Nickel-based amorphous alloy brazing filler metal strip and preparation method and brazing method thereof

Abstract

The invention provides a nickel-based amorphous alloy brazing filler metal strip and a preparation method and a brazing method thereof, and belongs to the field of amorphous brazing filler metal strips. The nickel-based amorphous alloy brazing filler metal strip provided by the invention consists of the following elements in percentage by mass: 5-11% of Cr, 0-6% of Fe, 1-5% of Si, 2-3.5% of B, 0-3% of Co, 0-1% of E and the balance of Ni, the sum of the mass percent of Si and B is less than or equal to 7.5%; and E is Y, Nb or V. The result of the embodiment shows that the nickel-based amorphous alloy solder strip has good wettability, the spreading area on a 304 stainless steel plate can reach 22.5 mm < 2 >, the shear strength of a soldered joint of the nickel-based amorphous alloy solder strip can reach 927.6 MPa, and the nickel-based amorphous alloy solder strip has excellent shear strength.

Description

Technical Field

[0001] The invention relates to the field of amorphous solder strips, and in particular to a nickel-based amorphous alloy solder strip and a preparation method and a soldering method thereof. Background Art

[0002] In order to further optimize the energy structure, reduce energy loss and improve conversion efficiency. As an important carrier of energy conversion and heat transfer, various heat exchange equipment have become the core equipment for improving energy utilization efficiency. In modern petrochemical, high temperature gas-cooled reactor, aviation and other fields, not only high heat exchange efficiency of equipment is required, but also small size and compact structure. In order to achieve the above goals, the key lies in the use of high temperature resistant, compact and efficient heat exchangers to recycle and utilize high temperature waste heat and improve energy utilization efficiency. The core components of the heat exchanger are basically manufactured by vacuum brazing, which greatly improves the compactness and heat exchange efficiency of the heat exchanger, but at the same time, a large number of brazing joints will be generated at the connection parts. Brazing filler metal is one of the most critical factors that determine the performance of brazing joints. Different brazing fillers have different melting temperatures, wettability and spreading properties. Nickel-based brazing filler metal is particularly suitable for brazing of stainless steel and high temperature alloys due to its excellent properties such as high strength, oxidation resistance, corrosion resistance and high temperature resistance of brazing joints. It is widely used in aviation, aerospace, electromechanical, energy and civil fields.

[0003] Nickel-based brazing filler metal is a high-temperature brazing filler metal alloy with a complex phase structure, which is formed by adding appropriate amounts of alloying elements such as chromium, boron, silicon, tungsten, phosphorus, and carbon to nickel solid solution. The addition of strengthening elements such as chromium, silicon, boron, and phosphorus can reduce the melting point of nickel-based brazing filler metal and improve its comprehensive performance, but it also makes the brazing filler metal brittle and poor in forming ability, making it impossible to perform plastic processing. It can usually only be supplied in powder or sticky tape form, which brings disadvantages to brazing, such as inconvenient addition and difficulty in controlling the amount of addition.

[0004] The preparation cost of amorphous alloy solder is low, the solder alloying degree is high, the composition is highly adjustable, and it has good ductility. It can be prefabricated into the required foil strip and accurately placed in the brazing gap, which can significantly improve the joint strength and reliability; the spatial atomic distribution of amorphous alloy solder is similar to that of liquid, in a disordered state, with uniform organization, narrow melting temperature range, shortened brazing time, significantly reduced segregation, increased diffusion depth, improved brazing joint quality, and good corrosion resistance; amorphous alloy solder has a low melting point, good fluidity, uniform spreading, and good wettability, and can obtain a high-strength welded joint with a dense brazing layer. Most of the nickel-based amorphous alloy solders currently used are Ni-Cr-Si-B, Ni-Cr-B, and Ni-Cr-WB. In order to reduce melting, the solder contains a large amount of B and Si elements, which leads to a certain brittleness of the joint, which is not conducive to the high-strength and toughness brazing connection of high-temperature alloys, limiting its use as a solder for nickel-based high-temperature alloys. In order to obtain a low-brittleness brazed joint of a Ni-based alloy, the conventional solution is to reduce the Si and B content of the Ni-based amorphous brazing filler metal. However, the reduction in the Si and B content will cause an increase in the melting point and lead to an increase in the brazing temperature. The increase in the brazing temperature will lead to the generation of some brittle phases, and the brittle phases inside the joint will increase, thereby reducing the shear strength of the brazed joint. Under current technical conditions, the shear strength of the brazed joint after brazing with a nickel-based amorphous alloy brazing filler metal is mostly concentrated at around 750MPa, which cannot meet the long-term operation requirements under harsh environments such as high temperature and high pressure. It is necessary to further improve the shear strength of the brazed joint after brazing. Summary of the invention

[0005] The purpose of the present invention is to provide a nickel-based amorphous alloy solder strip material and a preparation method and a brazing method thereof. When the nickel-based amorphous alloy solder strip material provided by the present invention is used for brazing, the brazed joint obtained by brazing has high shear strength.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The invention provides a nickel-based amorphous alloy brazing material strip, which is composed of the following elements by mass percentage: 5-11% of Cr, 0-6% of Fe, 1-5% of Si, 2-3.5% of B, 0-3% of Co, 0-1% of E and the balance of Ni; the total mass percentage of the Si and B elements is ≤7.5%; and E is Y, Nb or V.

[0008] Preferably, the nickel-based amorphous alloy brazing strip is composed of the following elements in percentage by mass: Cr 8-11%, Fe 2-5%, Si 2-4%, B 2.5-3.5%, Co 0-2%, E 0.1-0.6% and the balance Ni; the total percentage by mass of the Si and B elements is ≤7%.

[0009] Preferably, the nickel-based amorphous alloy brazing strip is composed of the following elements in percentage by mass: Cr 10-11%, Fe 3-4%, Si 3-4%, B 2.5-3%, Co 0-1%, E 0.2-0.4% and the balance Ni; the total mass percentage of the Si and B elements is ≤6.5%.

[0010] The present invention provides a method for preparing the nickel-based amorphous alloy brazing material strip described in the above technical solution, comprising the following steps:

[0011] (1) smelting the raw materials and then casting to obtain an alloy ingot;

[0012] (2) The alloy ingot obtained in step (1) is subjected to vacuum stripping to obtain a nickel-based amorphous alloy solder strip.

[0013] Preferably, the smelting in step (1) is carried out in an inert atmosphere; the pressure of the inert atmosphere is 0.01 to 0.10 MPa.

[0014] Preferably, the vacuum belt spinning in step (2) comprises: cooling the melt obtained by melting the alloy ingot by blowing the melt onto the surface of a rotating cooling device through a belt-blowing gas; the temperature of the melt is 900-1300°C.

[0015] Preferably, the pressure of the spray gas during the spraying is 0.10-0.12 MPa.

[0016] Preferably, during the spraying, the distance between the nozzle and the surface of the cooling device is 1 to 3 mm.

[0017] Preferably, the rotation speed of the cooling device is 32-39 m / s.

[0018] The present invention provides a brazing method for the nickel-based amorphous alloy brazing strip described in the above technical solution or the nickel-based amorphous alloy brazing strip prepared by the preparation method described in the above technical solution, wherein the brazing method is vacuum brazing; the brazing temperature of the vacuum brazing is 1130-1160°C.

[0019] The present invention provides a nickel-based amorphous alloy solder strip, which is composed of the following elements by mass percentage: Cr 5-11%, Fe 0-6%, Si 1-5%, B 2-3.5%, Co 0-3%, E 0-1% and the balance Ni; the sum of the mass percentages of the Si and B elements is ≤7.5%; and E is Y, Nb or V. The present invention reduces the brittle phase in the brazed joint by controlling the content of Si and B elements in the alloy and limiting the total content of Si and B elements to a smaller range, thereby improving the shear strength of the brazed joint of the nickel-based amorphous alloy solder; by adding Y, Nb or V elements, the wettability of the solder can be improved, the joint structure can be improved, and the nickel-based amorphous alloy solder has good wettability and shear strength, and can also improve the corrosion resistance of the brazed joint, further improving the welding performance of the brazed joint. The results of the embodiment show that the nickel-based amorphous solder strip provided by the present invention has good wettability, and the spreading area on the 304 stainless steel plate can reach 22.5 mm 2 The shear strength of the brazed joint of nickel-based amorphous alloy brazing strip can reach 927.6MPa, which has excellent shear strength. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a macroscopic photograph of a welded joint in a brazed component in Application Example 4 of the present invention, wherein the left picture is a top view and the right picture is a side view;

[0021] Figure 2 A bar graph of the shear strength of the brazed joints obtained in Application Example 4, Application Example 9, Comparative Application Example 1 and Comparative Application Example 2 of the present invention;

[0022] Figure 3 This is the organizational structure diagram of the brazed joint obtained in Comparative Application Example 1 of the present invention;

[0023] Figure 4 This is a diagram of the organizational structure of the brazed joint obtained in Application Example 9 of the present invention;

[0024] Figure 5 This is the organizational structure diagram of the brazed joint obtained in Application Example 4 of the present invention;

[0025] Figure 6 This is the organizational structure diagram of the brazed joint obtained in comparative application example 2 of the present invention;

[0026] Figure 7 It is a spreading diagram of the molten liquid of the alloy ingot in Example 4 of the present invention at a brazing temperature of 1160° C.;

[0027] Figure 8 This is a diagram showing the spread of the molten liquid of the nickel-based amorphous alloy solder strip in Example 4 of the present invention at a brazing temperature of 1160°C. DETAILED DESCRIPTION

[0028] The invention provides a nickel-based amorphous alloy solder strip, which is composed of the following elements by mass percentage: 5-11% Cr, 0-6% Fe, 1-5% Si, 2-3.5% B, 0-3% Co, 0-1% E and the balance Ni.

[0029] The nickel-based amorphous alloy solder strip provided by the present invention includes 5-11% Cr, preferably 8-11%, more preferably 10-11%, and further preferably 10.5% by mass percentage. The present invention limits the content of Cr element to the above range so that the nickel-based amorphous alloy solder has good mechanical properties.

[0030] The nickel-based amorphous alloy brazing material strip provided by the present invention includes Fe 0-6%, preferably 2-5%, and more preferably 3-4%, by mass percentage. The present invention limits the content of the Fe element to the above range to reduce the melting point of the material, improve the wettability of the material, and increase the brazing strength, thereby making the nickel-based amorphous alloy brazing material have good mechanical properties.

[0031] The nickel-based amorphous alloy solder strip provided by the present invention includes Si 1-5%, preferably 2-4%, and more preferably 3-4%, by mass percentage. The content of Si element is limited to the above range to improve the fluidity of the nickel-based amorphous solder material, thereby making the nickel-based amorphous alloy solder have good wettability and shear strength.

[0032] The nickel-based amorphous alloy solder strip provided by the present invention comprises 2-3.5% B, preferably 2.5-3.5%, and more preferably 2.5-3% B by mass percentage. The present invention limits the content of B element to the above range to reduce the brittle phase in the nickel-based amorphous alloy, thereby improving the toughness and shear strength of the nickel-based amorphous alloy solder.

[0033] The nickel-based amorphous alloy solder strip provided by the present invention comprises 0-3%, preferably 0-2%, and more preferably 0-1% Co by mass percentage. The Co element of the present invention can improve the hardness of the material, thereby making the nickel-based amorphous alloy solder have good wear resistance, corrosion resistance and higher strength.

[0034] In terms of mass percentage, the nickel-based amorphous alloy solder strip provided by the present invention includes E 0-1%, preferably 0.1-0.6%, and more preferably 0.2-0.4%. In the present invention, the E is Y, Nb or V, preferably V. The E element (Y, Nb or V element) of the present invention can improve the wettability of the solder, improve the joint structure, and thus make the nickel-based amorphous alloy solder have good wettability and shear strength. The present invention limits the content of the E element (Y, Nb or V element) to the above range to further improve the shear strength of the nickel-based amorphous alloy solder.

[0035] In the present invention, the sum of the mass percentages of Si and B elements is ≤7.5%, preferably ≤7%, more preferably ≤6.5%, and further preferably 6%. In the present invention, limiting the sum of the mass percentages of Si and B elements to the above range can reduce the brittle phase in the nickel-based amorphous alloy and make the nickel-based amorphous alloy brazing material have good shear strength.

[0036] The present invention controls the content of Si and B elements in the alloy and limits the total content of Si and B elements within a smaller range, thereby reducing the brittle phase in the brazed joint and improving the shear strength of the brazed joint of the nickel-based amorphous alloy solder; by adding Y, Nb or V elements, the wettability of the solder can be improved, the joint structure can be improved, and the nickel-based amorphous alloy solder has good wettability and shear strength, and the corrosion resistance of the brazed joint can be improved, and the welding performance of the solder brazed joint can be further improved.

[0037] The present invention provides a method for preparing the nickel-based amorphous alloy brazing material strip described in the above technical solution, comprising the following steps:

[0038] (1) smelting the raw materials and then casting to obtain an alloy ingot;

[0039] (2) The alloy ingot obtained in step (1) is subjected to vacuum stripping to obtain a nickel-based amorphous alloy solder strip.

[0040] The invention melts the raw materials and then casts them to obtain alloy ingots.

[0041] In the present invention, the raw materials are preferably Y, Nb or V particles, Cr particles, Fe particles, Si particles, B particles, Co particles and Ni particles with a purity of 99.99%. In the present invention, the particle sizes of the Y, Nb or V particles, Cr particles, Fe particles, Si particles, B particles, Co particles and Ni particles are preferably independently ≤3 mm. The present invention limits the type, purity and particle size of the raw materials to the above ranges to reduce impurities in the alloy and meet the requirements of the alloy ingot for the component content.

[0042] In the present invention, the raw materials are preferably placed in a quartz crucible for smelting.

[0043] In the present invention, the smelting is preferably carried out in an inert atmosphere; the pressure of the inert atmosphere is preferably 0.01-0.10 MPa; the inert atmosphere is preferably argon.

[0044] In the present invention, the equipment used for smelting is preferably a vacuum arc furnace; the vacuum degree of the vacuum arc furnace is preferably ≥3×10 -3 Pa.

[0045] In the present invention, the specific steps of smelting are preferably: placing the raw materials in a quartz crucible, evacuating the vacuum furnace to a vacuum degree of ≥3×10 -3 After reaching Pa, inert gas is introduced to reach 0.01~0.10MPa.

[0046] In the present invention, the smelting current is preferably 100-200 A, more preferably 120-160 A. In the present invention, setting the smelting current within the above range can ensure complete melting of the amorphous alloy raw material.

[0047] In the present invention, stirring is preferably performed during the smelting process; the stirring method is preferably mechanical stirring. The present invention has no special limitation on the stirring speed, and the conventional stirring speed of those skilled in the art can be used.

[0048] In the present invention, the smelting process is preferably repeated 2 to 3 times. In the present invention, limiting the number of repetitions of the smelting process to the above range can make the alloy composition more uniform.

[0049] The present invention has no particular limitation on the time of the single smelting, as long as it can melt the amorphous alloy raw material.

[0050] After obtaining the alloy ingot, the present invention performs vacuum stripping on the alloy ingot to obtain a nickel-based amorphous alloy solder strip.

[0051] As an embodiment of the present invention, the vacuum belt spinning is carried out in a vacuum belt spinning machine.

[0052] In the present invention, the vacuum belt spinning preferably includes: cooling the melt obtained by melting the alloy ingot by blowing the melt onto the surface of a rotating cooling device through a belt blowing gas.

[0053] In the present invention, the alloy ingot is preferably crushed before melting. The present invention has no special limitation on the crushing equipment, and crushing can be performed using crushing equipment familiar to those skilled in the art. The present invention has no special limitation on the particle size of the alloy particles after crushing, and it only needs to be able to be placed in a melting device.

[0054] As an implementation mode of the present invention, the alloy ingot is melted in a melting device to obtain a melt; in an embodiment of the present invention, the melting device is a quartz tube.

[0055] As an embodiment of the present invention, the temperature of the melt may be 900-1300° C., or 1000-1200° C. The present invention limits the temperature of the melt to the above range so that the alloy elements in the melt can be evenly distributed.

[0056] The present invention preferably performs vacuuming and filling with inert gas before melting to realize vacuum belting; as an embodiment of the present invention, the inert gas may be high-purity argon; the purity of the high-purity argon is preferably 99.999%; the specific steps of vacuuming and filling with inert gas are preferably: placing the quartz tube into a vacuum belting machine and vacuuming to ≥1×10 -3 After reaching the pressure of 0.05-0.10 MPa, argon is introduced to the pressure, and the vacuuming and argon introduction steps are repeated 2-3 times, and the argon is filled to 0.01 MPa for the last time. The present invention can prevent the alloy from being oxidized by vacuuming and filling with inert gas.

[0057] As an embodiment of the present invention, the gas for the spray belt is stored in a blowing device; the blowing device is arranged above the melting device; in an embodiment of the present invention, the blowing device is a gas storage tank. In the present invention, the gas for the spray belt is preferably high-purity argon; the purity of the high-purity argon is preferably 99.999%; the pressure in the cavity of the blowing device is preferably 0.11-0.13MPa. The present invention can prevent oxidation of the alloy by evacuating the blowing device and filling it with high-purity argon.

[0058] In the present invention, the pressure of the gas during the blowing is preferably 0.10-0.12 MPa, more preferably 0.12 MPa. In the present invention, setting the pressure of the gas during the blowing within the above range can facilitate the preparation of the solder strip.

[0059] In the present invention, the cooling device is preferably a cooling copper roller; the rotation speed of the cooling device is preferably 32 to 39 m / s. In the present invention, the rotation speed of the cooling device is set within the above range to prepare a complete strip.

[0060] In the present invention, the distance between the nozzle and the surface of the cooling device during the blowing is preferably 1 to 3 mm. The present invention limits the distance between the nozzle and the surface of the cooling device during the blowing to the above range to obtain a complete strip with a suitable thickness.

[0061] In the present invention, the frequency of the frequency converter of the cooling device is preferably 70-90 Hz. The present invention sets the frequency of the frequency converter within the above range to ensure that the rotation speed of the cooling device is 32-39 m / s.

[0062] In the present invention, the thickness of the nickel-based amorphous alloy solder strip is preferably 30-40 μm; the width of the nickel-based amorphous alloy solder strip is preferably 10-15 mm.

[0063] The present invention provides a brazing method for the nickel-based amorphous alloy brazing strip material described in the above technical solution or the nickel-based amorphous alloy brazing strip material prepared by the preparation method described in the above technical solution, wherein the brazing method is vacuum brazing; the brazing temperature of the vacuum brazing is 1130-1160°C. In an embodiment of the present invention, the brazing temperature of the vacuum brazing may be 1130°C, 1140°C, 1150°C or 1160°C. The present invention limits the brazing temperature of the vacuum brazing to the above range, which can further improve the shear strength of the brazed joint.

[0064] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0065] Example 1

[0066] A nickel-based amorphous alloy brazing material strip, composed of the following elements by mass percentage: 10.5% Cr, 4.5% Si, 3.0% B and the balance Ni; the total mass percentage of the Si and B elements is 7.5%;

[0067] The method for preparing the nickel-based amorphous alloy solder strip comprises the following steps:

[0068] (1) Weigh Cr particles, Si particles, B particles and Ni particles and place them in a quartz crucible. Evacuate the vacuum arc furnace to a vacuum degree of ≥3×10 -3 After the temperature reaches 0.05 MPa, high-purity argon gas is introduced to 0.05 MPa, and vacuum induction melting is performed by high-frequency power heating. The melting current is 120 A, and stirring is performed during the melting process. After the alloy is completely molten, the temperature is kept for 5 minutes. The operation is repeated 3 times to make the liquid metal melt evenly and then cast to obtain an alloy ingot.

[0069] (2) The alloy ingot obtained in step (1) is crushed and placed in a quartz tube, the quartz tube is placed in a vacuum belt spinning machine, the distance between the nozzle of the quartz tube and the surface of the cooling copper roller is adjusted to 1 mm, and the vacuum belt spinning machine cavity is evacuated to a vacuum degree of 3×10 -3After the temperature reaches 0.1 MPa, high-purity argon is filled in, and the vacuum and high-purity argon are repeated for 3 times, and the last filling is to 0.01 MPa; the blowing device is arranged above the melting device; the blowing device is a small gas storage tank; the small gas storage tank is filled with spray gas; the spray gas is high-purity argon; the pressure in the cavity of the blowing device is 0.13 MPa; the speed of the cooling copper roller is adjusted to 32 m / s; the alloy in the quartz tube is heated to 100°C above the melting point (melting temperature 1106°C) by an induction coil, and after the alloy is completely turned into liquid and the surface fluctuates, the blowing device is immediately used to blow the alloy melt onto the rotating cooling copper roller, and the nickel-based amorphous alloy solder strip is obtained by rapid cooling; the nickel-based amorphous alloy solder strip has a thickness of 35 μm and a width of 10.1 mm; the pressure of the gas during the blowing is 0.12 MPa;

[0070] The specific steps for setting the pressure in the cavity of the blowing device are preferably: evacuating the small gas storage tank, closing the exhaust valve when the vacuum gauge pointer drops to the lowest position, filling with high-purity argon gas to 0.13MPa, repeating the evacuation and filling with high-purity argon gas steps 3 times, and filling with high-purity argon gas to 0.13MPa for the last time.

[0071] Example 2

[0072] A nickel-based amorphous alloy brazing material strip, composed of the following elements by mass percentage: 10.5% Cr, 1% Fe, 4.0% Si, 3.0% B and the balance Ni; the total mass percentage of the Si and B elements is 7.0%;

[0073] The method for preparing the nickel-based amorphous alloy solder strip comprises the following steps:

[0074] (1) Weigh Cr particles, Fe particles, Si particles, B particles and Ni particles and place them in a quartz crucible. Evacuate the vacuum furnace to a vacuum degree of ≥3×10 -3 After the temperature reaches 0.05 MPa, high-purity argon gas is introduced to 0.05 MPa, and vacuum induction melting is performed by high-frequency power heating. The melting current is 120 A, and stirring is performed during the melting process. After the alloy is completely molten, the temperature is kept for 5 minutes. The operation is repeated 3 times to make the liquid metal melt evenly and then cast to obtain an alloy ingot.

[0075] (2) The alloy ingot obtained in step (1) is crushed and placed in a quartz tube, the quartz tube is placed in a vacuum belt spinning machine, the distance between the nozzle of the quartz tube and the surface of the cooling copper roller is adjusted to 1 mm, and the vacuum belt spinning machine cavity is evacuated to a vacuum degree of 3×10 -3After the temperature reaches 0.1 MPa, high-purity argon is filled in, and the vacuum and high-purity argon are repeated for 3 times, and the last filling is to 0.01 MPa; the blowing device is arranged above the melting device; the blowing device is a small gas storage tank; the small gas storage tank is filled with spray gas; the spray gas is high-purity argon; the pressure in the cavity of the blowing device is 0.13 MPa; the speed of the cooling copper roller is adjusted to 32 m / s; the alloy in the quartz tube is heated to 100°C above the melting point (melting temperature 1104°C) by an induction coil, and after the alloy is completely turned into liquid and the surface fluctuates, the blowing device is immediately used to blow the alloy melt onto the rotating cooling copper roller, and the nickel-based amorphous alloy solder strip is obtained by rapid cooling; the nickel-based amorphous alloy solder strip has a thickness of 35 μm and a width of 10.1 mm; the pressure of the gas during the blowing is 0.12 MPa;

[0076] The specific steps for setting the pressure in the cavity of the blowing device are preferably: evacuating the small gas storage tank, closing the exhaust valve when the vacuum gauge pointer drops to the lowest position, filling with high-purity argon gas to 0.13MPa, repeating the evacuation and filling with high-purity argon gas steps 3 times, and filling with high-purity argon gas to 0.13MPa for the last time.

[0077] Example 3

[0078] A nickel-based amorphous alloy brazing material strip, composed of the following elements by mass percentage: 10.5% Cr, 2% Fe, 3.5% Si, 3.0% B, 0.1% V and the balance Ni; the total mass percentage of the Si and B elements is 6.5%;

[0079] The method for preparing the nickel-based amorphous alloy solder strip comprises the following steps:

[0080] (1) Weigh V particles, Cr particles, Fe particles, Si particles, B particles and Ni particles and put them into a quartz crucible. Evacuate the vacuum arc furnace until the vacuum degree is ≥3×10 -3 After the temperature reaches 0.05 MPa, high-purity argon gas is introduced to 0.05 MPa, and vacuum induction melting is performed by high-frequency power heating. The melting current is 120 A, and stirring is performed during the melting process. After the alloy is completely molten, the temperature is kept for 5 minutes. The operation is repeated 3 times to make the liquid metal melt evenly and then cast to obtain an alloy ingot.

[0081] (2) The alloy ingot obtained in step (1) is crushed and placed in a quartz tube, the quartz tube is placed in a vacuum belt spinning machine, the distance between the nozzle of the quartz tube and the surface of the cooling copper roller is adjusted to 1 mm, and the vacuum belt spinning machine cavity is evacuated to a vacuum degree of 3×10 -3Pa, high-purity argon is filled to 0.1MPa, and vacuumization and filling with high-purity argon are repeated 3 times, and the last filling is to 0.01MPa; the blowing device is arranged above the melting device; the blowing device is a small gas storage tank; the small gas storage tank is filled with spray gas; the spray gas is high-purity argon; the pressure in the cavity of the blowing device is 0.13Pa; the speed of the cooling copper roller is adjusted to 32m / s; the alloy in the quartz tube is heated to 100℃ above the melting point (melting temperature 1100℃) by an induction coil, and after the alloy is completely turned into liquid and the surface fluctuates, the blowing device is immediately used to blow the alloy melt onto the rotating cooling copper roller, and a nickel-based amorphous alloy solder strip is obtained by rapid cooling; the nickel-based amorphous alloy solder strip has a thickness of 35μm and a width of 10.1mm; the pressure of the gas during the blowing is 0.12Pa;

[0082] The specific steps for setting the pressure in the cavity of the blowing device are preferably: evacuating the small gas storage tank, closing the exhaust valve when the vacuum gauge pointer drops to the lowest position, filling with high-purity argon gas to 0.13MPa, repeating the evacuation and filling with high-purity argon gas steps 3 times, and filling with high-purity argon gas to 0.13MPa for the last time.

[0083] Example 4

[0084] A nickel-based amorphous alloy brazing material strip, composed of the following elements by mass percentage: 10.5% Cr, 3.0% Fe, 3.0% Si, 3.0% B, 0.2% V and the balance Ni; the total mass percentage of the Si and B elements is 6.0%;

[0085] The method for preparing the nickel-based amorphous alloy solder strip comprises the following steps:

[0086] (1) Weigh V particles, Cr particles, Fe particles, Si particles, B particles and Ni particles and put them into a quartz crucible. Evacuate the vacuum arc furnace until the vacuum degree is ≥3×10 -3 After the temperature reaches 0.05 MPa, high-purity argon gas is introduced to 0.05 MPa, and vacuum induction melting is performed by high-frequency power heating. The melting current is 120 A, and stirring is performed during the melting process. After the alloy is completely molten, the temperature is kept for 5 minutes. The operation is repeated 3 times to make the liquid metal melt evenly and then cast to obtain an alloy ingot.

[0087] (2) The alloy ingot obtained in step (1) is crushed and placed in a quartz tube, the quartz tube is placed in a vacuum belt spinning machine, the distance between the nozzle of the quartz tube and the surface of the cooling copper roller is adjusted to 1 mm, and the vacuum belt spinning machine cavity is evacuated to a vacuum degree of 3×10 -3Pa, high-purity argon is filled to 0.1MPa, and vacuumization and filling with high-purity argon are repeated 3 times, and the last filling is to 0.01MPa; the blowing device is arranged above the melting device; the blowing device is a small gas storage tank; the small gas storage tank is filled with spray gas; the spray gas is high-purity argon; the pressure in the cavity of the blowing device is 0.13Pa; the speed of the cooling copper roller is adjusted to 32m / s; the alloy in the quartz tube is heated to 100℃ above the melting point (melting temperature 1090℃) by an induction coil, and after the alloy is completely turned into liquid and the surface fluctuates, the blowing device is immediately used to blow the alloy melt onto the rotating cooling copper roller, and a nickel-based amorphous alloy solder strip is obtained by rapid cooling; the nickel-based amorphous alloy solder strip has a thickness of 35μm and a width of 10.1mm; the pressure of the gas during the blowing is 0.12Pa;

[0088] The specific steps for setting the pressure in the cavity of the blowing device are preferably: evacuating the small gas storage tank, closing the exhaust valve when the vacuum gauge pointer drops to the lowest position, filling with high-purity argon gas to 0.13MPa, repeating the evacuation and filling with high-purity argon gas steps 3 times, and filling with high-purity argon gas to 0.13MPa for the last time.

[0089] Example 5

[0090] A nickel-based amorphous alloy brazing material strip, composed of the following elements by mass percentage: 10.5% Cr, 3.5% Fe, 2.5% Si, 3.0% B, 0.3% V and the balance Ni; the total mass percentage of the Si and B elements is 5.5%;

[0091] The method for preparing the nickel-based amorphous alloy solder strip comprises the following steps:

[0092] (1) Weigh V particles, Cr particles, Fe particles, Si particles, B particles and Ni particles and put them into a quartz crucible. Evacuate the vacuum arc furnace until the vacuum degree is ≥3×10 -3 After the temperature reaches 0.05 MPa, high-purity argon gas is introduced to 0.05 MPa, and vacuum induction melting is performed by high-frequency power heating. The melting current is 120 A, and stirring is performed during the melting process. After the alloy is completely molten, the temperature is kept for 5 minutes. The operation is repeated 3 times to make the liquid metal melt evenly and then cast to obtain an alloy ingot.

[0093] (2) The alloy ingot obtained in step (1) is crushed and placed in a quartz tube, the quartz tube is placed in a vacuum belt spinning machine, the distance between the nozzle of the quartz tube and the surface of the cooling copper roller is adjusted to 1 mm, and the vacuum belt spinning machine cavity is evacuated to a vacuum degree of 3×10 -3Pa, high-purity argon is filled to 0.1MPa, and vacuumization and filling with high-purity argon are repeated 3 times, and the last filling is to 0.01MPa; the blowing device is arranged above the melting device; the blowing device is a small gas storage tank; the small gas storage tank is filled with spray gas; the spray gas is high-purity argon; the pressure in the cavity of the blowing device is 0.13Pa; the speed of the cooling copper roller is adjusted to 32m / s; the alloy in the quartz tube is heated to 100℃ above the melting point (melting temperature 1090℃) by an induction coil, and after the alloy is completely turned into liquid and the surface fluctuates, the blowing device is immediately used to blow the alloy melt onto the rotating cooling copper roller, and a nickel-based amorphous alloy solder strip is obtained by rapid cooling; the nickel-based amorphous alloy solder strip has a thickness of 35μm and a width of 10.1mm; the pressure of the gas during the blowing is 0.12Pa;

[0094] The specific steps for setting the pressure in the cavity of the blowing device are preferably: evacuating the small gas storage tank, closing the exhaust valve when the vacuum gauge pointer drops to the lowest position, filling with high-purity argon gas to 0.13MPa, repeating the evacuation and filling with high-purity argon gas steps 3 times, and filling with high-purity argon gas to 0.13MPa for the last time.

[0095] Example 6

[0096] A nickel-based amorphous alloy brazing material strip, composed of the following elements by mass percentage: 10.5% Cr, 4.0% Fe, 2.0% Si, 3.0% B, 0.4% V and the balance Ni; the total mass percentage of the Si and B elements is 5.0%;

[0097] The method for preparing the nickel-based amorphous alloy solder strip comprises the following steps:

[0098] (1) Weigh V particles, Cr particles, Fe particles, Si particles, B particles and Ni particles and put them into a quartz crucible. Evacuate the vacuum arc furnace until the vacuum degree is ≥3×10 -3 After the temperature reaches 0.05 MPa, high-purity argon gas is introduced to 0.05 MPa, and vacuum induction melting is performed by high-frequency power heating. The melting current is 120 A, and stirring is performed during the melting process. After the alloy is completely molten, the temperature is kept for 5 minutes. The operation is repeated 3 times to make the liquid metal melt evenly and then cast to obtain an alloy ingot.

[0099] (2) The alloy ingot obtained in step (1) is crushed and placed in a quartz tube, the quartz tube is placed in a vacuum belt spinning machine, the distance between the nozzle of the quartz tube and the surface of the cooling copper roller is adjusted to 1 mm, and the vacuum belt spinning machine cavity is evacuated to a vacuum degree of 3×10 -3Pa, high-purity argon is filled to 0.1MPa, and vacuumization and filling with high-purity argon are repeated 3 times, and the last filling is to 0.01MPa; the blowing device is arranged above the melting device; the blowing device is a small gas storage tank; the small gas storage tank is filled with spray gas; the spray gas is high-purity argon; the pressure in the cavity of the blowing device is 0.13Pa; the speed of the cooling copper roller is adjusted to 32m / s; the alloy in the quartz tube is heated to 100℃ above the melting point (melting temperature 1100℃) by an induction coil, and after the alloy is completely turned into liquid and the surface fluctuates, the blowing device is immediately used to blow the alloy melt onto the rotating cooling copper roller, and a nickel-based amorphous alloy solder strip is obtained by rapid cooling; the nickel-based amorphous alloy solder strip has a thickness of 35μm and a width of 10.1mm; the pressure of the gas during the blowing is 0.12Pa;

[0100] The specific steps for setting the pressure in the cavity of the blowing device are preferably: evacuating the small gas storage tank, closing the exhaust valve when the vacuum gauge pointer drops to the lowest position, filling with high-purity argon gas to 0.13MPa, repeating the evacuation and filling with high-purity argon gas steps 3 times, and filling with high-purity argon gas to 0.13MPa for the last time.

[0101] Example 7

[0102] A nickel-based amorphous alloy brazing material strip, composed of the following elements by mass percentage: 10.5% Cr, 4.5% Fe, 1.5% Si, 3.0% B, 0.5% V and the balance Ni; the total mass percentage of the Si and B elements is 4.5%;

[0103] The method for preparing the nickel-based amorphous alloy solder strip comprises the following steps:

[0104] (1) Weigh V particles, Cr particles, Fe particles, Si particles, B particles and Ni particles and put them into a quartz crucible. Evacuate the vacuum arc furnace until the vacuum degree is ≥3×10 -3 After the temperature reaches 0.05 MPa, high-purity argon gas is introduced to 0.05 MPa, and vacuum induction melting is performed by high-frequency power heating. The melting current is 120 A, and stirring is performed during the melting process. After the alloy is completely molten, the temperature is kept for 5 minutes. The operation is repeated 3 times to make the liquid metal melt evenly and then cast to obtain an alloy ingot.

[0105] (2) The alloy ingot obtained in step (1) is crushed and placed in a quartz tube, the quartz tube is placed in a vacuum belt spinning machine, the distance between the nozzle of the quartz tube and the surface of the cooling copper roller is adjusted to 1 mm, and the vacuum belt spinning machine cavity is evacuated to a vacuum degree of 3×10 -3Pa, high-purity argon is filled to 0.1MPa, and vacuuming and filling with high-purity argon are repeated 3 times, and the last filling is to 0.01MPa; the blowing device is arranged above the melting device; the blowing device is a small gas storage tank; the small gas storage tank is filled with spray gas; the spray gas is high-purity argon; the pressure in the cavity of the blowing device is 0.13Pa; the speed of the cooling copper roller is adjusted to 32m / s; the alloy in the quartz tube is heated to 100℃ above the melting point (melting temperature 1102℃) by an induction coil, and after the alloy is completely turned into liquid and the surface fluctuates, the blowing device is immediately used to blow the alloy melt onto the rotating cooling copper roller, and a nickel-based amorphous alloy solder strip is obtained by rapid cooling; the nickel-based amorphous alloy solder strip has a thickness of 35μm and a width of 10.1mm; the pressure of the gas during the blowing is 0.12Pa;

[0106] The specific steps for setting the pressure in the cavity of the blowing device are preferably: evacuating the small gas storage tank, closing the exhaust valve when the vacuum gauge pointer drops to the lowest position, filling with high-purity argon gas to 0.13MPa, repeating the evacuation and filling with high-purity argon gas steps 3 times, and filling with high-purity argon gas to 0.13MPa for the last time.

[0107] Example 8

[0108] A nickel-based amorphous alloy brazing material strip, composed of the following elements by mass percentage: 10.5% Cr, 5.0% Fe, 1.0% Si, 3.0% B, 0.6% V and the balance Ni; the total mass percentage of the Si and B elements is 4.0%;

[0109] The method for preparing the nickel-based amorphous alloy solder strip comprises the following steps:

[0110] (1) Weigh V particles, Cr particles, Fe particles, Si particles, B particles and Ni particles and put them into a quartz crucible. Evacuate the vacuum arc furnace until the vacuum degree is ≥3×10 -3 After the temperature reaches 0.05 MPa, high-purity argon gas is introduced to 0.05 MPa, and vacuum induction melting is performed by high-frequency power heating. The melting current is 120 A, and stirring is performed during the melting process. After the alloy is completely molten, the temperature is kept for 5 minutes. The operation is repeated 3 times to make the liquid metal melt evenly and then cast to obtain an alloy ingot.

[0111] (2) The alloy ingot obtained in step (1) is crushed and placed in a quartz tube, the quartz tube is placed in a vacuum belt spinning machine, the distance between the nozzle of the quartz tube and the surface of the cooling copper roller is adjusted to 1 mm, and the vacuum belt spinning machine cavity is evacuated to a vacuum degree of 3×10 -3Pa, high-purity argon is filled to 0.1MPa, and vacuumization and filling with high-purity argon are repeated 3 times, and the last filling is to 0.01MPa; the blowing device is arranged above the melting device; the blowing device is a small gas storage tank; the small gas storage tank is filled with spray gas; the spray gas is high-purity argon; the pressure in the cavity of the blowing device is 0.13Pa; the speed of the cooling copper roller is adjusted to 32m / s; the alloy in the quartz tube is heated to 100℃ above the melting point (melting temperature 1105℃) by an induction coil, and after the alloy is completely turned into liquid and the surface fluctuates, the blowing device is immediately used to blow the alloy melt onto the rotating cooling copper roller, and a nickel-based amorphous alloy solder strip is obtained by rapid cooling; the nickel-based amorphous alloy solder strip has a thickness of 35μm and a width of 10.1mm; the pressure of the gas during the blowing is 0.12Pa;

[0112] The specific steps for setting the pressure in the cavity of the blowing device are preferably: evacuating the small gas storage tank, closing the exhaust valve when the vacuum gauge pointer drops to the lowest position, filling with high-purity argon gas to 0.13MPa, repeating the evacuation and filling with high-purity argon gas steps 3 times, and filling with high-purity argon gas to 0.13MPa for the last time.

[0113] Application Examples 1 to 8

[0114] The nickel-based amorphous alloy brazing material strip prepared in Examples 1 to 8 is used to braze Inconel 625 nickel-based alloy in a vacuum brazing furnace, specifically comprising the following steps:

[0115] (1) Before brazing, the surface of the Inconel 625 nickel-based alloy was polished smooth using 400#, 800#, 1500# and 2000# SiC sandpaper in turn; after polishing, the sample was polished with a polishing agent, and then the sample was placed in ethanol for 25 minutes to remove the residual polishing agent and other stains on the surface, and finally the sample was blown dry with a hair dryer;

[0116] (2) The brazing joint adopts the overlapping method. The nickel-based amorphous alloy brazing strip is pre-placed between two Inconel625 alloy plates to form a sandwich structure. The above-mentioned brazing workpiece is placed in a vacuum brazing furnace and the vacuum degree reaches 9.0×10 -3 Pa, start heating to 900℃ at a rate of 10℃ / min, keep warm for 10min, then heat to 1160℃ at a rate of 10℃ / min for brazing. After keeping warm for 60min, turn off the heating system, and let the brazed parts cool to room temperature with the furnace. After the brazed structure cools to room temperature, take it out of the vacuum brazing furnace.

[0117] The alloy composition of Inconel625 nickel-based alloy is shown in Table 1.

[0118] Table 1 Alloy composition of Inconel625 nickel-based alloy

[0119] element Ni C Mn Si S P Cr Mo W V Co Nb Wt.% 62.1 0.041 0.277 0.237 0.0014 0.0025 20.89 8.610 0.23 0.063 0.05 3.32

[0120] Application Example 9

[0121] The nickel-based amorphous alloy brazing material strip prepared in Example 4 was used to braze Inconel 625 nickel-based alloy in a vacuum brazing furnace. The difference between Application Example 9 and Application Example 4 was only that the brazing temperature was 1130° C., and the rest was the same as Application Example 4.

[0122] Comparative application example 1

[0123] The only difference between comparative application example 1 and application example 9 is that the brazing temperature is 1100° C., and the rest is the same as application example 9.

[0124] Comparative Application Example 2

[0125] The only difference between comparative application example 2 and application example 9 is that the brazing temperature is 1190° C., and the rest is the same as application example 9.

[0126] A 25-ton microcomputer-controlled universal testing machine model TSE255D was used to test the shear strength of the brazed joints in the brazed parts obtained from Example 1 to Example 9 and Comparative Application Examples 1 to 2. The test method is as follows: load the sample into the fixture of the testing machine and apply force to the sample until the sample is damaged. The force applied when the sample is damaged during the test is recorded and divided by the area of ​​the weld joint to obtain the shear strength. The test results are shown in Table 2. Table 2 Shear strength test results of the brazed joints in the brazed parts obtained from Example 1 to Example 9 and Comparative Application Examples 1 to 2

[0127] Application Examples Shear strength(MPa) Application Example 1 786.40 Application Example 2 797.40 Application Example 3 789.62 Application Example 4 927.60 Application Example 5 760.60 Application Example 6 776.60 Application Example 7 780.53 Application Example 8 762.27 Application Example 9 920.80 Comparative application example 1 734.80 Comparative Application Example 2 719.60

[0128] Application Example 4: Macroscopic photo of the welded joint in the brazing part Figure 1 As shown, the left picture is a top view, and the right picture is a side view. Figure 1 It can be seen that the welding structure is firm.

[0129] The statistics of the shear strength of the brazed joints obtained in Application Examples 4 and 9 and Comparative Application Examples 1 to 2 are shown in the bar graph. Figure 2 As shown, from Figure 2 It can be seen that the shear strength of the brazed joint first increases and then decreases with the increase of the brazing temperature. When the brazing temperature is 1160℃, the shear strength reaches a maximum of 927.60MPa.

[0130] The microstructure of the brazed joints in Comparative Application Example 1, Application Example 9, Application Example 4 and Comparative Application Example 2 was analyzed using a scanning electron microscope. The microstructure of the brazed joint obtained at a brazing temperature of 1100°C in Comparative Application Example 1 is shown in FIG. Figure 3 As shown, the organizational structure of the brazed joint obtained at a brazing temperature of 1130°C in Application Example 9 is shown in FIG. Figure 4 As shown in FIG. 4 , the organizational structure of the brazed joint obtained at a brazing temperature of 1160° C. in Application Example 4 is shown in FIG. Figure 5 As shown, the organizational structure diagram of the brazed joint obtained at a brazing temperature of 1190°C in comparative application example 2 is shown in Figure 6 As shown. Figures 3 to 6 It can be seen that when the brazing temperature is 1160℃ ( Figure 5 ), the boride in the brazing seam area disappears and the joint structure is uniform.

[0131] The wettability of the nickel-based amorphous alloy solder strip and the alloy ingot in Example 4 was tested by the spreading method. The specific testing method is: prepare 0.2g of nickel-based amorphous alloy solder strip and alloy ingot respectively, and use the nickel-based amorphous alloy solder strip and alloy ingot to braze on the 304 stainless steel plate mother material at a brazing temperature of 1160℃, and test the average spreading area of ​​the molten liquid. The spreading diagram of the molten liquid of the nickel-based amorphous alloy solder strip in Example 4 is shown in FIG. Figure 7 As shown, the molten liquid spreading diagram of the alloy ingot in Example 4 is as follows Figure 8 As shown, from Figure 7 and Figure 8 It can be seen that the average spreading area (wettability) of the nickel-based amorphous alloy brazing material strip is 22.502 mm 2 The average spreading area (wettability) of the alloy ingot is 12.977 mm 2 The wettability of nickel-based amorphous alloy solder strip is significantly higher than that of crystalline alloy (alloy ingot).

[0132] The nickel-based amorphous solder strip provided by the present invention has good wettability, and the spreading area on the 304 stainless steel plate can reach 22.5 mm 2 , which is 9.5mm larger than the spreading area of ​​crystalline solder with the same composition on the same substrate 2 The shear strength of the brazed joint of nickel-based amorphous alloy brazing strip can reach 927.6MPa, which has excellent shear strength.

[0133] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A nickel-based amorphous alloy brazing material strip, composed of the following elements by mass percentage: Cr5-11%, Fe 0-6%, Si 1-5%, B 2-3.5%, Co 0-3%, E 0-1% and the balance Ni; the total mass percentage of the Si and B elements is ≤7.5%; and E is Y, Nb or V.

2. The nickel-based amorphous alloy brazing material strip according to claim 1, characterized in that: The invention is composed of the following elements: 8-11% Cr, 2-5% Fe, 2-4% Si, 2.5-3.5% B, 0-2% Co, 0.1-0.6% E and the balance Ni; the total mass percentage of the Si and B elements is ≤7%.

3. The nickel-based amorphous alloy brazing material strip according to claim 2, characterized in that: The invention is composed of the following elements: 10-11% Cr, 3-4% Fe, 3-4% Si, 2.5-3% B, 0-1% Co, 0.2-0.4% E and the balance Ni; the total mass percentage of the Si and B elements is ≤6.5%.

4. The method for preparing the nickel-based amorphous alloy brazing material strip according to any one of claims 1 to 3, comprising the following steps: (1) smelting the raw materials and then casting to obtain an alloy ingot; (2) The alloy ingot obtained in step (1) is subjected to vacuum stripping to obtain a nickel-based amorphous alloy solder strip.

5. The preparation method according to claim 4, characterized in that: The smelting in step (1) is carried out in an inert atmosphere; the pressure of the inert atmosphere is 0.01 to 0.10 MPa.

6. The preparation method according to claim 4, characterized in that: The vacuum belt spinning in step (2) comprises: cooling the melt obtained by melting the alloy ingot by blowing the melt onto the surface of a rotating cooling device through a belt blowing gas; the temperature of the melt is 900-1300°C.

7. The preparation method according to claim 6, characterized in that: The pressure of the spray gas during the spraying is 0.10-0.12 MPa.

8. The preparation method according to claim 6, characterized in that: During the spraying, the distance between the nozzle and the surface of the cooling device is 1 to 3 mm.

9. The preparation method according to claim 6 or 8, characterized in that: The rotation speed of the cooling device is 32-39 m / s.

10. A method for brazing the nickel-based amorphous alloy brazing strip according to any one of claims 1 to 3 or the nickel-based amorphous alloy brazing strip prepared by the preparation method according to any one of claims 4 to 9, characterized in that: The brazing method is vacuum brazing; the brazing temperature of the vacuum brazing is 1130-1160°C.

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