni, Ti and Zr in the step (1) are sequentially added into a smelting device according to the sequence of single pure metal particles of Cu, Ni, Ti and Zr; the melting point temperature of the single pure metal particles is increased in sequence according to the sequence, and the low-melting-point metal can be prevented from volatilizing in the smelting process by feeding in the sequence from low melting point temperature to high melting point temperature.

Preferably, the raw material in the step (1) needs to be subjected to oxide film removal and impurity treatment, and specifically comprises the following steps: and (3) polishing the surfaces of the pure metal particles by using 180-mesh SiC abrasive paper, then carrying out acid cleaning, washing with absolute ethyl alcohol, blow-drying, and finally carrying out ultrasonic cleaning in an acetone bath agent and blow-drying.

Preferably, the smelting in the step (1) is carried out for 4-8 times in an inert gas or nitrogen atmosphere at 1900-2000 ℃, and each time lasts for 1-3 minutes; firstly, the furnace cavity of the smelting device is vacuumized to the vacuum degree<1×10^-3Torr, then introducing inert gas or nitrogen atmosphere, and finally removing oxygen through the titanium sponge.

Preferably, the smelting device in the step (1) is a vacuum arc furnace.

Preferably, the crushing in the step (2) is a mechanical crushing mode.

Preferably, the temperature of the heating melting in the step (2) may be determined by determining whether the metal is melted by observing a state of the metal being melted, thereby determining the temperature of the heating melting. Generally, the temperature is higher than the melting point of the material.

And (3) performing induction heating melting by adopting a flat-mouth quartz tube, and preferably performing induction heating melting by adopting a flat-mouth quartz tube with a tube opening gap specification of 0.6 x 10 mm.

Preferably, the rapid solidification of step (2) is carried out in a high vacuum single roll rotary quenching system. The rapid solidification technology is carried out in a high-vacuum single-roller rotary quenching system, and completely molten ingot casting alloy is sprayed onto a rotating copper wheel which is filled with cooling circulating water by utilizing the difference of internal and external pressure of a quartz tube to prepare the foil strip-shaped amorphous brazing filler metal.

More preferably, the process parameters of the rapid solidification in the step (2) are as follows: the linear velocity of the rotating copper roller is 27-32 m/s, the distance between the outlet of the melt (such as a quartz tube orifice) and the surface of the copper roller is 1.0-1.5 mm, and the pressure of argon gas for melt injection is 0.07-0.10 MPa.

Preferably, the Ti-Zr-Cu-Ni foil brazing filler metal in the step (2) has the thickness of 40-60 mu m and the width of 9-12 mm.

The Ti-Zr-Cu-Ni amorphous solder is applied to braze connection of a gamma-TiAl alloy and a Ni-based alloy.

The preparation principle of the invention is as follows:

(1) adding higher Zr content: zr can improve the creep resistance of Ti alloy and can improve alloy strength under the condition of not reducing titanium alloy plasticity, and a proper amount of Zr element can improve the amorphous forming capability of Ti-based brazing filler metal, improves the banding property of the brazing filler metal by increasing Zr content, increases the wetting spreadability of the brazing filler metal on the alloy surface, and reduces the difficulty in assembling the brazing filler metal caused by the brittleness of the brazing filler metal.

(2) Adding proper amount of Cu and Ni: by adding a proper amount of Cu and Ni elements, eutectic structures can be formed with Ti and Zr elements, the melting point of the Ti-based brazing filler metal is effectively reduced, the fluidity of the molten Ti-based brazing filler metal can be improved, the joint filling capacity is improved, and the brazing is facilitated.

(3) Controlling the ratio of Ti + Zr/Cu + Ni: the amorphous formability of the Ti + Zr/Cu + Ni solder with a lower proportion is poor, and complete amorphous can not be formed under the same preparation condition; the melting point of the Ti + Zr/Cu + Ni solder with higher proportion is higher; the DSC curve of the Ti + Zr/Cu + Ni solder with partial proportion is in a double peak phenomenon, which is not beneficial to the braze welding; therefore, a low-melting-point eutectic structure can be formed by a proper ratio of Ti + Zr/Cu + Ni, the melting range is short, the brazing is facilitated, the amorphous formability of the brazing filler metal can be improved, and the brazing filler metal foil strip has excellent plasticity.

The melting temperature range of the Ti-Zr-Cu-Ni brazing filler metal prepared by the method is 872.6-911.8 ℃, and the melting range is 20.3-37.0 ℃.

Compared with the prior art, the invention has the following advantages and beneficial effects:

(1) the amorphous brazing filler metal disclosed by the invention is low in melting point, the melting temperature range is 872.6-911.8 ℃, and the minimum melting range can reach 20.3 ℃;

(2) the amorphous solder is suitable for vacuum brazing of gamma-TiAl and Ni-based high-temperature alloy, and the room-temperature shear strength of a brazed joint obtained by brazing is up to 279 MPa;

(3) compared with the Ag-21Cu-25Pd brazing filler metal, the amorphous brazing filler metal has no raw materials of noble metals such as Ag, Pd and the like, and the cost is obviously reduced; and BNi₂Compared with the brazing filler metal, the ribbon brazing filler metal is simple in preparation process, simple and easy in equipment and low in melting point; compared with the traditional Ti-13Zr-21Cu-9Ni solder, the proportion of Ti + Zr/Cu + Ni elements is reduced, the melting point and the melting range of the solder are reduced, the mechanical property of a soldered joint is improved, the shear strength of the joint reaches 279MPa, and the shear resistance of the soldered joint is improved by 224.4 percent compared with that of the traditional Ti-13Zr-21Cu-9Ni solder;

(4) the amorphous brazing filler metal disclosed by the invention is high in banding property, good in amorphous formability, excellent in plasticity and easy to process into various shapes, and the brazing filler metal is good in wetting and spreading property on the surface of an alloy.

Drawings

FIG. 1 is an SEM photograph of the structure of a brazing filler metal ingot prepared in example 1.

Fig. 2 is an X-ray diffraction (XRD) pattern of the amorphous solder foil tape prepared in example 1.

FIG. 3 is a DSC curve, T, of the amorphous solder foil strip prepared in example 1_gIs the glass transition temperature, T_xIs the crystallization temperature, T_sIs solidus temperature, T_lIs the liquidus temperature.

Fig. 4 is a BEIs diagram of the amorphous solder foil strip prepared in example 1.

Fig. 5 is a line scan of the amorphous solder foil strip prepared in example 1.

Fig. 6 is an SEM image of the joint structure of gamma-TiAl brazed with Ni-based superalloy GH536 using the solder prepared in example 1.

Fig. 7 shows the shear resistance at different brazing temperatures for brazing joints of γ -TiAl and Ni-based superalloy GH536 using the brazing filler prepared in example 1, with 10 minutes soak time.

Fig. 8 shows the shear performance at different brazing soak times for brazing joints of γ -TiAl and Ni-based superalloy GH536 using the braze prepared in example 1, where the braze temperature was 1110 ℃.

Fig. 9 shows XRD patterns and DSC curves of solders with different Ti + Zr/Cu + Ni ratios (F1: Ti + Zr/Cu + Ni ═ 3, F2: Ti + Zr/Cu + Ni ═ 13/7, F3: Ti + Zr/Cu + Ni ═ 11/9, F4: Ti + Zr/Cu + Ni ═ 9/11).

Detailed Description

The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.

Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.

Example 1

(1) The method is characterized in that single pure metal particles of Ti, Zr, Cu and Ni are used as raw materials, the purity of each raw material is more than or equal to 99.99%, the single pure metal particles are respectively weighed according to the mass percentage of 27.5% of Ti, 27.5% of Zr, 22.5% of Cu and 22.5% of Ni, and before weighing, the surfaces of the raw material metal particles are required to be subjected to oxidation film removal and impurity treatment, and the method specifically comprises the following steps: polishing the surface of the metal particles by using 180-mesh SiC abrasive paper, then performing acid cleaning by using dilute hydrochloric acid, washing by using absolute ethyl alcohol, drying, and finally performing ultrasonic cleaning in an acetone bath agent for 10min and drying;

(2) smelting a solder alloy: sequentially putting the raw materials in the step (1) into a water-cooled copper crucible of a WS-4 type non-consumable vacuum arc furnace according to the sequence of single pure metal particles of Cu, Ni, Ti and Zr, and pumping the interior of the furnace chamber to vacuum degree before smelting<1×10^- ³Charging argon to 0.06MPa under the state of Torr, repeating the operation for 3 times, placing high-purity sponge titanium in a furnace chamber during smelting, then adopting tungsten electrode electric arc to smelt the high-purity sponge titanium firstly under the atmosphere of argon protection to remove oxygen (the electric arc furnace is normally arcing to completely melt the sponge titanium), smelting the prepared furnace burden (the electric arc furnace is normally arcing to completely melt the brazing filler metal alloy), and repeatedly smelting for 6 times at 2000 ℃ for 2 minutes each time to obtain a brazing filler metal alloy ingot;

(3) preparing a foil strip: crushing the brazing alloy ingot in the step (2) into small particles by adopting a mechanical crushing mode, cleaning and drying by using alcohol, then loading 3g of small-particle brazing filler metal into a flat-nozzle type quartz tube with the outlet width of 0.6mm and the length of 10mm, then installing the quartz tube filled with the brazing alloy particles on a WK-IIB type high-vacuum single-roller rotary quenching system, ensuring that the quartz tube is coaxial with a heating induction coil and the distance between the mouth of the quartz tube and the upper surface of a copper roller in the high-vacuum single-roller rotary quenching system is 1mm, and then pumping the vacuum degree in a furnace cavity of the high-vacuum single-roller rotary quenching system to 7.8 multiplied by 10^-4Pa, argon is charged again to enable 1ATM argon to exist in the furnace cavity, the operation is repeated for 5 times, the pressure value of the injected argon is adjusted to be 0.08MPa, the rotational linear speed of a copper roller of the liquid quenching device is set to be 30m/s, after the copper roller is accelerated to the set speed, a high-frequency power switch is turned on, the high-frequency heating switch is pressed to melt the brazing alloy in the quartz tube to be yellowish white (the liquid level of the brazing alloy in the tube is in a fluctuant state after the brazing alloy is completely melted and is in a dazzling yellowish white state, the molten alloy can be injected), the molten alloy starts to flow, the air blowing switch is immediately pressed, and when the molten alloy does not spill any more, the high-frequency heating switch; under the action of the jet gas, the liquid solder is jetted onto the surface of a copper roller rotating at a high speed, and a continuous Ti-Zr-Cu-Ni amorphous solder foil strip with the thickness of 50 mu m and the width of 10mm and excellent toughness and surface quality is formed under the condition of quenching.

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, the melting temperature range of the brazing filler metal is 872.6-892.9 ℃, and the melting range is 20.3 ℃. The solder prepared by the embodiment is used for carrying out vacuum brazing connection on the gamma-TiAl and the Ni-based high-temperature alloy GH536 under the conditions of heating temperature of 1110 ℃ and heat preservation for 10min, and the average value of the room-temperature shear strength of a brazed joint is 279 MPa.

FIG. 1 is an SEM photograph of the structure of a brazing filler metal ingot prepared in example 1. Fig. 2 is an X-ray diffraction (XRD) pattern of the amorphous solder foil tape prepared in example 1. Fig. 3 is a DSC curve of the amorphous solder foil strip prepared in example 1. Fig. 4 is a BEIs diagram of the amorphous solder foil strip prepared in example 1. Fig. 5 is a line scan of the amorphous solder foil strip prepared in example 1. Fig. 6 is an SEM image of the joint structure of gamma-TiAl brazed with Ni-based superalloy GH536 using the solder prepared in example 1. Fig. 7 shows the shear resistance at different brazing temperatures for brazing joints of γ -TiAl and Ni-based superalloy GH536 using the brazing filler prepared in example 1. FIG. 8 shows the shear resistance at different brazing soak times for brazing joints of γ -TiAl and Ni-based superalloy GH536 using the brazing filler prepared in example 1.

Example 2

(1) The method is characterized in that single pure metal particles of Ti, Zr, Cu and Ni are used as raw materials, the purity of each raw material is more than or equal to 99.99%, the single pure metal particles are respectively weighed according to the mass percentage of 28.5% of Ti, 28.5% of Zr, 21.5% of Cu and 21.5% of Ni, and before weighing, the surfaces of the raw material metal particles are required to be subjected to oxidation film removal and impurity treatment, and the method specifically comprises the following steps: polishing the surface of the metal particles by using 180-mesh SiC abrasive paper, then performing acid cleaning by using dilute hydrochloric acid, washing by using absolute ethyl alcohol, drying, and finally performing ultrasonic cleaning in an acetone bath agent for 10min and drying;

(3) preparing a foil strip: adopting a mechanical crushing mode to crush the mixture obtained in the step (2)Crushing a brazing alloy ingot into small particles, cleaning and drying by alcohol, then loading 3g of small-particle brazing filler metal into a flat-nozzle quartz tube with the outlet width of 0.6mm and the length of 10mm, then installing the quartz tube with the brazing alloy particles on a WK-IIB type high-vacuum single-roller rotary quenching system, ensuring that the quartz tube is coaxial with a heating induction coil and the distance between the mouth of the quartz tube and the upper surface of a copper roller in the high-vacuum single-roller rotary quenching system is 1.5mm, and then pumping the vacuum degree in a furnace cavity of the high-vacuum single-roller rotary quenching system to 7.8 multiplied by 10^-4Filling argon gas into the furnace cavity by Pa, repeatedly operating for 5 times, adjusting the pressure value of the sprayed argon gas to be 0.10MPa, setting the rotation linear speed of a copper roller of a liquid quenching device to be 27m/s, opening a high-frequency power switch after the copper roller is accelerated to the set speed, pressing the high-frequency heating switch to melt the brazing alloy in the quartz tube to be yellowish white (the liquid level of the brazing alloy in the tube is in a fluctuant state after the brazing alloy melt is completely melted and the molten liquid can be sprayed when the brazing alloy is in a dazzling yellowish white state) by adopting a high-frequency induction heating mode, starting to flow, immediately pressing a blowing switch, and loosening the high-frequency heating switch and the blowing switch when the melt is not splashed out any more; under the action of the jet gas, the liquid solder is jetted onto the surface of a copper roller rotating at a high speed, and a continuous Ti-Zr-Cu-Ni amorphous solder foil strip with the thickness of 60 mu m, the width of 12mm and excellent toughness and surface quality is formed under the condition of quenching.

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, the melting temperature range of the brazing filler metal is 863.5-891.9 ℃, and the melting range is 28.4 ℃. The brazing filler metal prepared by the embodiment is used for carrying out vacuum brazing connection on the gamma-TiAl and the Ni-based high-temperature alloy GH536 under the conditions of heating temperature of 1110 ℃ and heat preservation for 10min, and the average value of the room-temperature shear strength of a brazed joint is 261 MPa.

Example 3

(1) The method is characterized in that single pure metal particles of Ti, Zr, Cu and Ni are used as raw materials, the purity of each raw material is more than or equal to 99.99%, the single pure metal particles are respectively weighed according to the mass percentage of 26.5% of Ti, 26.5% of Zr, 23.5% of Cu and 23.5% of Ni, and before weighing, the surfaces of the raw material metal particles are required to be subjected to oxidation film removal and impurity treatment, and the method specifically comprises the following steps: polishing the surface of the metal particles by using 180-mesh SiC abrasive paper, then performing acid cleaning by using dilute hydrochloric acid, washing by using absolute ethyl alcohol, drying, and finally performing ultrasonic cleaning in an acetone bath agent for 10min and drying;

(3) preparing a foil strip: crushing the brazing alloy ingot in the step (2) into small particles by adopting a mechanical crushing mode, cleaning and drying by using alcohol, then loading 3g of small-particle brazing filler metal into a flat-mouth quartz tube with the outlet width of 0.6mm and the length of 10mm, then installing the quartz tube with the brazing alloy particles on a WK-IIB type high-vacuum single-roller rotary quenching system, ensuring that the quartz tube is coaxial with a heating induction coil and the distance between the mouth of the quartz tube and the upper surface of a copper roller in the high-vacuum single-roller rotary quenching system is 1mm, and then pumping the vacuum degree in a furnace cavity of the high-vacuum single-roller rotary quenching system to 7.8 multiplied by 10^-4Filling argon gas into the furnace cavity by Pa, repeatedly operating for 5 times, adjusting the pressure value of the sprayed argon gas to be 0.7MPa, setting the rotation linear speed of a copper roller of a liquid quenching device to be 32m/s, opening a high-frequency power switch after the copper roller is accelerated to a set speed, pressing the high-frequency heating switch to melt the brazing alloy in the quartz tube to be yellowish white (the liquid level of the brazing alloy in the tube is in a fluctuant state after the brazing alloy melt is completely melted and the molten liquid can be sprayed when the brazing alloy is in a dazzling yellowish white state) by adopting a high-frequency induction heating mode, starting to flow, immediately pressing a blowing switch, and loosening the high-frequency heating switch and the blowing switch when the melt is not splashed out any more; under the action of the jet gas, the liquid solder is jetted onto the surface of a copper roller rotating at a high speed to form a continuous Ti-Zr-Cu-Ni amorphous solder with the thickness of 40 mu m and the width of 9mm and excellent toughness and surface quality under the condition of quenchingA foil strip.

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, the melting temperature range of the brazing filler metal is 874.8-911.8 ℃, and the melting range is 37.0 ℃. The solder prepared by the embodiment is used for carrying out vacuum brazing connection on the gamma-TiAl and the Ni-based high-temperature alloy GH536 under the conditions of heating temperature of 1110 ℃ and heat preservation for 10min, and the average value of the room-temperature shear strength of a brazed joint is 254 MPa.

Comparative example 1

(1) The method is characterized in that single pure metal particles of Ti, Zr, Cu and Ni are used as raw materials, the purity of each raw material is more than or equal to 99.99%, the single pure metal particles are respectively weighed according to the mass percentage of 37.5% of Ti, 37.5% of Zr, 12.5% of Cu and 12.5% of Ni, and before weighing, the surfaces of the raw material metal particles are required to be subjected to oxidation film removal and impurity treatment, and the method specifically comprises the following steps: polishing the surface of the metal particles by using 180-mesh SiC abrasive paper, then performing acid cleaning by using dilute hydrochloric acid, washing by using absolute ethyl alcohol, drying, and finally performing ultrasonic cleaning in an acetone bath agent for 10min and drying;

(3) preparing a foil strip: crushing the brazing alloy ingot in the step (2) into small particles by adopting a mechanical crushing mode, cleaning and drying by using alcohol, then loading 3g of small-particle brazing filler metal into a flat-nozzle type quartz tube with the outlet width of 0.6mm and the length of 10mm, and then installing the quartz tube filled with the brazing alloy particles on a WK-IIB type high-vacuum single-roller rotary quenching system to ensure that the quartz tube is coaxial with a heating induction coil and the orifice of the quartz tube and the upper surface of a copper roller in the high-vacuum single-roller rotary quenching systemIs 1mm, then the vacuum degree in the furnace cavity of the high-vacuum single-roller rotary quenching system is pumped to 7.8 multiplied by 10^-4Filling argon gas into the furnace cavity by Pa, repeatedly operating for 5 times, adjusting the pressure value of the sprayed argon gas to be 0.08MPa, setting the rotation linear speed of a copper roller of a liquid quenching device to be 30m/s, opening a high-frequency power switch after the copper roller is accelerated to a set speed, pressing the high-frequency heating switch to melt the brazing alloy in the quartz tube to be yellowish white (the liquid level of the brazing alloy in the tube is in a fluctuant state after the brazing alloy melt is completely melted and the molten liquid can be sprayed when the brazing alloy is in a dazzling yellowish white state) by adopting a high-frequency induction heating mode, starting to flow, immediately pressing a blowing switch, and loosening the high-frequency heating switch and the blowing switch when the melt is not splashed out any more; under the action of the jet gas, the liquid solder is jetted onto the surface of a copper roller rotating at a high speed, and a continuous Ti-Zr-Cu-Ni solder foil strip with the thickness of 50 mu m and the width of 9mm is formed under the condition of quenching.

The Ti-Zr-Cu-Ni solder prepared by the comparative example is not completely amorphous, and has poor toughness and is not easy to be made into a complex solder shape because of less Cu and Ni contents. The melting temperature range of the brazing filler metal is 831.9-859.3 ℃, and the melting range is 27.4 ℃. The brazing filler metal prepared by the comparative example is used for carrying out vacuum brazing connection on the gamma-TiAl and the Ni-based high-temperature alloy GH536 under the conditions of heating temperature of 1110 ℃ and heat preservation for 10min, and the average value of the room-temperature shear strength of a brazed joint is 241 MPa.

Comparative example 2

(1) The method is characterized in that single pure metal particles of Ti, Zr, Cu and Ni are used as raw materials, the purity of each raw material is more than or equal to 99.99%, the single pure metal particles are respectively weighed according to the mass percentage of 32.5% of Ti, 32.5% of Zr, 17.5% of Cu and 17.5% of Ni, and before weighing, the surfaces of the raw material metal particles are required to be subjected to oxidation film removal and impurity treatment, and the method specifically comprises the following steps: polishing the surface of the metal particles by using 180-mesh SiC abrasive paper, then performing acid cleaning by using dilute hydrochloric acid, washing by using absolute ethyl alcohol, drying, and finally performing ultrasonic cleaning in an acetone bath agent for 10min and drying;

(2) smelting a solder alloy: sequentially putting the raw materials in the step (1) into a water-cooled copper crucible of a WS-4 type non-consumable vacuum arc furnace according to the sequence of single pure metal particles of Cu, Ni, Ti and Zr, and vacuumizing the interior of the furnace chamber before smeltingDegree of hollowness<1×10^- ³Charging argon to 0.06MPa under the state of Torr, repeating the operation for 3 times, placing high-purity sponge titanium in a furnace chamber during smelting, then adopting tungsten electrode electric arc to smelt the high-purity sponge titanium firstly under the atmosphere of argon protection to remove oxygen (the electric arc furnace is normally arcing to completely melt the sponge titanium), smelting the prepared furnace burden (the electric arc furnace is normally arcing to completely melt the brazing filler metal alloy), and repeatedly smelting for 6 times at 2000 ℃ for 2 minutes each time to obtain a brazing filler metal alloy ingot;

(3) preparing a foil strip: crushing the brazing alloy ingot in the step (2) into small particles by adopting a mechanical crushing mode, cleaning and drying by using alcohol, then loading 3g of small-particle brazing filler metal into a flat-nozzle type quartz tube with the outlet width of 0.6mm and the length of 10mm, then installing the quartz tube filled with the brazing alloy particles on a WK-IIB type high-vacuum single-roller rotary quenching system, ensuring that the quartz tube is coaxial with a heating induction coil and the distance between the mouth of the quartz tube and the upper surface of a copper roller in the high-vacuum single-roller rotary quenching system is 1mm, and then pumping the vacuum degree in a furnace cavity of the high-vacuum single-roller rotary quenching system to 7.8 multiplied by 10^-4Filling argon gas into the furnace cavity by Pa, repeatedly operating for 5 times, adjusting the pressure value of the sprayed argon gas to be 0.08MPa, setting the rotation linear speed of a copper roller of a liquid quenching device to be 30m/s, opening a high-frequency power switch after the copper roller is accelerated to a set speed, pressing the high-frequency heating switch to melt the brazing alloy in the quartz tube to be yellowish white (the liquid level of the brazing alloy in the tube is in a fluctuant state after the brazing alloy melt is completely melted and the molten liquid can be sprayed when the brazing alloy is in a dazzling yellowish white state) by adopting a high-frequency induction heating mode, starting to flow, immediately pressing a blowing switch, and loosening the high-frequency heating switch and the blowing switch when the melt is not splashed out any more; under the action of the jet gas, the liquid solder is jetted onto the surface of a copper roller rotating at a high speed, and a continuous Ti-Zr-Cu-Ni solder foil strip with the thickness of 60 mu m and the width of 10mm is formed under the condition of quenching.

The DSC curve of the Ti-Zr-Cu-Ni brazing filler metal prepared by the comparative example shows a double peak phenomenon, and the melting range is large, so that the Ti-Zr-Cu-Ni brazing filler metal is not beneficial to the brazing. The melting temperature range of the brazing filler metal is 836.6-879.2 ℃, and the melting range is 42.6 ℃. The brazing filler metal prepared by the embodiment is used for carrying out vacuum brazing connection on the gamma-TiAl and the Ni-based high-temperature alloy GH536 under the conditions of heating temperature of 1110 ℃ and heat preservation for 10min, and the average value of the room-temperature shear strength of a brazed joint is 229 MPa.

Comparative example 3

(1) The method is characterized in that single pure metal particles of Ti, Zr, Cu and Ni are used as raw materials, the purity of each raw material is more than or equal to 99.99%, the single pure metal particles are respectively weighed according to the mass percentage of 22.5% of Ti, 22.5% of Zr, 27.5% of Cu and 27.5% of Ni, and before weighing, the surfaces of the raw material metal particles are required to be subjected to oxidation film removal and impurity treatment, and the method specifically comprises the following steps: polishing the surface of the metal particles by using 180-mesh SiC abrasive paper, then performing acid cleaning by using dilute hydrochloric acid, washing by using absolute ethyl alcohol, drying, and finally performing ultrasonic cleaning in an acetone bath agent for 10min and drying;

(3) preparing a foil strip: crushing the brazing alloy ingot in the step (2) into small particles by adopting a mechanical crushing mode, cleaning and drying by using alcohol, then loading 3g of small-particle brazing filler metal into a flat-nozzle type quartz tube with the outlet width of 0.6mm and the length of 10mm, then installing the quartz tube filled with the brazing alloy particles on a WK-IIB type high-vacuum single-roller rotary quenching system, ensuring that the quartz tube is coaxial with a heating induction coil and the distance between the mouth of the quartz tube and the upper surface of a copper roller in the high-vacuum single-roller rotary quenching system is 1mm, and then pumping the vacuum degree in a furnace cavity of the high-vacuum single-roller rotary quenching system to 7.8 multiplied by 10^-4Filling argon gas into the furnace cavity by Pa, repeating the operation for 5 times, adjusting the pressure value of the sprayed argon gas to be 0.08MPa, setting the rotation linear speed of the copper roller of the liquid quenching device to be 30m/s, opening a high-frequency power switch after the copper roller is accelerated to the set speed, and pressing the high-frequency power switchThe high-frequency heating switch adopts a high-frequency induction heating mode to melt the brazing alloy in the quartz tube to be yellowish white (the liquid level of the brazing alloy melt in the tube is in a fluctuant state after the brazing alloy melt is completely melted, and the melt can be sprayed when the brazing alloy melt is dazzling yellowish white), and the high-frequency heating switch and the air blowing switch are released after the brazing alloy melt begins to flow and the air blowing switch is immediately pressed down, when the melt is not splashed out any more; under the action of the jet gas, the liquid solder is jetted onto the surface of a copper roller rotating at a high speed, and a continuous Ti-Zr-Cu-Ni solder foil strip with the thickness of 55 mu m and the width of 10mm is formed under the condition of quenching.

The Ti-Zr-Cu-Ni solder prepared by the comparative example has high DSC curve melting point and large melting range, and is not beneficial to the braze welding. The melting temperature range of the brazing filler metal is 926.6-974.8 ℃, and the melting range is 48.2 ℃. The solder prepared by the embodiment is used for carrying out vacuum brazing connection on the gamma-TiAl and the Ni-based high-temperature alloy GH536 under the conditions of heating temperature of 1110 ℃ and heat preservation for 10min, and the average value of the room-temperature shear strength of a brazed joint is 234 MPa.

Fig. 9 is a solder XRD pattern and DSC curve for different Ti + Zr/Cu + Ni ratios (F1: Ti + Zr/Cu + Ni ═ 3, F2: Ti + Zr/Cu + Ni ═ 13/7, F3: Ti + Zr/Cu + Ni ═ 11/9, F4: Ti + Zr/Cu + Ni ═ 9/11) where F1: ti + Zr/Cu + Ni ═ 3 for comparative example 1, F2: ti + Zr/Cu + Ni 13/7 comparative example 2, F3: ti + Zr/Cu + Ni 11/9 for example 1, F4: ti + Zr/Cu + Ni 9/11 is comparative example 3.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims

1. The Ti-Zr-Cu-Ni amorphous solder is characterized by comprising the following components in percentage by mass: 26.0-29.0% Zr, 21.0-24.0% Ni, 21.0-24.0% Cu and the balance Ti.

2. The Ti-Zr-Cu-Ni amorphous solder according to claim 1, characterized by comprising the following components in percentage by mass: 26.5-28.5% of Zr, 21.5-23.5% of Ni, 21.5-23.5% of Cu and the balance of Ti.

3. A method for preparing Ti-Zr-Cu-Ni amorphous solder according to any one of claims 1 to 2, characterized by comprising the following steps:

4. The method for preparing the Ti-Zr-Cu-Ni amorphous solder according to claim 3, wherein the raw materials of Cu, Ni, Ti and Zr in the step (1) are all single pure metal bulk particles, and the purity of the single pure metal bulk particles is higher than 99.99%.

5. The method for preparing the Ti-Zr-Cu-Ni amorphous solder according to claim 3, wherein the raw materials of Cu, Ni, Ti and Zr in the step (1) are sequentially added into a smelting device according to the feeding sequence of single pure metal particles of Cu, Ni, Ti and Zr.

6. The method for preparing the Ti-Zr-Cu-Ni amorphous solder according to claim 3, wherein the melting in the step (1) is performed for 4 to 8 times in an inert gas or nitrogen atmosphere at 1900 to 2000 ℃ for 1 to 3 minutes each time; and (2) the smelting device in the step (1) is a vacuum arc furnace.

7. The method for preparing a Ti-Zr-Cu-Ni amorphous solder according to claim 3, wherein the step (2) is performed by induction heating melting using a flat-nose quartz tube.

8. The method for preparing the Ti-Zr-Cu-Ni amorphous solder according to claim 3, wherein the rapid solidification in the step (2) is carried out in a high vacuum single-roller rotary quenching system, and the process parameters of the rapid solidification are as follows: the linear velocity of the rotating copper roller is 27-32 m/s, the distance between the outlet of the melt and the surface of the copper roller is 1.0-1.5 mm, and the argon pressure for melt injection is 0.07-0.10 MPa.

9. The method for preparing the Ti-Zr-Cu-Ni amorphous solder according to claim 3, wherein the Cu, Ni, Ti and Zr raw materials in the step (1) are subjected to oxide film removal and impurity treatment, and specifically comprises the following steps: and (3) polishing the surfaces of the pure metal particles by using 180-mesh SiC abrasive paper, then carrying out acid cleaning, washing with absolute ethyl alcohol, blow-drying, and finally carrying out ultrasonic cleaning in an acetone bath agent and blow-drying.

10. Use of a Ti-Zr-Cu-Ni amorphous solder according to any of claims 1 to 2 for braze joining of γ -TiAl alloys and Ni-based alloys.