WO2020118613A1 - Sn-zn lead-free solder material and preparation method therefor - Google Patents

Sn-zn lead-free solder material and preparation method therefor Download PDF

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Publication number
WO2020118613A1
WO2020118613A1 PCT/CN2018/120872 CN2018120872W WO2020118613A1 WO 2020118613 A1 WO2020118613 A1 WO 2020118613A1 CN 2018120872 W CN2018120872 W CN 2018120872W WO 2020118613 A1 WO2020118613 A1 WO 2020118613A1
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Prior art keywords
alloy
vacuum
free solder
snzn
lead
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PCT/CN2018/120872
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French (fr)
Chinese (zh)
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李凯
刘刚
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北京联金高新科技有限公司
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Priority to CN201880010115.5A priority Critical patent/CN110402181A/en
Priority to PCT/CN2018/120872 priority patent/WO2020118613A1/en
Publication of WO2020118613A1 publication Critical patent/WO2020118613A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/40—Making wire or rods for soldering or welding

Definitions

  • This application relates to the field of electronic materials, in particular to a SnZn lead-free solder and a preparation method thereof.
  • Sn-Cu lead-free solder The melting point of Sn-Cu lead-free solder is 227°C, and its alloy structure is a eutectic structure formed by the Sn-Cu and Cu 6 Sn 5 intermetallic combination. Because Cu 6 Sn 5 has poor thermal stability, it is easy to coarsen, so Sn-Cu The lead-free solder has poor strength and plasticity, and its poor wetting and mechanical properties also limit its application in industry. Sn-Ag-Cu lead-free solder combines the advantages of Sn-Ag lead-free solder and Sn-Cu lead-free solder, but when the content of Ag is higher, the raw material cost is higher; when the content of Ag is lower, and There are problems with poor performance and poor reliability.
  • Sn-Ag-based lead-free solder, Sn-Cu-based lead-free solder and Sn-Ag-Cu-based lead-free solder all have higher melting points (usually higher than 220°C), on the one hand, they are different from existing processes. Incompatible conditions, on the other hand, will lead to increased energy consumption in the production process and increase production costs; at the same time, these three solders have poor wetting properties and reliability problems.
  • the Sn-Bi alloy its melting point is relatively low (eutectic melting point 139°C) compared to the existing process conditions.
  • the Bi phase is deposited in the Sn matrix and does not react with Sn, resulting in poor plasticity of the alloy solder. It has high brittleness, poor processing performance, and poor reliability, so there are huge restrictions in production and use.
  • the purpose of this application is to provide a SnZn-based lead-free solder and a preparation method thereof.
  • the SnZn-based lead-free solder has good wetting properties, a moderate melting point, high bonding strength with the substrate, and reliability The advantages of good and low cost.
  • the present application provides a SnZn-based lead-free solder, which has a composition of Zn, 8.0% to 15%; Bi, 0.5% to 3.0% in mass percentage; In , 0.5% to 2.0%; Ni, 0.10% to 1.0%; Mn, 0.10% to 1.0%; P, 0.050% to 1.0%; the balance is Sn.
  • the present application provides a method for preparing SnZn-based lead-free solder, which is used to prepare the SnZn-based lead-free solder according to the first aspect of the present application, which includes the steps of: (1) Weighing the raw material Sn , Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn respectively, and then perform the first vacuum melting respectively, after the end to get SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy , SnP alloy; (2) According to the composition of SnZn lead-free solder to be prepared, mix SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy with the raw materials Sn and Zn, and then conduct the second vacuum melting to complete After pouring into the mold, cooling and solidification to obtain SnZn lead-free solder.
  • the SnZn series lead-free solder of the present application has the characteristics of good wetting performance, moderate melting point, high bonding strength with the substrate, good reliability and low cost, and can be used as a complete substitute for SnPb series solder.
  • FIG. 1 is a microstructure diagram of SnZn-based lead-free solder of Example 2 and Comparative Example 2 of the present application, where (a) is a microstructure diagram of SnZn-based lead-free solder of Example 2, and (b) is a comparative example 2 Microstructure of SnZn lead-free solder.
  • Example 16 is a soldering effect diagram of Example 16 of the present application, where (a) is a printed circuit board with a ball grid array structure, (b) is a lead element, and (c) is a resistance element.
  • the SnZn series lead-free solder according to the first aspect of the present application will be described.
  • the composition is: Zn, 8.0% to 15%; Bi, 0.50% to 3.0%; In, 0.50% to 2.0%; Ni, 0.10% to 1.0%; Mn, 0.10% to 1.0%; P, 0.050% to 1.0%; the balance is Sn.
  • Zn existing in the needle-like zinc-rich phase can lower the melting point of the alloy solder, but if the Zn content is too high, the melting point of the alloy solder will be raised again.
  • the content of Zn in SnZn lead-free solder is controlled to 8.0% to 15%, which can reduce the melting point of alloy solder to a certain extent.
  • the content of Zn is 8.0% to 13% in terms of mass percentage.
  • the addition of Bi element can adjust the melting point of the alloy solder, and at the same time can reduce the difference in thermal expansion coefficient of the alloy solder and the copper substrate parts, thereby reducing the tendency of cracking at the solder interface.
  • the addition of Bi element is also conducive to improving the wettability of the alloy solder and enhancing the strength of the joint, but excessive Bi element will cause the brittleness of the alloy solder to increase, thereby reducing the plasticity of the alloy solder.
  • the content of Bi element is controlled to 0.50% to 3.0%, which can effectively reduce the melting point of the alloy solder, reduce cracking at the welding interface, and also improve the wetting properties of the alloy solder and the joint strength.
  • the Bi content is 0.50% to 2.5% in terms of mass percentage.
  • the addition of In element can improve the wettability of the alloy solder on the one hand, and can also reduce the melting point of the alloy solder on the other hand.
  • the content of the In element is controlled to 0.50% to 2.0%, which can simultaneously improve the total wetting performance of the solder and reduce the melting point of the alloy solder.
  • the Bi content is 0.6% to 1.6% in terms of mass percentage.
  • the added Ni element can replace part of the Cu atoms on the copper substrate part during the reaction between the alloy solder and the copper substrate part to form an intermetallic compound of Ni and Sn, which can Enhance the interface bonding strength of alloy solder and copper substrate parts.
  • the content of Ni is less than 0.10% of the total mass of SnZn lead-free solder, its effect is not obvious; when the content of Ni is higher than 1.0% of the total mass of SnZn lead-free solder, a Ni oxide film will be formed on the surface of the alloy solder Layer, which deteriorates the wetting properties of the alloy solder.
  • the content of Ni element is controlled to 0.10% to 1.0%, which can enhance the interface bonding strength of the alloy solder and the copper substrate without deteriorating other properties of the alloy solder.
  • the added Mn element can refine the coarse Zn-rich phase in the alloy structure, thereby improving the mechanical properties and solderability of the alloy solder, which is beneficial to enhance the interface between the alloy solder and the copper substrate parts
  • the bonding strength, while the refined alloy structure can also improve the wetting performance, oxidation resistance and corrosion resistance of alloy solder.
  • the content of Mn element is controlled to 0.10% to 1.0%, which can effectively refine the coarse rich phase in the alloy structure, and enhance the wetting performance, oxidation resistance and corrosion resistance of the alloy solder.
  • the added P element can keep the molten Sn in the alloy solder fresh during the brazing process, improve the oxidation resistance of the liquid solder, and thus enhance the reliability of the solder joint.
  • the content of P is controlled to 0.050% to 1.0%, which can effectively improve the oxidation resistance of the alloy solder and enhance the reliability of the solder joint.
  • the melting point of the SnZn-based lead-free solder is 196°C to 210°C.
  • the shear strength of the SnZn-based lead-free solder is 35 MPa to 45 MPa. It should be noted here that the shear strength of the SnZn-based lead-free solder refers to It is the bonding strength between SnZn lead-free solder and copper substrate parts.
  • the existence form of the SnZn-based lead-free solder is not limited, and can be selected according to actual use requirements.
  • the SnZn-based lead-free solder may be in the form of paste, powder, or bulk, but it is not limited thereto.
  • a method for preparing a SnZn-based lead-free solder according to the second aspect of the present application for preparing the SnZn-based lead-free solder according to the first aspect of the present application, includes the steps of: (1) Weighing raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn respectively, and then perform the first vacuum melting respectively, and after the end, get SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy; 2) Mix the SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy with the raw materials Sn and Zn according to the composition of the SnZn-based lead-free solder to be prepared, and then perform the second vacuum melting and pour into the mold after the end After cooling and solidification, SnZn lead-free solder is obtained.
  • SnZn series lead-free solder of the present application a series of intermediate alloys (SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy) are prepared respectively, and then SnZn is prepared through the intermediate alloy and the raw materials Sn and Zn
  • the lead-free solder method can ensure that the resulting SnZn-based lead-free solder has high composition accuracy.
  • the first vacuum melting can be performed in a vacuum induction furnace, it should be noted that each element raw material is subjected to the first vacuum
  • the smelting parameters need to be consistent.
  • the temperature of the first vacuum melting is 460 °C ⁇ 480 °C
  • the vacuum degree of the first vacuum melting is less than or equal to 10 -4 Pa
  • the time of the first vacuum melting is 30min ⁇ 40min .
  • the second vacuum melting may be performed in a vacuum induction furnace.
  • step (2) China, the vacuum melting temperature is 580°C to 650°C, the vacuum degree is less than or equal to 10 -4 Pa, and the vacuum melting time is 60 min to 75min.
  • the mass percentages of Zn, Bi, In, Ni, Mn, P, Sn in the finally obtained SnZn series lead-free solder are: Zn is 13%, Bi is 2.0%, In is 0.90%, Ni is 0.50%, Mn is 0.20%, P is 0.20%, and the remainder is Sn.
  • Zn 12%
  • Bi 0.70%
  • In is 0.70%
  • Ni 0.20%
  • Mn 0.40%
  • P is 0.50%
  • the balance is Sn
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, SnZn based lead-free solder is obtained.
  • Zn is 11%
  • Bi is 3.0%
  • In is 1.5%
  • Ni is 0.50%
  • Mn is 0.90%
  • P is 0.20%
  • the remainder is Sn.
  • Zn is 10%
  • Bi is 2.6%
  • In is 1.2%
  • Ni is 0.90%
  • Mn is 0.30%
  • P is 0.80%
  • the remainder is Sn.
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn is 15%
  • Bi is 0.70%
  • In is 0.70%
  • Ni is 0.20%
  • Mn is 0.40%
  • P is 0.50%
  • SnBi alloy SnIn alloy
  • SnNi alloy SnNi alloy
  • SnMn alloy SnP alloy
  • the raw materials Sn and Zn weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace.
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn is 8.0%
  • Bi is 0.70%
  • In is 0.70%
  • Ni is 0.20%
  • Mn is 0.40%
  • P is 0.50%
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn 12%
  • Bi 0.50%
  • In is 0.70%
  • Ni is 0.20%
  • Mn is 0.40%
  • P is 0.50%
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn 12%
  • Bi 0.70%
  • In is 0.50%
  • Ni 0.20%
  • Mn 0.40%
  • P is 0.50%
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn is 12.0%
  • Bi is 0.70%
  • In is 2.0%
  • Ni is 0.20%
  • Mn is 0.40%
  • P is 0.50%
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn is 12.0%, Bi is 0.7%, In is 0.7%, Ni is 0.1%, Mn is 0.4%, P is 0.5%, and the remainder is Sn.
  • Zn 12%
  • Bi 0.70%
  • In 0.70%
  • Ni 1.0%
  • Mn 0.40%
  • P 0.50%
  • the balance is Sn.
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn 12%
  • Bi 0.70%
  • In is 0.70%
  • Ni is 0.20%
  • Mn is 0.10%
  • P is 0.50%
  • the balance is Sn
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn 12%
  • Bi 0.70%
  • In is 0.70%
  • Ni is 0.20%
  • Mn is 1.0%
  • P is 0.50%
  • Sn weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn and mix them, and then place them in a vacuum induction furnace.
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn 12%
  • Bi 0.70%
  • In 0.70%
  • Ni 0.20%
  • Mn 0.40%
  • P 0.050%
  • the remainder is Sn.
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn 12%
  • Bi 0.70%
  • In 0.70%
  • Ni 0.20%
  • Mn 0.40%
  • P 1.0%
  • the remainder Sn.
  • Sn-Ag 3 -Cu 0.5 series solder is used as lead-free solder.
  • the mass percentages of Zn, Bi, In, Ni, P, Sn in the SnZn lead-free solder finally obtained are: Zn is 14%, Bi is 0.50%, In is 0.50%, Ni is 0.10%, P is 0.10% ⁇ The balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnP alloy and the raw materials Sn and Zn and mix them, and then put them in the vacuum induction furnace for the second vacuum melting.
  • the second The vacuum degree of the next true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • the mass percentages of Zn, Bi, In, Ni, Mn, Sn in the SnZn-based lead-free solder finally obtained are: Zn is 12%, Bi is 0.70%, In is 0.70%, Ni is 0.20%, Mn is 0.40% ⁇ The balance is Sn. Weigh proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy and raw materials Sn and Zn and mix them, and then put them in the vacuum induction furnace for the second vacuum smelting.
  • the second The vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn 12%
  • Bi 0.70%
  • In 0.70%
  • Mn 0.40%
  • P 0.50%
  • Sn 0.50%
  • the mass percentages of Zn, Bi, Ni, Mn, P, Sn in the SnZn lead-free solder finally obtained are: Zn 12%, Bi 0.70%, Ni 0.20%, Mn 0.40%, P 0.50% ⁇ The balance is Sn. Weigh the proper amount of SnBi alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn and mix them, and then put them in the vacuum induction furnace for the second vacuum melting, of which, the second The vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • the mass percentages of Zn, In, Ni, Mn, P, Sn in the SnZn lead-free solder finally obtained are: Zn is 12%, In is 0.70%, Ni is 0.20%, Mn is 0.40%, P is 0.50% ⁇ The balance is Sn. Weigh proper amount of SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and raw materials Sn and Zn and mix them, and then put them in the vacuum induction furnace for the second vacuum smelting.
  • the second The vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn is 17%
  • Bi is 0.70%
  • In is 0.70%
  • Ni is 0.20%
  • Mn is 0.40%
  • P is 0.50%
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn is 5.0%
  • Bi is 0.70%
  • In is 0.70%
  • Ni is 0.20%
  • Mn is 0.40%
  • P is 0.50%
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • the mass percentages of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn lead-free solder finally obtained are: Zn is 12%, Bi is 3.5%, In is 0.70%, Ni is 0.20%, Mn is 0.40%, P is 0.50%, and the balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace.
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn 12%
  • Bi 0.30%
  • In 0.70%
  • Ni 0.20%
  • Mn 0.40%
  • P 0.50%
  • SnBi alloy SnIn alloy
  • SnNi alloy SnNi alloy
  • SnMn alloy SnP alloy
  • the raw materials Sn and Zn weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace.
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn 12%
  • Bi 0.70%
  • In is 0.30%
  • Ni is 0.20%
  • Mn is 0.40%
  • P is 0.50%
  • SnBi alloy SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace.
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn 12%
  • Bi 0.70%
  • In 2.5%
  • Ni 0.20%
  • Mn 0.40%
  • P 0.50%
  • Sn the balance is Sn.
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn 12%
  • Bi 0.70%
  • In is 0.70%
  • Ni is 0.050%
  • Mn is 0.40%
  • P is 0.50%
  • SnBi alloy SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace.
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn 12%
  • Bi 0.70%
  • In is 0.70%
  • Ni 1.50%
  • Mn 0.40%
  • P is 0.50%
  • Sn weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace.
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn 12%
  • Bi 0.70%
  • In is 0.70%
  • Ni is 0.20%
  • Mn is 0.050%
  • P is 0.50%
  • the balance is Sn
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn 12%
  • Bi 0.70%
  • In 0.70%
  • Ni 0.20%
  • Mn 1.5%
  • P 0.5%
  • the remainder is Sn.
  • Zn 12%
  • Bi 0.70%
  • In is 0.70%
  • Ni is 0.20%
  • Mn is 0.40%
  • P 0.010%
  • the balance is Sn
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • Zn 12%
  • Bi 0.70%
  • In 0.70%
  • Ni 0.20%
  • Mn 0.40%
  • P 1.5%
  • the remainder is Sn.
  • the second vacuum smelting in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 °C, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
  • the melting point of the solder was tested by DSC differential scanning calorimetry (DSC), and the mass of solder required for the measurement was about 0.02 g.
  • DSC DSC differential scanning calorimetry
  • about 0.02 g of alloy solder was put into the DSC device, and heated to 250° C. at a heating rate of 10° C./min, and nitrogen gas was passed into the sample chamber as a protective atmosphere to obtain a DSC curve of the solder. According to the DSC curve, take the extrapolated starting point as the melting point of the solder.
  • the shear strength is measured with a shear strength tester, that is, the bonding strength of the solder and the copper substrate.
  • the shearing speed is 100 ⁇ m/s, and the height of the grip from the copper substrate during the shearing test is 50 ⁇ m.
  • the number of cycles that the solder joint can maintain without failure after soldering under accelerated thermal cycling is used to characterize the reliability of the solder.
  • the temperature of the thermal cycle is controlled between -40°C and 125°C, and the heating time and cooling time are 15min.
  • 30min is a cycle, based on the failure of the solder joint (that is, the solder joint is open after energization) as the basis for judgment, record the thermal cycle of the solder joint when the solder joint fails, the higher the number of cycles, the better the reliability of the solder.
  • Adopt the metal price calculate the cost of solder according to its percentage, without considering the cost of processing technology, etc., taking the cost of a mainstream Sn-Ag-Cu lead-free solder on the market as the standard1.
  • Example 3 the SnZn-based lead-free solder powder obtained in Example 3 was combined with a flux containing rosin as a main component to prepare a solder paste.
  • PCB printed circuit boards
  • solder 68 0603 components Take 20 printed circuit boards (PCB) and solder 68 0603 components on each PCB. After welding, record the welding temperature and the number of failed solder joints, and calculate the solder joint qualification rate.
  • the push-pull force value of the 0603 element is greater than 1.2Kgf.
  • PCB printed circuit boards
  • solder 214 0603 components On each PCB. After welding, record the welding temperature and the number of failed solder joints, and calculate the solder joint qualification rate.
  • PCB printed circuit boards
  • solder 487 0603 components on each PCB. After welding, record the welding temperature and the number of failed solder joints, and calculate the solder joint qualification rate.
  • PCB printed circuit boards
  • solder 2045 0603 components on each PCB. After welding, record the welding temperature and the number of failed solder joints, and calculate the solder joint qualification rate.
  • the SnZn lead-free solder of the present application has good wetting performance, moderate melting point, high bonding strength and reliability The advantages of good performance and low cost can be used as a complete substitute for SnPb solder.
  • Example 2 and Comparative Examples 2-6 From the analysis of the test results of Example 2 and Comparative Examples 2-6, it can be seen that the SnZn series lead-free solder including Zn, Bi, In, Ni, Mn, P, and Sn elements in the present application has good wetting performance, moderate melting point, It has the characteristics of high bonding strength, good reliability and low cost.
  • Example 2 and Comparative Example 2 further analysis in conjunction with FIG. 1 shows that the Mn element in the SnZn lead-free solder of the present application can eliminate the coarse Zn-rich phase in the alloy solder structure, thereby enhancing the interface bonding strength. And improve the wetting performance and reliability of alloy solder.

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Abstract

An Sn-Zn lead-free solder material, containing, by mass percent: Zn, 8.0%-15%; Bi, 0.50%-3.0%; In, 0.50%-2.0%; Ni, 0.10%-1.0%; Mn, 0.10%-1.0%; P, 0.050%-1.0%; and the remainder being Sn. The present Sn-Zn lead-free solder material features excellent wettability, a well-located melting point, high bonding strength with a substrate, good dependability, and low costs, and may serve as a substitute for Sn-Pb solder materials.

Description

SnZn系无铅焊料及其制备方法SnZn series lead-free solder and preparation method thereof 技术领域Technical field
本申请涉及电子材料领域，尤其涉及一种SnZn系无铅焊料及其制备方法。This application relates to the field of electronic materials, in particular to a SnZn lead-free solder and a preparation method thereof.
背景技术Background technique
在传统电子封装工业中，共晶与近共晶的Sn-Pb钎料由于具有众多的优异性能，例如操作简单、成本低廉、对铜基板润湿性良好等，而得到了广泛应用。近年来，随着人们对铅及其合金的危害性的深入了解和环保意识的提高，世界各国及相关组织推出了很多法案限制甚至禁止含铅钎料在电子封装工业中的应用，这使得电子封装领域的无铅化成为当下发展的必然趋势。In the traditional electronic packaging industry, eutectic and near-eutectic Sn-Pb solders have been widely used because of their many excellent properties, such as simple operation, low cost, and good wettability on copper substrates. In recent years, with people's in-depth understanding of the harmfulness of lead and its alloys and the improvement of environmental awareness, countries and relevant organizations around the world have introduced many laws restricting or even prohibiting the application of leaded solders in the electronic packaging industry, which makes electronic Lead-free in the field of packaging has become an inevitable trend of current development.
目前国内外对中低温无铅焊料的研究主要集中在Sn-Ag系无铅焊料、Sn-Cu系无铅焊料、Sn-Ag-Cu系无铅焊料和Sn-Bi系无铅焊料等，并通过添加少量或微量的Ag、Bi、Cu、In、Ni、P、Sb等元素以改善合金焊料的性能。Sn-Ag系无铅焊料的熔点为221℃，该焊料在Cu基体上的润湿性较差，市场接受度较差。Sn-Cu系无铅焊料的熔点为227℃，其合金组织为Sn基体和Cu 6Sn 5金属间化合形成的共晶组织，由于Cu 6Sn 5热稳定性差，容易粗化，因此Sn-Cu系无铅焊料的强度和塑性都较差，此外其较差的润湿性能和机械性能也限制了其在工业中的应用。Sn-Ag-Cu系无铅焊料综合了Sn-Ag无铅焊料和Sn-Cu无铅焊料的优点，但当其中Ag的含量较高时，原料成本较高；Ag的含量较低时，又存在性能不佳、可靠性差的问题。由此可见，Sn-Ag系无铅焊料、Sn-Cu系无铅焊料和Sn-Ag-Cu系无铅焊料都有较高的熔点(通常高于220℃)，一方面与现有的工艺条件不兼容，另一方面会导致生产过程中能耗的上升，提高生产成本；同时，这三种焊料的润湿性能不良，可靠性方面也存在问题。至于Sn-Bi系合金，相对现有工艺条件而言其熔点偏低(共晶熔点139℃)，此外Bi相在Sn基体中沉积，并不与Sn发生反应，导致该合金焊料的塑性差、脆性大、加工性能不佳、可靠性差，因此在生产中及使 用存在巨大的限制。 At present, domestic and foreign researches on medium and low temperature lead-free solders mainly focus on Sn-Ag lead-free solders, Sn-Cu lead-free solders, Sn-Ag-Cu lead-free solders, Sn-Bi lead-free solders, etc., and By adding small or trace elements of Ag, Bi, Cu, In, Ni, P, Sb and other elements to improve the performance of alloy solder. The melting point of Sn-Ag based lead-free solder is 221 ℃, the solder has poor wettability on the Cu substrate, and the market acceptance is poor. The melting point of Sn-Cu lead-free solder is 227°C, and its alloy structure is a eutectic structure formed by the Sn-Cu and Cu 6 Sn 5 intermetallic combination. Because Cu 6 Sn 5 has poor thermal stability, it is easy to coarsen, so Sn-Cu The lead-free solder has poor strength and plasticity, and its poor wetting and mechanical properties also limit its application in industry. Sn-Ag-Cu lead-free solder combines the advantages of Sn-Ag lead-free solder and Sn-Cu lead-free solder, but when the content of Ag is higher, the raw material cost is higher; when the content of Ag is lower, and There are problems with poor performance and poor reliability. It can be seen that Sn-Ag-based lead-free solder, Sn-Cu-based lead-free solder and Sn-Ag-Cu-based lead-free solder all have higher melting points (usually higher than 220℃), on the one hand, they are different from existing processes. Incompatible conditions, on the other hand, will lead to increased energy consumption in the production process and increase production costs; at the same time, these three solders have poor wetting properties and reliability problems. As for the Sn-Bi alloy, its melting point is relatively low (eutectic melting point 139°C) compared to the existing process conditions. In addition, the Bi phase is deposited in the Sn matrix and does not react with Sn, resulting in poor plasticity of the alloy solder. It has high brittleness, poor processing performance, and poor reliability, so there are huge restrictions in production and use.
发明内容Summary of the invention
鉴于背景技术中存在的问题，本申请的目的在于提供一种SnZn系无铅焊料及其制备方法，所述SnZn系无铅焊料具有润湿性能好、熔点适中、与基底结合强度高、可靠性好、成本低廉的优点。In view of the problems in the background art, the purpose of this application is to provide a SnZn-based lead-free solder and a preparation method thereof. The SnZn-based lead-free solder has good wetting properties, a moderate melting point, high bonding strength with the substrate, and reliability The advantages of good and low cost.
为了达到上述目的，在本申请的第一方面，本申请提供了一种SnZn系无铅焊料，按质量百分比计，其组成为Zn，8.0％～15％；Bi，0.5％～3.0％；In，0.5％～2.0％；Ni，0.10％～1.0％；Mn，0.10％～1.0％；P，0.050％～1.0％；余量为Sn。In order to achieve the above object, in the first aspect of the present application, the present application provides a SnZn-based lead-free solder, which has a composition of Zn, 8.0% to 15%; Bi, 0.5% to 3.0% in mass percentage; In , 0.5% to 2.0%; Ni, 0.10% to 1.0%; Mn, 0.10% to 1.0%; P, 0.050% to 1.0%; the balance is Sn.
在本申请的第二方面，本申请提供了一种SnZn系无铅焊料的制备方法，用于制备本申请第一方面所述的SnZn系无铅焊料，包括步骤：(1)称取原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn进行混合，然后分别进行第一次真空熔炼，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金；(2)按照待制备的SnZn系无铅焊料的成分，将SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn混合，然后进行第二次真空熔炼，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。In the second aspect of the present application, the present application provides a method for preparing SnZn-based lead-free solder, which is used to prepare the SnZn-based lead-free solder according to the first aspect of the present application, which includes the steps of: (1) Weighing the raw material Sn , Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn respectively, and then perform the first vacuum melting respectively, after the end to get SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy , SnP alloy; (2) According to the composition of SnZn lead-free solder to be prepared, mix SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy with the raw materials Sn and Zn, and then conduct the second vacuum melting to complete After pouring into the mold, cooling and solidification to obtain SnZn lead-free solder.
相对于现有技术，本申请的有益效果为：Compared with the prior art, the beneficial effects of this application are:
本申请的SnZn系无铅焊料具有润湿性能好、熔点适中、与基底结合强度高、可靠性好、成本低廉的特点，可作为SnPb系焊料的完全替代品。The SnZn series lead-free solder of the present application has the characteristics of good wetting performance, moderate melting point, high bonding strength with the substrate, good reliability and low cost, and can be used as a complete substitute for SnPb series solder.
附图说明BRIEF DESCRIPTION
图1是本申请的实施例2和对比例2的SnZn系无铅焊料的微观组织图，其中，(a)是实施例2的SnZn系无铅焊料的微观组织图，(b)是对比例2的SnZn系无铅焊料的微观组织图。FIG. 1 is a microstructure diagram of SnZn-based lead-free solder of Example 2 and Comparative Example 2 of the present application, where (a) is a microstructure diagram of SnZn-based lead-free solder of Example 2, and (b) is a comparative example 2 Microstructure of SnZn lead-free solder.
图2是本申请的实施例16的焊接效果图，其中，(a)是球栅阵列结构的印刷电路板，(b)是引脚元件，(c)是电阻元件。2 is a soldering effect diagram of Example 16 of the present application, where (a) is a printed circuit board with a ball grid array structure, (b) is a lead element, and (c) is a resistance element.
具体实施方式detailed description
下面详细说明根据本申请的SnZn系无铅焊料及其制备方法。The SnZn series lead-free solder according to the present application and its preparation method are described in detail below.
首先说明根据本申请第一方面的SnZn系无铅焊料，其按质量百分比计，组成为：Zn，8.0％～15％；Bi，0.50％～3.0％；In，0.50％～2.0％；Ni，0.10％～1.0％；Mn，0.10％～1.0％；P，0.050％～1.0％；余量为Sn。First, the SnZn series lead-free solder according to the first aspect of the present application will be described. In terms of mass percentage, the composition is: Zn, 8.0% to 15%; Bi, 0.50% to 3.0%; In, 0.50% to 2.0%; Ni, 0.10% to 1.0%; Mn, 0.10% to 1.0%; P, 0.050% to 1.0%; the balance is Sn.
在本申请的SnZn系无铅焊料中，以针状富锌相存在的Zn可以降低合金焊料的熔点，但Zn含量过高会使合金焊料的熔点重新升高。本申请将SnZn系无铅焊料中Zn的含量控制为8.0％～15％，可以一定程度地降低合金焊料的熔点。In the SnZn series lead-free solder of the present application, Zn existing in the needle-like zinc-rich phase can lower the melting point of the alloy solder, but if the Zn content is too high, the melting point of the alloy solder will be raised again. In this application, the content of Zn in SnZn lead-free solder is controlled to 8.0% to 15%, which can reduce the melting point of alloy solder to a certain extent.
优选地，在本申请的SnZn系无铅焊料中，按质量百分比计，Zn的含量为8.0％～13％。Preferably, in the SnZn series lead-free solder of the present application, the content of Zn is 8.0% to 13% in terms of mass percentage.
在本申请的SnZn系无铅焊料中，添加Bi元素可以调整合金焊料的熔点，同时可以降低合金焊料与铜基板制件的热膨胀系数差异，从而可减少焊接界面产生裂纹的趋势。此外，添加Bi元素还有利于改善合金焊料的润湿性能，提升接头强度，但过量的Bi元素会导致合金焊料的脆性增加，从而降低合金焊料的塑性。本申请将Bi元素的含量控制为0.50％～3.0％，可以有效地降低合金焊料的熔点，同时减少焊接界面的裂纹产生，同时还可以改善合金焊料的润湿性能，提升接头强度。In the SnZn lead-free solder of the present application, the addition of Bi element can adjust the melting point of the alloy solder, and at the same time can reduce the difference in thermal expansion coefficient of the alloy solder and the copper substrate parts, thereby reducing the tendency of cracking at the solder interface. In addition, the addition of Bi element is also conducive to improving the wettability of the alloy solder and enhancing the strength of the joint, but excessive Bi element will cause the brittleness of the alloy solder to increase, thereby reducing the plasticity of the alloy solder. In this application, the content of Bi element is controlled to 0.50% to 3.0%, which can effectively reduce the melting point of the alloy solder, reduce cracking at the welding interface, and also improve the wetting properties of the alloy solder and the joint strength.
优选地，在本申请的SnZn系无铅焊料中，按质量百分比计，Bi的含量为0.50％～2.5％。Preferably, in the SnZn series lead-free solder of the present application, the Bi content is 0.50% to 2.5% in terms of mass percentage.
在本申请的SnZn系无铅焊料中，添加In元素一方面可以改善合金焊料的润湿性能，另一方面还可以降低合金焊料的熔点。本申请将In元素的含量控制为0.50％～2.0％，可以同时起到改善焊料合计润湿性能和降低合金焊料熔点的作用。In the SnZn series lead-free solder of the present application, the addition of In element can improve the wettability of the alloy solder on the one hand, and can also reduce the melting point of the alloy solder on the other hand. In this application, the content of the In element is controlled to 0.50% to 2.0%, which can simultaneously improve the total wetting performance of the solder and reduce the melting point of the alloy solder.
优选地，在本申请的SnZn系无铅焊料中，按质量百分比计，Bi的含量为0.6％～1.6％。Preferably, in the SnZn series lead-free solder of the present application, the Bi content is 0.6% to 1.6% in terms of mass percentage.
在本申请的SnZn系无铅焊料中，添加的Ni元素能够在合金焊料与铜基板制件界面的反应过程中取代铜基板制件上的部分Cu原子，形成Ni和Sn金属间化合物，从而可以增强合金焊料与铜基板制件的界面结合强度。当Ni的含量低于SnZn系无铅焊料总质量的0.10％时，其作用不明显；当Ni含量 高于SnZn系无铅焊料总质量的1.0％时，会在合金焊料表面形成Ni的氧化膜层，恶化合金焊料的润湿性能。本申请将Ni元素的含量控制为0.10％～1.0％，可以增强合金焊料与铜基板的界面结合强度，同时不恶化合金焊料的其他性能。In the SnZn lead-free solder of the present application, the added Ni element can replace part of the Cu atoms on the copper substrate part during the reaction between the alloy solder and the copper substrate part to form an intermetallic compound of Ni and Sn, which can Enhance the interface bonding strength of alloy solder and copper substrate parts. When the content of Ni is less than 0.10% of the total mass of SnZn lead-free solder, its effect is not obvious; when the content of Ni is higher than 1.0% of the total mass of SnZn lead-free solder, a Ni oxide film will be formed on the surface of the alloy solder Layer, which deteriorates the wetting properties of the alloy solder. In this application, the content of Ni element is controlled to 0.10% to 1.0%, which can enhance the interface bonding strength of the alloy solder and the copper substrate without deteriorating other properties of the alloy solder.
在本申请的SnZn系无铅焊料中，添加的Mn元素能够细化合金组织中粗大的富Zn相，从而改善合金焊料的力学性能和焊接性能，有利于增强合金焊料与铜基板制件界面的结合强度，同时细化后的合金组织还能提高合金焊料的润湿性能、抗氧化性能和耐腐蚀能力。但当Mn元素量超过SnZn系无铅焊料总质量的1％时，会导致合金组织中形成粗大的金属间化合物，降低SnZn系无铅焊料的综合性能。本申请将Mn元素的含量控制为0.10％～1.0％，可以有效地细化合金组织中粗大的富相，增强合金焊料的润湿性能、抗氧化性能和耐腐蚀能力。In the SnZn series lead-free solder of the present application, the added Mn element can refine the coarse Zn-rich phase in the alloy structure, thereby improving the mechanical properties and solderability of the alloy solder, which is beneficial to enhance the interface between the alloy solder and the copper substrate parts The bonding strength, while the refined alloy structure can also improve the wetting performance, oxidation resistance and corrosion resistance of alloy solder. However, when the amount of Mn element exceeds 1% of the total mass of SnZn lead-free solder, it will lead to the formation of coarse intermetallic compounds in the alloy structure, reducing the overall performance of SnZn lead-free solder. In this application, the content of Mn element is controlled to 0.10% to 1.0%, which can effectively refine the coarse rich phase in the alloy structure, and enhance the wetting performance, oxidation resistance and corrosion resistance of the alloy solder.
在本申请的SnZn系无铅焊料中，添加的P元素能够使得合金焊料中熔融Sn在钎焊过程中保持新鲜状态，提高液态焊锡的抗氧化能力，从而增强焊点的可靠性。本申请将P的含量控制为0.050％～1.0％，可以有效地提高合金焊料的抗氧化能力，增强焊点的可靠性。In the SnZn series lead-free solder of the present application, the added P element can keep the molten Sn in the alloy solder fresh during the brazing process, improve the oxidation resistance of the liquid solder, and thus enhance the reliability of the solder joint. In this application, the content of P is controlled to 0.050% to 1.0%, which can effectively improve the oxidation resistance of the alloy solder and enhance the reliability of the solder joint.
在本申请第一方面所述的SnZn系无铅焊料中，所述SnZn系无铅焊料的熔点196℃～210℃。In the SnZn-based lead-free solder according to the first aspect of the present application, the melting point of the SnZn-based lead-free solder is 196°C to 210°C.
在本申请第一方面所述的SnZn系无铅焊料中，所述SnZn系无铅焊料的剪切强度为35MPa～45MPa，此处需要注意的是，SnZn系无铅焊料的剪切强度指的是SnZn系无铅焊料与铜基板制件之间的结合强度。In the SnZn-based lead-free solder according to the first aspect of the present application, the shear strength of the SnZn-based lead-free solder is 35 MPa to 45 MPa. It should be noted here that the shear strength of the SnZn-based lead-free solder refers to It is the bonding strength between SnZn lead-free solder and copper substrate parts.
在本申请第一方面所述的SnZn系无铅焊料中，所述SnZn系无铅焊料的存在形式没有任何的限制，可以根据实际使用需求进行选择。例如，所述SnZn系无铅焊料可以是膏状、粉状、块状，但并不限制于此。In the SnZn-based lead-free solder according to the first aspect of the present application, the existence form of the SnZn-based lead-free solder is not limited, and can be selected according to actual use requirements. For example, the SnZn-based lead-free solder may be in the form of paste, powder, or bulk, but it is not limited thereto.
其次说明根据本申请第二方面的SnZn系无铅焊料的制备方法，用于制备本申请第一方面所述的SnZn系无铅焊料，包括步骤：(1)称取原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn进行混合，然后分别进行第一次真空熔炼，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金；(2)按照待制备的SnZn系无铅焊料的成分，将SnBi合 金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn混合，然后进行第二次真空熔炼，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。Next, a method for preparing a SnZn-based lead-free solder according to the second aspect of the present application, for preparing the SnZn-based lead-free solder according to the first aspect of the present application, includes the steps of: (1) Weighing raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn respectively, and then perform the first vacuum melting respectively, and after the end, get SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy; 2) Mix the SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy with the raw materials Sn and Zn according to the composition of the SnZn-based lead-free solder to be prepared, and then perform the second vacuum melting and pour into the mold after the end After cooling and solidification, SnZn lead-free solder is obtained.
在本申请的SnZn系无铅焊料的制备方法中，先分别制备一系列中间合金(SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金)，然后再通过中间合金和原料Sn、Zn制备SnZn系无铅焊料的方法可以确保最终得到的SnZn系无铅焊料具有较高的成分精度。In the preparation method of the SnZn series lead-free solder of the present application, a series of intermediate alloys (SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy) are prepared respectively, and then SnZn is prepared through the intermediate alloy and the raw materials Sn and Zn The lead-free solder method can ensure that the resulting SnZn-based lead-free solder has high composition accuracy.
在本申请第二方面所述的SnZn系无铅焊料的制备方法中，步骤(1)中，第一次真空熔炼可以在真空感应炉中进行，需要注意的是，各元素原料进行第一真空熔炼的参数需要保持一致，优选地，第一次真空熔炼的温度为460℃～480℃，第一次真空熔炼的真空度小于等于10 -4Pa，第一次真空熔炼的时间为30min～40min。 In the preparation method of the SnZn series lead-free solder according to the second aspect of the present application, in step (1), the first vacuum melting can be performed in a vacuum induction furnace, it should be noted that each element raw material is subjected to the first vacuum The smelting parameters need to be consistent. Preferably, the temperature of the first vacuum melting is 460 ℃ ~ 480 ℃, the vacuum degree of the first vacuum melting is less than or equal to 10 -4 Pa, the time of the first vacuum melting is 30min ~ 40min .
在本申请第二方面所述的SnZn系无铅焊料的制备方法中，步骤(2)中，第二次真空熔炼可以在真空感应炉中进行。In the preparation method of the SnZn series lead-free solder according to the second aspect of the present application, in step (2), the second vacuum melting may be performed in a vacuum induction furnace.
在本申请第二方面所述的SnZn系无铅焊料的制备方法中，步骤(2)中国，真空熔炼温度为580℃～650℃，真空度小于等于10 -4Pa，真空熔炼时间为60min～75min。 In the preparation method of SnZn series lead-free solder according to the second aspect of the present application, step (2) China, the vacuum melting temperature is 580°C to 650°C, the vacuum degree is less than or equal to 10 -4 Pa, and the vacuum melting time is 60 min to 75min.
下面结合实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。The present application is further described below in conjunction with the embodiments. It should be understood that these embodiments are only used to illustrate the present application and not to limit the scope of the present application.
实施例1Example 1
称取适量的原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first One-time vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为13％、Bi为2.0％、In为0.90％、Ni为0.50％、Mn为0.20％、P为0.20％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进 行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 The mass percentages of Zn, Bi, In, Ni, Mn, P, Sn in the finally obtained SnZn series lead-free solder are: Zn is 13%, Bi is 2.0%, In is 0.90%, Ni is 0.50%, Mn is 0.20%, P is 0.20%, and the remainder is Sn. Appropriate amounts of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and raw materials Sn and Zn are weighed and mixed, and then placed in a vacuum induction furnace The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
实施例2Example 2
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为0.70％、Ni为0.20％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 12%, Bi is 0.70%, In is 0.70%, Ni is 0.20%, Mn is 0.40%, P is 0.50%, the balance is Sn, weigh the appropriate amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn, Zn and mix them, and then put them in the vacuum induction furnace The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, SnZn based lead-free solder is obtained.
实施例3Example 3
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为11％、Bi为3.0％、In为1.5％、Ni为0.50％、Mn为0.90％、P为0.20％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass percentage of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 11%, Bi is 3.0%, In is 1.5%, Ni is 0.50%, Mn is 0.90%, P is 0.20%, and the remainder is Sn. Appropriate amounts of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and raw materials Sn and Zn are weighed and mixed, and then placed in a vacuum induction furnace The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
实施例4Example 4
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真 空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为10％、Bi为2.6％、In为1.2％、Ni为0.90％、Mn为0.30％、P为0.80％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn series lead-free solder: Zn is 10%, Bi is 2.6%, In is 1.2%, Ni is 0.90%, Mn is 0.30%, P is 0.80%, and the remainder is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn and mix them, and then place them in a vacuum induction furnace The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
实施例5Example 5
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为15％、Bi为0.70％、In为0.70％、Ni为0.20％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn based lead-free solder: Zn is 15%, Bi is 0.70%, In is 0.70%, Ni is 0.20%, Mn is 0.40%, P is 0.50%, and the balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace. The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
实施例6Example 6
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为8.0％、Bi为0.70％、In为0.70％、Ni为0.20％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应 炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 8.0%, Bi is 0.70%, In is 0.70%, Ni is 0.20%, Mn is 0.40%, P is 0.50%, and the balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace. The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
实施例7Example 7
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.50％、In为0.70％、Ni为0.20％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn series lead-free solder: Zn is 12%, Bi is 0.50%, In is 0.70%, Ni is 0.20%, Mn is 0.40%, P is 0.50%, and the balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace. The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
实施例8Example 8
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为0.50％、Ni为0.20％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn series lead-free solder: Zn is 12%, Bi is 0.70%, In is 0.50%, Ni is 0.20%, Mn is 0.40%, P is 0.50%, and the balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace. The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
实施例9Example 9
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P 与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12.0％、Bi为0.70％、In为2.0％、Ni为0.20％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn series lead-free solder: Zn is 12.0%, Bi is 0.70%, In is 2.0%, Ni is 0.20%, Mn is 0.40%, P is 0.50%, and the balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace. The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
实施例10Example 10
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12.0％、Bi为0.7％、In为0.7％、Ni为0.1％、Mn为0.4％、P为0.5％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 12.0%, Bi is 0.7%, In is 0.7%, Ni is 0.1%, Mn is 0.4%, P is 0.5%, and the remainder is Sn. Appropriate amounts of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and raw materials Sn and Zn are weighed and mixed, and then placed in a vacuum induction furnace The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
实施例11Example 11
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为0.70％、Ni为1.0％、Mn为0.40％、 P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 12%, Bi is 0.70%, In is 0.70%, Ni is 1.0%, Mn is 0.40%, P is 0.50%, and the balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn and mix them, and then place them in a vacuum induction furnace The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
实施例12Example 12
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为0.70％、Ni为0.20％、Mn为0.10％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 12%, Bi is 0.70%, In is 0.70%, Ni is 0.20%, Mn is 0.10%, P is 0.50%, the balance is Sn, weigh the appropriate amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn, Zn and mix them, and then put them in the vacuum induction furnace The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
实施例13Example 13
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为0.70％、Ni为0.20％、Mn为1.0％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 12%, Bi is 0.70%, In is 0.70%, Ni is 0.20%, Mn is 1.0%, P is 0.50%, and the balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn and mix them, and then place them in a vacuum induction furnace. The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
实施例14Example 14
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为0.70％、Ni为0.20％、Mn为0.40％、P为0.050％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 12%, Bi is 0.70%, In is 0.70%, Ni is 0.20%, Mn is 0.40%, P is 0.050%, and the remainder is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn and mix them, and then place them in a vacuum induction furnace The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
实施例15Example 15
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为0.70％、Ni为0.20％、Mn为0.40％、P为1.0％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 12%, Bi is 0.70%, In is 0.70%, Ni is 0.20%, Mn is 0.40%, P is 1.0%, and the remainder is Sn. Appropriate amounts of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and raw materials Sn and Zn are weighed and mixed, and then placed in a vacuum induction furnace The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例1Comparative Example 1
以Sn-Ag 3-Cu 0.5系焊料作为无铅焊料。 Sn-Ag 3 -Cu 0.5 series solder is used as lead-free solder.
对比例2Comparative Example 2
称取适量原料Sn、Bi、In、Ni、P并分别将Bi、In、Ni、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，结束后得到SnBi合金、SnIn合金、SnNi合金、SnP合金，备用；Weigh the proper amount of raw materials Sn, Bi, In, Ni, P and mix Bi, In, Ni, P and Sn respectively according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first vacuum melting, After the completion of SnBi alloy, SnIn alloy, SnNi alloy, SnP alloy, spare;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、P、Sn的质量百分比为：Zn为14％、Bi为0.50％、In为0.50％、Ni为0.10％、P为0.10％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 The mass percentages of Zn, Bi, In, Ni, P, Sn in the SnZn lead-free solder finally obtained are: Zn is 14%, Bi is 0.50%, In is 0.50%, Ni is 0.10%, P is 0.10% 、The balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnP alloy and the raw materials Sn and Zn and mix them, and then put them in the vacuum induction furnace for the second vacuum melting. Among them, the second The vacuum degree of the next true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例3Comparative Example 3
称取适量原料Sn、Bi、In、Ni、Mn并分别将Bi、In、Ni、Mn与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金，备用；Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn and mix Bi, In, Ni, Mn and Sn respectively according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first vacuum melting, After the completion of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, spare;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为0.70％、Ni为0.20％、Mn为0.40％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 The mass percentages of Zn, Bi, In, Ni, Mn, Sn in the SnZn-based lead-free solder finally obtained are: Zn is 12%, Bi is 0.70%, In is 0.70%, Ni is 0.20%, Mn is 0.40% 、The balance is Sn. Weigh proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy and raw materials Sn and Zn and mix them, and then put them in the vacuum induction furnace for the second vacuum smelting. Among them, the second The vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例4Comparative Example 4
称取适量原料Sn、Bi、In、Mn、P并分别将Bi、In、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，结束后得到SnBi合金、SnIn合金、SnMn合金、SnP合金，备用；Weigh the proper amount of raw materials Sn, Bi, In, Mn, P and mix Bi, In, Mn, P and Sn respectively according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first vacuum melting, After the completion of SnBi alloy, SnIn alloy, SnMn alloy, SnP alloy, spare;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为0.70％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 The mass percentages of Zn, Bi, In, Mn, P and Sn in the SnZn lead-free solder finally obtained are: Zn is 12%, Bi is 0.70%, In is 0.70%, Mn is 0.40%, P is 0.50% 、The balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn and mix them, and then put them in the vacuum induction furnace for the second vacuum melting, of which, the second The vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例5Comparative Example 5
称取适量原料Sn、Bi、Ni、Mn、P并分别将Bi、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，结束后得到SnBi合金、SnNi合金、SnMn合金、SnP合金，备用；Weigh the proper amount of raw materials Sn, Bi, Ni, Mn, P and mix Bi, Ni, Mn, P and Sn respectively according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first vacuum melting, After the completion of the SnBi alloy, SnNi alloy, SnMn alloy, SnP alloy, spare;
按照最终得到的SnZn系无铅焊料中Zn、Bi、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、Ni为0.20％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 The mass percentages of Zn, Bi, Ni, Mn, P, Sn in the SnZn lead-free solder finally obtained are: Zn 12%, Bi 0.70%, Ni 0.20%, Mn 0.40%, P 0.50% 、The balance is Sn. Weigh the proper amount of SnBi alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn and mix them, and then put them in the vacuum induction furnace for the second vacuum melting, of which, the second The vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例6Comparative Example 6
称取适量原料Sn、In、Ni、Mn、P并分别将In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，结束后得到SnIn合金、SnNi合金、SnMn合金、SnP合金，备用；Weigh the proper amount of raw materials Sn, In, Ni, Mn, P and mix In, Ni, Mn, P and Sn respectively according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first vacuum melting, After the completion of SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy, spare;
按照最终得到的SnZn系无铅焊料中Zn、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、In为0.70％、Ni为0.20％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 The mass percentages of Zn, In, Ni, Mn, P, Sn in the SnZn lead-free solder finally obtained are: Zn is 12%, In is 0.70%, Ni is 0.20%, Mn is 0.40%, P is 0.50% 、The balance is Sn. Weigh proper amount of SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and raw materials Sn and Zn and mix them, and then put them in the vacuum induction furnace for the second vacuum smelting. Among them, the second The vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例7Comparative Example 7
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为17％、Bi为0.70％、In为0.70％、Ni为0.20％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进 行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 17%, Bi is 0.70%, In is 0.70%, Ni is 0.20%, Mn is 0.40%, P is 0.50%, and the balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace. The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例8Comparative Example 8
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为5.0％、Bi为0.70％、In为0.70％、Ni为0.20％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 5.0%, Bi is 0.70%, In is 0.70%, Ni is 0.20%, Mn is 0.40%, P is 0.50%, and the balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace. The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例9Comparative Example 9
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为3.5％、In为0.70％、Ni为0.20％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 The mass percentages of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn lead-free solder finally obtained are: Zn is 12%, Bi is 3.5%, In is 0.70%, Ni is 0.20%, Mn is 0.40%, P is 0.50%, and the balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace. The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例10Comparative Example 10
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P 与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.30％、In为0.70％、Ni为0.20％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn series lead-free solder: Zn is 12%, Bi is 0.30%, In is 0.70%, Ni is 0.20%, Mn is 0.40%, P is 0.50%, and the balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace. The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例11Comparative Example 11
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为0.30％、Ni为0.20％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 12%, Bi is 0.70%, In is 0.30%, Ni is 0.20%, Mn is 0.40%, P is 0.50%, and the balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace. The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例12Comparative Example 12
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为2.5％、Ni为0.20％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、 SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 The mass percentages of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn lead-free solder finally obtained are: Zn is 12%, Bi is 0.70%, In is 2.5%, Ni is 0.20%, Mn is 0.40%, P is 0.50%, and the balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn and mix them, and then place them in a vacuum induction furnace The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例13Comparative Example 13
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为0.70％、Ni为0.050％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 12%, Bi is 0.70%, In is 0.70%, Ni is 0.050%, Mn is 0.40%, P is 0.50%, and the balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace. The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例14Comparative Example 14
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为0.70％、Ni为1.50％、Mn为0.40％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn series lead-free solder: Zn is 12%, Bi is 0.70%, In is 0.70%, Ni is 1.50%, Mn is 0.40%, P is 0.50%, and the balance is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn, and then mix them, and then place them in a vacuum induction furnace. The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例15Comparative Example 15
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为0.70％、Ni为0.20％、Mn为0.050％、P为0.50％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 12%, Bi is 0.70%, In is 0.70%, Ni is 0.20%, Mn is 0.050%, P is 0.50%, the balance is Sn, weigh the appropriate amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn, Zn and mix them, and then place in the vacuum induction furnace The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例16Comparative Example 16
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为0.70％、Ni为0.20％、Mn为1.5％、P为0.5％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 12%, Bi is 0.70%, In is 0.70%, Ni is 0.20%, Mn is 1.5%, P is 0.5%, and the remainder is Sn. Appropriate amounts of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and raw materials Sn and Zn are weighed and mixed, and then placed in a vacuum induction furnace The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例17Comparative Example 17
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为0.70％、Ni为0.20％、Mn为0.40％、 P为0.010％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 12%, Bi is 0.70%, In is 0.70%, Ni is 0.20%, Mn is 0.40%, P is 0.010%, the balance is Sn, weigh the appropriate amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn, Zn and mix them, and then put them in the vacuum induction furnace The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
对比例18Comparative Example 18
称取适量原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn按照质量比为1:1进行混合，然后分别置于真空感应炉中进行第一次真空熔炼，其中，真空熔炼的温度为470℃、真空度为10 -4Pa、时间为30min，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金，备用； Weigh the proper amount of raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn according to the mass ratio of 1:1, and then put them in the vacuum induction furnace for the first Sub-vacuum smelting, in which the temperature of vacuum smelting is 470°C, the degree of vacuum is 10 -4 Pa, and the time is 30 min. After the end, SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy are obtained for use;
按照最终得到的SnZn系无铅焊料中Zn、Bi、In、Ni、Mn、P、Sn的质量百分比为：Zn为12％、Bi为0.70％、In为0.70％、Ni为0.20％、Mn为0.40％、P为1.5％、余量为Sn，分别称取适量的SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn并将其混合，然后置于真空感应炉中进行第二次真空熔炼，其中，第二次真熔炼的真空度为10 -4Pa，温度为600℃，时间为70min，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。 According to the final mass ratio of Zn, Bi, In, Ni, Mn, P, Sn in the SnZn-based lead-free solder: Zn is 12%, Bi is 0.70%, In is 0.70%, Ni is 0.20%, Mn is 0.40%, P is 1.5%, and the remainder is Sn. Weigh the proper amount of SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy and the raw materials Sn and Zn and mix them, and then place them in a vacuum induction furnace The second vacuum smelting, in which the vacuum degree of the second true smelting is 10 -4 Pa, the temperature is 600 ℃, the time is 70min, after the end is poured into the mold, after cooling and solidification, the SnZn series lead-free solder is obtained.
接下来说明焊料的测试过程Next, the solder testing process is explained
(1)焊料的铺展率测量(1) Spreading rate measurement of solder
将得到的直径为D的球形焊料置于铜基板正中央，同时将助焊剂覆盖于焊料之上，将上述载有焊料与助焊剂的铜基板放在加热板上加热至250℃，待焊料熔化后保温1min使其充分铺展，之后取下铜基板，室温冷却后得到在铜基板上润湿的焊料。测量在铜基板上润湿后的焊料的铺展面积和高度H，通过计算即可得到焊料铺展率。Place the obtained spherical solder with a diameter of D in the center of the copper substrate, and at the same time, cover the solder with the flux. Put the copper substrate carrying the solder and flux on the heating plate and heat to 250°C until the solder melts After heat preservation for 1 min, it was fully spread, and then the copper substrate was removed, and the solder wetted on the copper substrate was obtained after cooling at room temperature. The spreading area and height H of the solder after wetting on the copper substrate are measured, and the solder spreading ratio can be obtained by calculation.
Figure PCTCN2018120872-appb-000001
Figure PCTCN2018120872-appb-000001
(2)焊料的熔点测量(2) Melting point measurement of solder
通过DSC差示扫描量热法(DSC)测试焊料的熔点，测量需要焊料的质量约为0.02g。采用工具切割焊料，并切割后的焊料用无水乙醇超声清洗10min，以去除焊料表面污垢和油渍。之后将约0.02g合金焊料放入DSC设备中，以10℃/min的加热速度加热到250℃，样品室通入氮气作为保护气氛， 得到焊料的DSC曲线。根据DSC曲线，取其外推起始点作为焊料的熔点。The melting point of the solder was tested by DSC differential scanning calorimetry (DSC), and the mass of solder required for the measurement was about 0.02 g. Use a tool to cut the solder, and the cut solder is ultrasonically cleaned with absolute ethanol for 10 minutes to remove dirt and grease on the surface of the solder. After that, about 0.02 g of alloy solder was put into the DSC device, and heated to 250° C. at a heating rate of 10° C./min, and nitrogen gas was passed into the sample chamber as a protective atmosphere to obtain a DSC curve of the solder. According to the DSC curve, take the extrapolated starting point as the melting point of the solder.
(3)焊料的剪切强度测试(3) Shear strength test of solder
将3mm×3mm的焊料薄片置于铜基板上，然后在氮气保护下采用回流焊工艺进行焊接，焊接后用剪切强度测试仪测量其剪切强度，即焊料与铜基板的结合强度，其中，剪切速度为100μm/s，剪切测试时夹持处距离铜基板的高度为50μm。Place a 3mm×3mm solder sheet on the copper substrate, and then use a reflow soldering process under the protection of nitrogen. After soldering, the shear strength is measured with a shear strength tester, that is, the bonding strength of the solder and the copper substrate. The shearing speed is 100 μm/s, and the height of the grip from the copper substrate during the shearing test is 50 μm.
(4)焊料的可靠性测试(4) Solder reliability test
采用加速热循环下焊料焊接后焊点能保持不失效所经历的循环次数来表征焊料的可靠性，控制加入热循环的温度在-40℃至125℃之间，加热时间和冷却时间均为15min，30min为一个周期，以焊点失效(即通电后焊点出现断路)为判断依据，记录焊点失效时焊点所经历的热循环周期，循环次数越高，说明焊料的可靠性越好。The number of cycles that the solder joint can maintain without failure after soldering under accelerated thermal cycling is used to characterize the reliability of the solder. The temperature of the thermal cycle is controlled between -40℃ and 125℃, and the heating time and cooling time are 15min. , 30min is a cycle, based on the failure of the solder joint (that is, the solder joint is open after energization) as the basis for judgment, record the thermal cycle of the solder joint when the solder joint fails, the higher the number of cycles, the better the reliability of the solder.
(5)焊料的成本核算(5) Cost accounting of solder
采用金属价格，按其百分比进行核算焊料的成本，不考虑加工工艺等成本，以市场上某款主流的Sn-Ag-Cu系无铅焊料的成本为标准1。Adopt the metal price, calculate the cost of solder according to its percentage, without considering the cost of processing technology, etc., taking the cost of a mainstream Sn-Ag-Cu lead-free solder on the market as the standard1.
表1实施例1-15和对比例1-18的性能测试结果Table 1 Performance test results of Examples 1-15 and Comparative Examples 1-18
Figure PCTCN2018120872-appb-000002
Figure PCTCN2018120872-appb-000002
Figure PCTCN2018120872-appb-000003
Figure PCTCN2018120872-appb-000003
接下来说明将焊料应用于表面组装技术(SMT)中的性能表现Next, the performance of applying solder to surface mount technology (SMT) is explained.
首先，将实施例3得到的SnZn系无铅焊粉与以松香为主要成分的助焊剂配合，制成焊膏。First, the SnZn-based lead-free solder powder obtained in Example 3 was combined with a flux containing rosin as a main component to prepare a solder paste.
其次，说明将焊料应用于SMT中的测试过程。Next, the test process of applying solder to SMT is explained.
实施例16Example 16
取20块印制电路板(PCB)并在每块PCB上焊接68个0603元件，焊接完成后记录焊接温度和失效焊点数，并计算焊点合格率。Take 20 printed circuit boards (PCB) and solder 68 0603 components on each PCB. After welding, record the welding temperature and the number of failed solder joints, and calculate the solder joint qualification rate.
Figure PCTCN2018120872-appb-000004
Figure PCTCN2018120872-appb-000004
在每块PCB上取5个不同位置的0603元件，用推力测试仪将其推落，记录最高推力并取5个位置0603元件推力值的平均值作为0603元件在此块PCB板的平均推拉力。Take 5603 components at different positions on each PCB, push them down with a thrust tester, record the highest thrust and take the average of the thrust values of 0603 components at 5 positions as the average push-pull force of 0603 components on this PCB board .
此处需要注意的是，通常认为0603元件的推拉力值大于1.2Kgf即为合格。It should be noted here that it is generally considered that the push-pull force value of the 0603 element is greater than 1.2Kgf.
实施例17Example 17
取48块印制电路板(PCB)并在每块PCB上焊接214个0603元件，焊接完成后记录焊接温度和失效焊点数，并计算焊点合格率。Take 48 printed circuit boards (PCB) and solder 214 0603 components on each PCB. After welding, record the welding temperature and the number of failed solder joints, and calculate the solder joint qualification rate.
Figure PCTCN2018120872-appb-000005
Figure PCTCN2018120872-appb-000005
在每块PCB上取5个不同位置的0603元件，用推力测试仪将其推落，记录最高推力并取5个位置0603元件推力值的平均值作为0603元件在此块PCB板的平均推拉力。Take 5603 components at different positions on each PCB, push them down with a thrust tester, record the highest thrust and take the average of the thrust values of 0603 components at 5 positions as the average push-pull force of 0603 components on this PCB board .
实施例18Example 18
取24块印制电路板(PCB)并在每块PCB上焊接487个0603元件，焊接完成后记录焊接温度和失效焊点数，并计算焊点合格率。Take 24 printed circuit boards (PCB) and solder 487 0603 components on each PCB. After welding, record the welding temperature and the number of failed solder joints, and calculate the solder joint qualification rate.
Figure PCTCN2018120872-appb-000006
Figure PCTCN2018120872-appb-000006
在每块PCB上取5个不同位置的0603元件，用推力测试仪将其推落，记录最高推力并取5个位置0603元件推力值的平均值作为0603元件在此块PCB板的平均推拉力。Take 5603 components at different positions on each PCB, push them down with a thrust tester, record the highest thrust and take the average of the thrust values of 0603 components at 5 positions as the average push-pull force of 0603 components on this PCB board .
实施例19Example 19
取23块印制电路板(PCB)并在每块PCB上焊接2045个0603元件，焊接完成后记录焊接温度和失效焊点数，并计算焊点合格率。Take 23 printed circuit boards (PCB) and solder 2045 0603 components on each PCB. After welding, record the welding temperature and the number of failed solder joints, and calculate the solder joint qualification rate.
Figure PCTCN2018120872-appb-000007
Figure PCTCN2018120872-appb-000007
在每块PCB上取5个不同位置的0603元件，用推力测试仪将其推落，记录最高推力并取5个位置0603元件推力值的平均值作为0603元件在此块 PCB板的平均推拉力。Take 5603 components at different positions on each PCB, push them down with a thrust tester, record the highest thrust and take the average of the thrust values of 0603 components at 5 positions as the average push-pull force of 0603 components on this PCB board .
表2实施例16-19的测试结果Table 2 Test results of Examples 16-19
Figure PCTCN2018120872-appb-000008
Figure PCTCN2018120872-appb-000008
从表1和表2的测试结果分析可知，与常规的Sn-Ag-Cu系无铅焊料相比，本申请的SnZn系无铅焊料总体具有润湿性能好、熔点适中、结合强度高、可靠性好、成本低廉的优点，可作为SnPb系焊料的完全替代品。From the analysis of the test results in Table 1 and Table 2, it can be seen that compared with the conventional Sn-Ag-Cu lead-free solder, the SnZn lead-free solder of the present application has good wetting performance, moderate melting point, high bonding strength and reliability The advantages of good performance and low cost can be used as a complete substitute for SnPb solder.
从实施例2和对比例2-6的测试结果分析可知，本申请同时包括Zn、Bi、In、Ni、Mn、P以及Sn元素的SnZn系无铅焊料具有具有润湿性能好、熔点适中、与基底结合强度高、可靠性好、成本低廉的特点。特别是在实施例2和对比例2中，进一步结合图1分析可知，本申请的SnZn系无铅焊料中的Mn元素可以消除合金焊料组织中粗大的富Zn相，从而可增强界面结合强度，并改善合金焊料的润湿性能和可靠性。From the analysis of the test results of Example 2 and Comparative Examples 2-6, it can be seen that the SnZn series lead-free solder including Zn, Bi, In, Ni, Mn, P, and Sn elements in the present application has good wetting performance, moderate melting point, It has the characteristics of high bonding strength, good reliability and low cost. Especially in Example 2 and Comparative Example 2, further analysis in conjunction with FIG. 1 shows that the Mn element in the SnZn lead-free solder of the present application can eliminate the coarse Zn-rich phase in the alloy solder structure, thereby enhancing the interface bonding strength. And improve the wetting performance and reliability of alloy solder.
同时，从实施例1-15和对比例7-18中分析可知，当SnZn系无铅焊料中的各元素的含量保持在本申请的范围内时，SnZn系无铅焊料的润湿性能、熔点、与基底结合强度、可靠性及成本方面的表现更加优异。Meanwhile, from the analysis in Examples 1-15 and Comparative Examples 7-18, it can be seen that when the content of each element in the SnZn-based lead-free solder is kept within the scope of this application, the wettability and melting point of the SnZn-based lead-free solder , The performance of bonding strength, reliability and cost with the substrate is more excellent.

Claims (10)

  1. 一种SnZn系无铅焊料，其特征在于，按质量百分比计，组成为：A SnZn series lead-free solder, characterized in that, in terms of mass percentage, the composition is:
    Zn，8.0％～15％；Zn, 8.0%～15%;
    Bi，0.50％～3.0％；Bi, 0.50%～3.0%;
    In，0.50％～2.0％；In, 0.50%～2.0%;
    Ni，0.10％～1.0％；Ni, 0.10%～1.0%;
    Mn，0.10％～1.0％；Mn, 0.10%～1.0%;
    P，0.050％～1.0％；P, 0.050%～1.0%;
    余量为Sn。The balance is Sn.
  2. 根据权利要求1所述的SnZn系无铅焊料，其特征在于，所述SnZn系无铅焊料的熔点为196℃～210℃。The SnZn-based lead-free solder according to claim 1, wherein the melting point of the SnZn-based lead-free solder is 196°C to 210°C.
  3. 根据权利要求1所述的SnZn系无铅焊料，其特征在于，所述Zn的含量为8.0％～13％。The SnZn-based lead-free solder according to claim 1, wherein the content of Zn is 8.0% to 13%.
  4. 根据权利要求1所述的SnZn系无铅焊料，其特征在于，所述Bi的含量为0.50％～2.5％。The SnZn-based lead-free solder according to claim 1, wherein the Bi content is 0.50% to 2.5%.
  5. 根据权利要求1所述的SnZn系无铅焊料，其特征在于，所述In的含量为0.60％～1.6％。The SnZn-based lead-free solder according to claim 1, wherein the content of In is 0.60% to 1.6%.
  6. 一种SnZn系无铅焊料的制备方法，用于制备权利要求1-5中任一项所述的SnZn系无铅焊料，包括步骤：A method for preparing SnZn-based lead-free solder for preparing the SnZn-based lead-free solder according to any one of claims 1 to 5 includes the steps of:
    (1)称取原料Sn、Bi、In、Ni、Mn、P并分别将Bi、In、Ni、Mn、P与Sn进行混合，然后分别进行第一次真空熔炼，结束后得到SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金；(1) Weigh the raw materials Sn, Bi, In, Ni, Mn, P and mix Bi, In, Ni, Mn, P and Sn respectively, and then perform the first vacuum smelting separately, and then get SnBi alloy, SnIn Alloys, SnNi alloys, SnMn alloys, SnP alloys;
    (2)按照待制备的SnZn系无铅焊料的成分，将SnBi合金、SnIn合金、SnNi合金、SnMn合金、SnP合金与原料Sn、Zn混合，然后进行第二次真 空熔炼，结束后浇注到模具中，冷却凝固后得到SnZn系无铅焊料。(2) Mix SnBi alloy, SnIn alloy, SnNi alloy, SnMn alloy, SnP alloy with raw materials Sn and Zn according to the composition of SnZn-based lead-free solder to be prepared, and then perform the second vacuum melting and pour into the mold after the end During the cooling and solidification, SnZn-based lead-free solder is obtained.
  7. 根据权利要求6所述的SnZn系无铅焊料的制备方法，其特征在于，步骤(1)中，第一次真空熔炼的温度为460℃～480℃，第一次真空熔炼的真空度小于等于10 -4Pa，第一次真空熔炼的时间为30min～40min。 The method for preparing a SnZn-based lead-free solder according to claim 6, wherein in step (1), the temperature of the first vacuum melting is 460°C to 480°C, and the vacuum degree of the first vacuum melting is less than or equal to 10 -4 Pa, the time of the first vacuum melting is 30min～40min.
  8. 根据权利要求6所述的SnZn系无铅焊料的制备方法，其特征在于，步骤(2)中，第二次真空熔炼的温度为580℃～650℃。The method for preparing a SnZn-based lead-free solder according to claim 6, wherein in step (2), the temperature of the second vacuum melting is 580°C to 650°C.
  9. 根据权利要求6所述的SnZn系无铅焊料的制备方法，其特征在于，步骤(2)中，第二次真空熔炼的真空度小于等于10 -4Pa。 The method for preparing a SnZn-based lead-free solder according to claim 6, wherein in step (2), the vacuum degree of the second vacuum melting is less than or equal to 10 -4 Pa.
  10. 根据权利要求6所述的SnZn系无铅焊料的制备方法，其特征在于，步骤(2)中，第二次真空熔炼的时间为60min～75min。The method for preparing SnZn-based lead-free solder according to claim 6, wherein in step (2), the time of the second vacuum melting is 60 min to 75 min.
PCT/CN2018/120872 2018-12-13 2018-12-13 Sn-zn lead-free solder material and preparation method therefor WO2020118613A1 (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001239392A (en) * 2000-02-29 2001-09-04 Mitsubishi Electric Corp Lead-free solder, solder junction and it's jointing method using the same
CN1337293A (en) * 2001-09-05 2002-02-27 北京工业大学 Rare earth-containing tin-base lead-less brazing alloy and its prepn
CN1481970A (en) * 2003-07-25 2004-03-17 南昌大学 Tin-zinc base plumbum-free solder alloy and its preparing technology
CN101817126A (en) * 2009-12-23 2010-09-01 株洲冶炼集团股份有限公司 Tin-zinc lead-free solder and preparation method thereof
CN102166690A (en) * 2011-05-27 2011-08-31 东南大学 Tin-zinc base composite soldering flux
CN103240541A (en) * 2013-05-13 2013-08-14 金封焊宝有限责任公司 Tin zinc multi-element alloy solder for soldering copper and aluminum and preparation method thereof
US20150231740A1 (en) * 2014-02-18 2015-08-20 Heraeus Precious Metals North America Conshohocken Llc Soldering method for polymer thick film compositions
CN105234580A (en) * 2015-11-17 2016-01-13 镇江市锶达合金材料有限公司 High-strength lead-free brazing filler metal for brazing

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1176779C (en) * 2001-11-27 2004-11-24 深圳市格林美环境材料有限公司 Lead-free welding material and its prepn
CN1651180A (en) * 2005-02-03 2005-08-10 复旦大学 Sn-zn or Sn-AgBi series leadless parent metal containing trace doped metal and its preparation method
JP2011156558A (en) * 2010-01-30 2011-08-18 Nihon Superior Co Ltd Lead-free solder alloy
CN102489893A (en) * 2010-12-31 2012-06-13 广东中实金属有限公司 SnZn-based lead-free brazing alloy
CN106808107A (en) * 2015-12-01 2017-06-09 青岛森美克化工技术有限公司 A kind of Sn-Zn solders for solder solder stick and preparation method thereof
CN107866644A (en) * 2016-09-26 2018-04-03 青岛九洲千和机械有限公司 A kind of Sn Zn solders for solder solder stick and preparation method thereof
CN108465971A (en) * 2018-02-28 2018-08-31 西安理工大学 A kind of preparation method of low melting point Sn-Zn-Bi brazing filler metal alloys

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001239392A (en) * 2000-02-29 2001-09-04 Mitsubishi Electric Corp Lead-free solder, solder junction and it's jointing method using the same
CN1337293A (en) * 2001-09-05 2002-02-27 北京工业大学 Rare earth-containing tin-base lead-less brazing alloy and its prepn
CN1481970A (en) * 2003-07-25 2004-03-17 南昌大学 Tin-zinc base plumbum-free solder alloy and its preparing technology
CN101817126A (en) * 2009-12-23 2010-09-01 株洲冶炼集团股份有限公司 Tin-zinc lead-free solder and preparation method thereof
CN102166690A (en) * 2011-05-27 2011-08-31 东南大学 Tin-zinc base composite soldering flux
CN103240541A (en) * 2013-05-13 2013-08-14 金封焊宝有限责任公司 Tin zinc multi-element alloy solder for soldering copper and aluminum and preparation method thereof
US20150231740A1 (en) * 2014-02-18 2015-08-20 Heraeus Precious Metals North America Conshohocken Llc Soldering method for polymer thick film compositions
CN105234580A (en) * 2015-11-17 2016-01-13 镇江市锶达合金材料有限公司 High-strength lead-free brazing filler metal for brazing

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