CN113843546A - CuPSnAg Ni-Re ultra-silver solder, preparation method and application - Google Patents

CuPSnAg Ni-Re ultra-silver solder, preparation method and application Download PDF

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Publication number
CN113843546A
CN113843546A CN202111114795.5A CN202111114795A CN113843546A CN 113843546 A CN113843546 A CN 113843546A CN 202111114795 A CN202111114795 A CN 202111114795A CN 113843546 A CN113843546 A CN 113843546A
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silver
alloy
cupsnag
ultra
solder
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Inventor
骆静宜
王星星
刘安琪
骆华明
何鹏
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Jinhua Jinzhong Welding Materials Co ltd
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Jinhua Jinzhong Welding Materials Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/30Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/30Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/302Cu as the principal constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/40Making wire or rods for soldering or welding

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

The invention discloses a CuPSnAg-Re ultra-silver solder which comprises the following substances in percentage by weight: 0.1% to 5.0% silver; 1.0% to 3.50% nickel; 9.5% to 9.95% tin; 0.05% to 1.0% Re; the balance of copper-phosphorus alloy; the invention also discloses a preparation method of the CuPSnAg-Re ultra-silver solder and application of the CuPSnAg-Re ultra-silver solder to medium-temperature soldering of a large motor; the invention effectively reduces the silver content and simultaneously ensures the solder performance.

Description

CuPSnAg Ni-Re ultra-silver solder, preparation method and application
Technical Field
The invention relates to the technical field of welding materials, in particular to a CuPSnAg Ni-Re ultra-silver solder, a preparation method and application thereof.
Background
Silver solder as an important hard solder can be used for soldering all metal materials except light alloys such as aluminum alloy, magnesium alloy and the like, and is widely applied to the industries such as household appliances, aerospace, hard alloy and the like. However, the silver solder has high silver content, generally the mass fraction is higher than 20%, and the cost is too high for enterprises and customers, so that the silver-saving and silver-reducing requirements of the actual industry cannot be met. The development of low-silver, silver-substituted, silver-saving and super-silver solder, namely solder with low silver content and better performance than silver solder, is urgently needed, and has important practical significance.
The application number 2019102725855 patent application discloses a brazing connection method of a CoCrCuFeNi high-entropy alloy, and discloses a copper-based brazing filler metal taking CoCrCuFeNi as a main element, which is used for brazing a CoCrCuFeNi high-entropy alloy plate and has the highest strength of 411 MPa; the invention patent application with application number 2019105263190 discloses a tin-silver-copper-silicon high-entropy alloy solder and a preparation method thereof, wherein the shear strength of a T2 copper alloy joint is 102.3 MPa. The patent application with the application number of 2019108920673 discloses a preparation method and application of a high-entropy alloy solder, wherein a solder alloy of 15-35% of Ni powder, 15-35% of Cr, 15-35% of Co and 15-35% of Fe is prepared by ball milling. Therefore, the development of silver-saving or ultra-silver solder with low silver content, good performance and low cost is urgently needed.
Disclosure of Invention
The first purpose of the invention is to provide a CuPSnAg-Re ultra-silver solder, which effectively reduces the silver content and ensures the performance of the solder.
In order to solve the technical problem, the technical scheme of the invention is as follows: the CuPSnAg Ni-Re super-silver solder comprises the following substances in percentage by weight:
Figure BDA0003275180200000011
Figure BDA0003275180200000021
preferably, the Re is any one or more of La, Ce, Pr and Nd.
Further preferably comprises the following substances in percentage by weight:
Figure BDA0003275180200000022
it is further preferred that Re comprises 0.2625% La and 0.2625% Pr by weight fraction.
The second purpose of the invention is to provide a preparation method of the CuPSnAg-Re ultra-silver solder, which prevents the solder alloy from generating component segregation by smelting the alloy in groups and ensures the accurate control of the solder components.
In order to solve the technical problem, the technical scheme of the invention is as follows: a preparation method of CuPSnAg Ni-Re ultra-silver solder comprises the following steps:
step one, batching;
preparing raw materials according to the weight percentage, and dividing the raw materials into two groups, wherein one group is copper-phosphorus alloy, nickel and tin, and the other group is silver and rare earth element Re;
step two, smelting;
c1, sequentially putting the copper-phosphorus alloy, the nickel and the tin into a graphite crucible, then adding a covering agent on the surfaces of the copper-phosphorus alloy, the nickel and the tin which are put into the crucible, and heating and smelting in a high-frequency induction furnace filled with inert gas, wherein the alloy is recorded as A1 alloy;
c2, sequentially putting silver and rare earth element Re into a graphite crucible, adding a covering agent on the surfaces of the silver and the rare earth element Re put into the crucible, and heating and smelting in a high-frequency induction furnace filled with inert gas to be recorded as A2 alloy;
c3, putting the melted A1 alloy and A2 alloy into a graphite crucible in sequence, then adding covering agents on the surfaces of A1 and A2 placed in the crucible, and heating and melting in a high-frequency induction furnace filled with inert gas to obtain an A3 alloy;
step three, processing and forming;
and annealing and heating the A3 alloy in sequence, and extruding, rolling or drawing to form the target brazing filler metal.
The heating and melting temperature in the second step C1 is preferably 700-770 ℃. Generally 80-100 ℃ higher than the solder temperature.
The third purpose of the invention is to provide a CuPSnAg-Re ultra-silver solder which is applied to medium-temperature brazing of motors, effectively reduces the silver content and ensures the brazing performance.
In order to solve the technical problem, the technical scheme of the invention is as follows: the CuPSnAg-Re ultra-silver solder is applied to medium-temperature welding of motors.
The temperature of the warm welding in the invention is 690-720 ℃.
By adopting the technical scheme, the invention has the beneficial effects that:
1. compared with the traditional national standard BAg45CuZn solder, the CuPSnAg Ni-Re ultra-silver solder provided by the invention has the advantages of low liquidus temperature, good wetting spreadability, high mechanical properties of soldering seams, particularly high tensile strength, and plays a role in worthy process, the properties of the ultra-silver solder are superior to those of the traditional silver solder, namely the inherent meaning of ultra-silver is well explained.
2. The CuPSnAg-Re ultra-silver solder provided by the invention has the advantages that the melting temperature is reduced by trace rare earth elements, the flowing of the solder is promoted, and the wettability of the solder is improved.
3. The invention provides a super-silver solder, which utilizes the cocktail effect, determines the mass fractions of copper-phosphorus alloy, silver, nickel, tin and rare earth element Re through multiple tests and optimization and regulation of production process, and prepares the CuPSnAg-Re alloy solder with excellent comprehensive performance.
4. The CuPSnAg-Re ultra-silver solder multi-element alloy provided by the invention has multiple beneficial effects of corrosion resistance (containing chloride ion solution), high temperature resistance (300 ℃) and the like.
5. The CuPSnAg Ni-Re super-silver solder provided by the invention can effectively avoid or inhibit a brittle compound Cu by adding nickel3P、Cu6Sn5The generation of the silver solder has adverse effect on the brazing performance of the silver alloy, and the wettability, the fluidity and the mechanical property of the silver solder are improved.
6. The CuPSnAg-Re ultra-silver solder provided by the invention can be widely used for medium-temperature high-efficiency brazing of large motors, is mature and applied in units such as Hunan pool motors, Zhongche Yongji motors, eastern electric group company, Nanjing Changfeng New energy resource company, and the like, and the application shows that: the CuPSnAg-Re super-silver solder provided by the invention has the comprehensive performance superior to that of the traditional BAg45CuZn, BAg56CuNi and BAg54CuZnNi solder, has good conductivity, low cost and low silver content, is green and environment-friendly, has a very good application prospect, and can break through the barrier of the traditional technology.
7. According to the preparation method of the ultra-silver solder, the covering agent is added on the surface under the protection of the inert gas, so that the oxidation inclusion and excessive burning loss in the smelting process can be effectively prevented; in addition, the A1 and A2 alloys are melted in groups, so that the component segregation of the brazing alloy is prevented, and the percentage of the brazing alloy components is ensured.
Thereby achieving the above object of the present invention.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
The embodiment discloses a CuPSnAg-Re ultra-silver solder which mainly comprises a copper-phosphorus alloy, silver, nickel, tin and a rare earth element Re, and the specific weight percentage is as follows: 5.0 percent of silver, 1.00 percent of nickel, 9.50 percent of tin, 0.05 percent of rare earth element Re and the balance of copper-phosphorus alloy. The rare earth element Re is 0.025 percent of La and 0.025 percent of Ce. The copper-phosphorus alloy in this example generally comprises, by mass, 79 to 91 parts of Cu, 8.5 to 20 parts of P, and the trace elements are Ni and a rare earth element Re.
In this example, the spreading areas of 200mg of CuPSnAg Ni-Re ultra-silver solder on the surfaces of red copper and brass of 4cm × 4cm × 2cm were 310mm2And 292mm2The spreading areas of national standard BAg45CuZn solder with the same quality are respectively 260mm2And 215mm2The CuPSnAg Ni-Re ultra-silver solder has larger spreading area on the surfaces of red copper and brass.
In the embodiment, the brazing seam tensile strength of the CuPSnAg Ni-Re ultra-silver brazing filler metal brazing brass and the brazing seam tensile strength of the red copper are 331MPa and 323MPa respectively, the brazing seam tensile strength of the BAg45CuZn brazing filler metal brazing brass and the brazing seam tensile strength of the red copper are 317MPa and 301MPa respectively, and the brazing seam tensile strength of the CuPSnAg Ni-Re ultra-silver brazing filler metal brazing brass and the brazing seam tensile strength of the red copper are high.
The liquidus temperature of the CuPSnAg Ni-Re ultra-silver solder in the embodiment is lower than 626 ℃.
The CuPSnAg-Re super-silver solder in the embodiment has the resistivity of 0.20015 mu omega at 20 ℃, and is mainly used for medium-temperature high-efficiency brazing of large motors.
The specific preparation method of the ultra-silver solder in the embodiment is as follows:
step one, batching;
preparing raw materials according to the weight percentage, and dividing the raw materials into two groups, wherein one group is copper-phosphorus alloy, nickel and tin, and the other group is silver and rare earth element Re;
step two, smelting;
c1: sequentially putting the prepared copper-phosphorus alloy, nickel and tin into a graphite crucible, then adding a covering agent on the surfaces of the copper-phosphorus alloy, the nickel and the tin which are put into the crucible, and heating and smelting in a high-frequency induction furnace filled with inert gas, wherein the heating and smelting temperature is 700-770 ℃, and the alloy is recorded as A1 alloy;
c2: putting the prepared silver and rare earth element Re into a graphite crucible in sequence, adding a covering agent on the surfaces of the silver and the rare earth element Re put into the crucible, and heating and smelting in a high-frequency induction furnace filled with inert gas to obtain an A2 alloy;
c3: sequentially putting the melted A1 and A2 alloys into a graphite crucible, then adding covering agents on the surfaces of A1 and A2 placed in the graphite crucible, and heating and melting in a high-frequency induction furnace filled with inert gas, wherein the alloy is recorded as an A3 alloy;
step three, processing and forming;
the a3 alloy is annealed and then extruded, rolled or drawn.
Example 2
The embodiment discloses a CuPSnAg-Re ultra-silver solder which mainly comprises a copper-phosphorus alloy, silver, nickel, tin and a rare earth element Re, and the specific weight percentage is as follows: 0.1% of silver, 3.50% of nickel, 9.95% of tin, 1.0% of rare earth element Re, and the balance of copper-phosphorus alloy, which is the same as that in example 1. The rare earth element Re is 0.05 percent of Pr and 0.05 percent of Nd.
In this example, the spreading areas of 200mg of CuPSnAg Ni-Re ultra-silver solder on the surfaces of red copper and brass of 4 cm. times.4 cm. times.2 cm were 374mm respectively2、319mm2The spreading area of the equivalent national standard BAg45CuZn solder is 260mm2And 215mm2The spreading area of the CuPSnAg Ni-Re ultra-silver solder is larger.
In this example, the brazing strengths of the brazing gaps of CuPSnAg Ni-Re ultra-silver solder and red copper are 327MPa and 321MPa respectively, the brazing gaps of BAg45CuZn solder and red copper are 317MPa and 301MPa respectively, and the brazing gaps of CuPSnAg Ni-Re ultra-silver solder and red copper are high in tensile strength.
In this example, the liquidus temperature of CuPSnAg Ni-Re ultra-silver solder is lower than 622 ℃.
The resistivity of the CuPSnAg-Re ultra-silver solder in the embodiment at 20 ℃ is 0.20039 mu omega, and the CuPSnAg-Re ultra-silver solder is mainly used for medium-temperature high-efficiency soldering of large motors.
The specific preparation method of the brazing filler metal in this example was the same as that of example 1.
Example 3
The embodiment discloses a CuPSnAg-Re ultra-silver solder which mainly comprises a copper-phosphorus alloy, silver, nickel, tin and a rare earth element Re, and the specific weight percentage is as follows: 2.55% of silver, 2.25% of nickel, 9.725% of tin, 0.525% of rare earth element Re, and the balance of copper-phosphorus alloy, which is the same as that in example 1. The rare earth element Re is 0.2625% La and 0.2625% Pr.
The spreading areas of 200mg of CuPSnAg Ni-Re ultra-silver solder in this example on the surfaces of red copper and brass of 4cm X2 cm were 338mm respectively2And 303mm2The spreading area of national standard BAg45CuZn solder with the same quality is 260mm2And 215mm2The spreading area of the CuPSnAg Ni-Re ultra-silver solder on the surfaces of red copper and brass is larger.
In the embodiment, the brazing seam tensile strength of the CuPSnAg Ni-Re super silver brazing filler metal brazing brass and the brazing filler metal red copper is 342MPa and 326MPa respectively, the brazing seam tensile strength of the BAg45CuZn brazing filler metal brazing brass and the brazing filler metal red copper is 317MPa and 301MPa respectively, and the brazing seam tensile strength of the CuPSnAg-Re super silver brazing filler metal brazing brass and the brazing filler metal red copper is high.
In the embodiment, the liquidus temperature of the CuPSnAg Ni-Re ultra-silver solder is lower than 626 ℃.
In the embodiment, the resistivity of the CuPSnAg-Re ultra-silver solder at 20 ℃ is 0.20031 mu omega, and the CuPSnAg-Re ultra-silver solder is mainly used for medium-temperature high-efficiency brazing of large motors.
The temperature of the ultra-silver solder obtained in the examples 1 to 3 is 50 to 100 ℃ higher than the liquidus temperature of the solder when the ultra-silver solder is welded in a large motor at medium temperature, and more preferably 690 to 720 ℃. The CuPSnAg-Re ultra-silver solder provided by the invention can be widely used for medium-temperature high-efficiency brazing of large motors, is mature and applied in units such as Hunan pool motors, Zhongche Yongji motors, eastern electric group company, Nanjing Changfeng New energy resource company, and the like, and the application shows that: the CuPSnAg-Re super-silver solder provided by the invention has the comprehensive performance superior to that of the traditional BAg45CuZn, BAg56CuNi and BAg54CuZnNi solder, has good conductivity, low cost and low silver content, is green and environment-friendly, has a very good application prospect, and can break through the barrier of the traditional technology.

Claims (7)

1. A CuPSnAg-Re ultra-silver solder is characterized in that: the material comprises the following substances in percentage by weight:
Figure FDA0003275180190000011
2. the CuPSnAgNi-Re ultra-silver solder as claimed in claim 1, wherein: the Re is any one or more of La, Ce, Pr and Nd.
3. The CuPSnAgNi-Re ultra-silver solder as claimed in claim 1, wherein:
the material comprises the following substances in percentage by weight:
Figure FDA0003275180190000012
4. the CuPSnAg-Re solder according to claim 3, wherein:
re includes, in weight fraction, 0.2625% La and 0.2625% Pr.
5. A method for preparing a CuPSnAg-Re solder according to any one of claims 1 to 4, which is characterized in that: the method comprises the following steps:
step one, batching;
preparing raw materials according to the weight percentage, and dividing the raw materials into two groups, wherein one group is copper-phosphorus alloy, nickel and tin, and the other group is silver and rare earth element Re;
step two, smelting;
c1, sequentially putting the copper-phosphorus alloy, the nickel and the tin into a graphite crucible, then adding a covering agent on the surfaces of the copper-phosphorus alloy, the nickel and the tin which are put into the crucible, and heating and smelting in a high-frequency induction furnace filled with inert gas, wherein the alloy is recorded as A1 alloy;
c2, sequentially putting silver and rare earth element Re into a graphite crucible, adding a covering agent on the surfaces of the silver and the rare earth element Re put into the crucible, and heating and smelting in a high-frequency induction furnace filled with inert gas to be recorded as A2 alloy;
c3, putting the melted A1 alloy and A2 alloy into a graphite crucible in sequence, then adding covering agents on the surfaces of A1 and A2 placed in the crucible, and heating and melting in a high-frequency induction furnace filled with inert gas to obtain an A3 alloy;
step three, processing and forming;
and annealing and heating the A3 alloy in sequence, and extruding, rolling or drawing to form the target brazing filler metal.
6. The method of claim 5, wherein: the heating and melting temperature in the second step C1 is 700-770 ℃.
7. Applying the CuPSnAg-Re ultra-silver solder as claimed in any one of claims 1 to 4 to medium temperature welding of an electric machine.
CN202111114795.5A 2021-09-23 2021-09-23 CuPSnAg Ni-Re ultra-silver solder, preparation method and application Pending CN113843546A (en)

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CN101003109A (en) * 2006-12-29 2007-07-25 哈尔滨工业大学 Active mesothermal copper base solder, and preparation method
CN101342644A (en) * 2007-07-13 2009-01-14 金华市信和焊材制造有限公司 High-ductility environment friendly silver-saving medium-temperature brazing filler metal
CN101214588A (en) * 2008-01-14 2008-07-09 哈尔滨工业大学 Low silver oxidation resistance active leadless solder
CN101264556A (en) * 2008-05-07 2008-09-17 哈尔滨工业大学 Silver base cadmiumless middle temperature solder and preparation thereof
CN101791749A (en) * 2009-11-12 2010-08-04 金华市双环钎焊材料有限公司 Low-sliver brazing filler metal and production method and equipment thereof
CN101700606A (en) * 2009-11-27 2010-05-05 浙江一远电子科技有限公司 Sn-Ag-Cu misch metal lead-free solder with low content of Cu and preparation method thereof
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