CN111085798A - High-reliability silver-free tin-based solder and preparation method thereof - Google Patents
High-reliability silver-free tin-based solder and preparation method thereof Download PDFInfo
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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
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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
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
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Abstract
The high-reliability silver-free tin-based solder is a silver-free SnCuBiNiCoMn lead-free solder, and comprises the following components in percentage by weight: 0.1 to 1.0 wt% of Cu, 0.03 to 1.0 wt% of Bi, 0.03 to 1.0 wt% of Ni, 0.5 to 1.0 wt% of nano Co particles, 0.5 to 1.0 wt% of nano Mn particles, and the balance of Sn; wherein, part of the nanometer Co particles and the nanometer Mn particles are uniformly distributed in the lead-free solder melt in a dispersion mode. The preparation method comprises the steps of firstly preparing the SnCuBiNi alloy, placing the SnCuBiNi alloy in a vacuum intermediate frequency furnace, heating the furnace body to 500-600 ℃, preserving the temperature for 5min, vacuumizing, introducing nitrogen, adding the nanometer Co particles and the nanometer Mn particles into a melt by using the nitrogen, and then cooling the mixture along with the furnace to obtain the brazing alloy. The solder has stable quality, high reliability, simple preparation process and cost saving.
Description
Technical Field
The invention relates to the technical field of tin-based solder and a preparation method thereof.
Background
The electronic industry is one of the most rapidly developing industries, especially the promotion of automation and intellectualization, and electronic equipment is taken as the most important control element, and the assembly process of the electronic equipment plays a decisive role in the quality of electronic products. The lead-free solder alloy is used as the most basic material of an electronic assembly process, the performance of the lead-free solder alloy is one of the focuses of electronic packaging process attention, and the excellent wettability can effectively reduce the problems of insufficient solder, missing solder and the like generated in the welding process.
On the other hand, the electronic products are being miniaturized and miniaturized at present, and the required welding solder is less and less, so that the performance of the solder has higher requirements, the solder alloy is required to have excellent welding performance, and the quality after welding is ensured. The appearance of the IMC layer of the welding interface has important influence on the quality after welding, and due to the particularity of welding materials, the intermetallic compound layer formed on the welding interface is often uneven, so that the reliability of a welding joint is reduced, the appearance of the welding interface is controlled, and the welding interface with moderate, even and smooth thickness is obtained, which is also the target pursued by solder developers.
Researches find that the addition of cobalt and nickel elements in the solder alloy can effectively improve the microstructure, mechanical property, electrical property, welding property and the like of the alloy. Because the relative melting point of the simple substance of cobalt is very high, namely 1495 ℃, the relative melting point of the simple substance of manganese is also very high, namely 1244 ℃, and the melting point of the simple substance of tin is relatively very low, namely only 232 ℃: when the tin alloy is normally melted, cobalt and manganese elements are difficult to enter the tin melt; the increase in melting temperature causes severe oxidation of tin, resulting in large variations in alloy composition. If the intermediate alloy of cobalt and manganese with tin is adopted, although the difficulty of cobalt and manganese elements entering the tin alloy is relatively reduced, the preparation cost of the intermediate alloy of cobalt and manganese with tin is higher. Therefore, the cost of cobalt and manganese is higher no matter the cobalt and manganese simple substance is smelted at high temperature in vacuum or the tin-cobalt and tin-manganese intermediate alloy is smelted at low temperature.
At present, solder developers have succeeded in introducing various nanophase, for example, nanophase Ag, Cu, Si, TiO, into solder alloy2、Al2O3、Ag3Sn、Cu6Sn5The nano wires such as particles, CNTs and the like not only can improve the effect of alloy structure to a certain extent, but also can neglect the problem of high melting point of alloy elements to a certain extent. However, as the nano particles are easy to float upwards, the nano particles are difficult to be uniformly distributed in the solder alloy and the adding efficiency is low, so that the solder quality is unstable, the production process consumes too long time, and the production efficiency is reduced.
Disclosure of Invention
The invention aims to solve the defects of the prior art, and provides the SnCuBiNiCoMn lead-free solder alloy which can ensure that nano particles can be uniformly distributed in the solder alloy and has high adding efficiency and the preparation method thereof, so as to improve the microstructure, the mechanical property, the electrical property, the welding property and the like of the lead-free solder alloy and ensure the stable quality of the lead-free solder alloy.
The technical scheme adopted by the invention is as follows:
the high-reliability silver-free tin-based solder is a silver-free SnCuBiNiCoMn lead-free solder, and comprises the following components in percentage by weight: 0.1 to 1.0 wt% of Cu, 0.03 to 1.0 wt% of Bi, 0.03 to 1.0 wt% of Ni, 0.5 to 1.0 wt% of nano Co particles, 0.5 to 1.0 wt% of nano Mn particles, and the balance of Sn; wherein, part of the nanometer Co particles and the nanometer Mn particles are uniformly distributed in the lead-free solder melt in a dispersion mode.
Furthermore, the particle size of the Co nanoparticles and the Mn nanoparticles is 20-100 nm.
A preparation method of a high-reliability silver-free tin-based solder comprises the following steps:
(1) putting the prepared SnCuBiNi alloy into a vacuum intermediate frequency furnace;
(2) the vacuum intermediate frequency furnace is vacuumized and then filled with nitrogen, so that the pressure in the furnace is slightly higher than the atmospheric pressure, the nitrogen is always filled in the furnace and the pressure in the furnace is kept slightly higher than the atmospheric pressure in the subsequent whole preparation process, and the redundant gas is discharged through a constant pressure valve of the vacuum intermediate frequency furnace;
(3) heating the vacuum intermediate frequency furnace to 500-600 ℃, and preserving heat for 5min to obtain a SnCuBiNi melt A;
(4) uniformly blowing the Co nanoparticles and the Mn nanoparticles into the melt A through a thin tube by using nitrogen;
keeping the electromagnetic stirring of the vacuum intermediate frequency furnace in 20min from the beginning of the step (2) to the end of blowing the nano Co particles and the nano Mn particles into the melt A, and mechanically stirring the alloy in the furnace by adopting a mechanical stirring device while keeping the electromagnetic stirring of the alloy in the furnace in the vacuum intermediate frequency furnace so as to uniformly distribute the nano particles in the melt A;
(5) and after the preparation process is finished, the alloy in the furnace is cooled along with the furnace to obtain the high-reliability silver-free tin-based solder.
The mechanical stirring device is inserted into the furnace from the top of the vacuum intermediate frequency furnace and is provided with one or more than two layers of stirring blades.
Further, in the process of preparing the silver-free tin-based solder, the outlet of a thin tube for blowing in the nano Co particles and the nano Mn particles is arranged at the bottom of a crucible of a vacuum intermediate frequency furnace, a mechanical stirring device is arranged at the upper part of the outlet of the thin tube, and the nano particles are continuously stirred by the mechanical stirring action in the process of floating bubbles from the outlet of the thin tube, and are finally melted into a melt to obtain an alloy melt containing the high-dispersity nano particles.
Furthermore, when the nanometer Co particles and the nanometer Mn particles are uniformly blown into the melt A through the thin tube by using nitrogen, the inner diameter of the thin tube is 1-3 mm, the gas pressure is 0.1-0.3 MPa, and the nanometer particles are added into the melt at the speed of 0.3-0.5 g/s.
Furthermore, the raw materials for preparing the SnCuBiNi alloy are pure Sn, SnCu10, SnBi58, SnCuBiNi and SnNi4, Sn in the SnCuBiNi melt A is realized by adding pure Sn, Cu is realized by adding SnCu10, Bi is realized by adding SnBi58, and Ni is realized by adding SnNi 4.
Further, the method comprises the steps of reducing the Co nanoparticles and the Mn nanoparticles, and then blowing the Co nanoparticles and the Mn nanoparticles into the melt A; the reduction treatment method comprises the steps of putting the nanometer Co particles and the nanometer Mn particles into a tube furnace, introducing reducing gas, and preserving heat for a period of time.
Furthermore, the reducing gas refers to a mixed gas of nitrogen and hydrogen, and the volume ratio of the nitrogen to the hydrogen is (10-20): 1, the heat preservation temperature of the tube furnace is 120 ℃, and the heat preservation time is 30 min.
The invention has the following beneficial effects:
(1) according to the invention, by adding Co and Mn nano particles into the SnCuBiNi alloy, the problem that high-melting-point elements such as Co and Mn are difficult to manufacture intermediate alloy can be effectively solved;
(2) part of metal nano particles exist in a simple substance form and are adsorbed on the surfaces of crystal grains of a welding spot structure, so that the growth speed of the crystal grains can be reduced; meanwhile, the addition of Co and Mn nano particles provides non-uniform nucleation and can reduce Cu6Sn5Freezing supercooling degree to promote Cu6Sn5The phase is refined, the micron Cu6Sn5 is dispersed and distributed to provide a pinning effect, and the creep resistance of the alloy is improved under the combined action of the phase and the pinning effect, so that the wettability of the nano Co and Mn particles on the surface of a welding spot tissue is better, and the creep property of the alloy is better;
(3) the introduction of the nano Co and Mn particles blows a melt through a thin tube outlet positioned at the bottom of the crucible, and the electromagnetic stirring of an intermediate frequency furnace and the continuous stirring of a mechanical stirring device are carried out in the floating process of the nano particles, so that the nano particles can be uniformly dispersed in the melt, the efficiency of the nano particles entering the melt is higher, the production efficiency can be improved, the nano particles can be uniformly dispersed in the melt, and the high-reliability and stable-quality solder alloy can be obtained;
(4) the Co and Mn nano particles are subjected to reduction treatment before being blown into a furnace, so that oxygen on the surfaces of the particles is removed, the problem that the nano particles are difficult to enter a melt due to the fact that the nano particles absorb a large amount of oxygen due to high surface energy and the nano particles directly blow into the nano particles easily form an oxidation film with the melt, and the efficiency of the nano particles entering the alloy melt is improved;
(5) the method has simple process and cost saving, and the prepared lead-free solder alloy has excellent performance and does not cause pollution to the environment.
Drawings
FIGS. 1(a) and 1(b) are metallographic photographs of an Sn-0.7Cu-0.1Bi-0.1Ni alloy prepared by the method of the present invention and an Sn-0.7Cu-0.1Bi-0.1 Mn silver-free solder alloy obtained by adding nano Co particles and nano Mn particles to an Sn-0.7Cu-0.1Bi-0.1Ni alloy, respectively;
fig. 2 is a schematic diagram of the coordination of stirring and blowing of Co and Mn nanoparticles during the preparation of the lead-free solder alloy of the present invention.
Detailed Description
The invention will be further described with reference to the drawings and the embodiments without limiting the scope of the invention thereto.
Example 1
Sn-0.7Cu-0.1Bi-0.1Ni-0.5Co-0.5Mn silver-free solder alloy is prepared by the following method:
(1) the Sn-0.7Cu-0.1Bi-0.1Ni alloy is prepared by a conventional method, and the metallographic structure of the alloy is shown in figure 1. The raw materials for preparing the Sn-0.7Cu-0.1Bi-0.1Ni alloy are pure Sn, SnCu10, SnBi58, SnCuBiNi and SnNi4, wherein Sn in the alloy is realized by adding pure Sn, Cu is realized by adding SnCu10, Bi is realized by adding SnBi58, and Ni is realized by adding SnNi 4;
(2) and (2) placing the alloy prepared in the step (1) into a crucible of a vacuum intermediate frequency furnace, vacuumizing until the air pressure in the furnace is slightly larger than atmospheric pressure, heating to 500-600 ℃, and preserving heat for 5min to obtain Sn-0.7Cu-0.1Bi-0.1Ni melt A. As shown in FIG. 2, a crucible 1 of a vacuum intermediate frequency furnace is internally provided with a mechanical stirring device 2 inserted into the furnace from the top of the furnace for stirring a melt A, and the mechanical stirring device is provided with one layer or more than two layers of stirring blades 21;
(3) reducing the Co nanoparticles and Mn nanoparticles with the particle size of 20-30 nm to remove oxygen molecules adsorbed on the surfaces of the nanoparticles, so as to improve the efficiency of the nanoparticles entering the alloy melt; the reduction treatment method comprises the steps of putting the nano Co particles and the nano Mn particles into a tube furnace, introducing nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 20: 1), and preserving heat for 30min at 120 ℃;
(4) nitrogen is filled into a crucible of the vacuum intermediate frequency furnace through an air charging port 3, and then 0.6 wt% of nano Co particles and 0.6 wt% of nano Mn particles which are subjected to reduction treatment are uniformly blown into the melt through a thin tube 4. The inner diameter of the used thin tube is 2mm, the gas pressure of nitrogen is 0.1MPa, and the nano particles are added into the melt A at the speed of 0.5 g/s. When blowing in nanometer Co granule and nanometer Mn granule into the fuse-element, the crucible bottom of vacuum intermediate frequency furnace is arranged in to the tubule export, and mechanical stirring device is located the fuse-element, begins from blowing in nanometer Co granule and nanometer Mn granule, opens mechanical stirring device promptly, and mechanical stirring device's rotational speed is 10r/min, touches agitating unit after the bubble that comes out from the tubule export upwards floats, and until partial nanometer granule floats to the whole in-process above the fuse-element surface, the nanometer granule is constantly stirred, finally melts into in the fuse-element A. And after the nano particles are completely melted into the melt, continuously stirring for 25min under the condition of heat preservation. The alloy in the furnace is mechanically stirred by an electromagnetic stirring device and a mechanical stirring device of the vacuum intermediate frequency furnace, so that the nano particles are uniformly distributed in the melt, and the alloy melt containing the high-dispersity nano particles is obtained. And cooling the alloy melt along with the furnace to obtain the Sn-0.7Cu-0.1Bi-0.1Ni-0.5Co-0.5Mn silver-free solder alloy. And in the whole preparation process, the nitrogen is always introduced into the furnace, the air pressure in the furnace is kept slightly higher than the atmospheric pressure, and redundant gas is discharged through a constant pressure valve 5 of the vacuum intermediate frequency furnace.
The solder alloy prepared by the steps comprises 0.71% of Cu, 0.095% of Bi, 0.1% of Ni, 0.52% of Co0.50% of Mn and the balance of Sn. The metallographic structure is shown in FIG. 2. By using the same experimental conditions, compared with the conventional SnCu0.7 (the content of Cu is 0.7 percent, and the balance is Sn) silver-free solder, the thickness growth rate of the IMC layer is reduced by 38.6 percent, the failure rate of a welding spot is reduced by 3 percent by the cyclic aging treatment at the temperature of 1000-40-125 ℃, the tensile strength is improved by 25.5 percent, and the shear strength is improved by 37.2 percent; compared with the conventional SnAg0.3Cu0.7(Ag content is 0.3%, Cu content is 0.7%, and the balance is Sn) low-silver solder, the thickness increase speed of the IMC layer is reduced by 9.1%, the failure rate of a welding spot is basically consistent after 1500-40-125 ℃ temperature cycle aging treatment, the tensile strength is improved by 6.9%, and the shear strength is improved by 10.5%.
Example 2
Sn-0.7Cu-0.5Bi-0.5Ni-0.9Co-0.7Mn silver-free solder alloy is prepared by the following method:
(1) the Sn-0.7Cu-0.5Bi-0.5Ni alloy is prepared by adopting the method of the prior art. The raw materials for preparing the Sn-0.7Cu-0.5Bi-0.5Ni alloy are pure Sn, SnCu10, SnBi58, SnCuBiNi and SnNi 4;
(2) placing the alloy prepared in the step (1) into a crucible of a vacuum intermediate frequency furnace, vacuumizing until the air pressure in the furnace is slightly larger than atmospheric pressure, heating to 500 ℃, and preserving heat for 5min to obtain Sn-0.7Cu-0.5Bi-0.5Ni melt A;
(3) carrying out reduction treatment on nano Co particles and nano Mn particles with the particle size of 30-50 nm, wherein the reduction treatment method comprises the steps of putting the nano Co particles and the nano Mn particles into a tube furnace, introducing nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 10: 1), and carrying out heat preservation for 30min at 120 ℃;
(4) and (3) filling nitrogen into the vacuum intermediate frequency furnace, and blowing the reduced 1.0 wt% of nano Co particles and 0.8 wt% of nano Mn particles into the melt A through a thin tube, wherein the gas pressure is 0.2MPa, and the nano particles are added into the melt at the speed of 0.5 g/s. When the nano Co particles and the nano Mn particles are blown into the melt A, the outlet of the thin tube is arranged at the bottom of a crucible of the vacuum intermediate frequency furnace, the mechanical stirring device is positioned in the melt, the mechanical stirring device is started from the blowing of the nano Co particles and the nano Mn particles, the rotating speed of the mechanical stirring device is 10r/min, after all the nano particles are melted into the melt, the heat preservation stirring is continued for 20min, so that the nano particles are uniformly distributed in the melt A, and the alloy melt containing the high-dispersity nano particles is obtained. And cooling the alloy melt along with the furnace to obtain the Sn-0.7Cu-0.5Bi-0.5Ni-0.9Co-0.7Mn silver-free solder alloy. And in the whole preparation process, the nitrogen is always introduced into the furnace, the air pressure in the furnace is kept slightly higher than the atmospheric pressure, and redundant gas is discharged through a constant pressure valve of the vacuum intermediate frequency furnace.
The brazing alloy prepared by the steps comprises 0.70% of Cu, 0.48% of Bi, 0.502% of Ni, 0.95% of Co, 0.74% of Mn and the balance of Sn. By using the same experimental conditions, compared with the conventional SnCu0.7 (the content of Cu is 0.7 percent, and the balance is Sn) silver-free solder, the thickness growth rate of the IMC layer is reduced by 40.6 percent, the failure rate of a welding spot is reduced by 5 percent by the cyclic aging treatment at the temperature of 1000-40-125 ℃, the tensile strength is improved by 42.9 percent, and the shear strength is improved by 45.8 percent; compared with the conventional SnAg0.3Cu0.7(Ag content is 0.3%, Cu content is 0.7%, and the balance is Sn) low-silver brazing filler metal, the thickness increase speed of the IMC layer is reduced by 11.2%, the failure rate of a welding spot is reduced by 2% through 1500-40-125 ℃ temperature cycle aging treatment, the tensile strength is improved by 9.5%, and the shear strength is improved by 10.7%; compared with the conventional SnAg1.0Cu0.5 (the Ag content is 1.0%, the Cu content is 0.5%, and the balance is Sn) silver-containing brazing filler metal, the thickness of the IMC layer is increased by 1.54%, after 1500-40-125 ℃ temperature cyclic aging treatment, the failure rate of welding spots is basically consistent, the tensile strength is improved by 1.34%, and the shear strength is reduced by 2.56%.
Comparative example of conventional process: putting the SnCu0.7 alloy block into a heating furnace, heating to 500 ℃, pressing 0.6 wt% Co and 0.6 wt% Mn nano particles into the bottom of the furnace body by using a bell jar after melting, preserving heat and stirring for 2 hours, and sampling to make a sub-analysis, wherein the Co content is 0.24 wt% and the Mn content is 0.09 wt%. In the experimental process, most of Co and Mn nano particles float on the surface of the melt and cannot be fused into the melt.
Example 3
Sn-0.1Cu-0.03Bi-0.03Ni-1Co-1Mn silver-free solder alloy is prepared by the following method:
(1) preparing Sn-0.1Cu-0.03Bi-0.03Ni alloy by using pure Sn, SnCu10, SnBi58, SnCuBiNi and SnNi4 by adopting a method in the prior art;
(2) placing the alloy prepared in the step (1) into a crucible of a vacuum intermediate frequency furnace, vacuumizing until the air pressure in the furnace is slightly larger than atmospheric pressure, heating to 600 ℃, and preserving heat for 5min to obtain Sn-0.1Cu-0.03Bi-0.03Ni melt A;
(3) carrying out reduction treatment on nano Co particles and nano Mn particles with the particle size of 80-100 nm, wherein the reduction treatment method comprises the steps of putting the nano Co particles and the nano Mn particles into a tube furnace, introducing nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 15: 1), and carrying out heat preservation for 30min at 120 ℃;
(4) and (3) filling nitrogen into the vacuum intermediate frequency furnace, and blowing the reduced 1.1 wt% of nano Co particles and 1.1 wt% of nano Mn particles into the melt A through a thin tube, wherein the gas pressure is 0.3MPa, and the nano particles are added into the melt at the speed of 0.4 g/s. When the nano Co particles and the nano Mn particles are blown into the melt A, the outlet of the thin tube is arranged at the bottom of a crucible of the vacuum intermediate frequency furnace, the mechanical stirring device is positioned in the melt, the mechanical stirring device is started from the blowing of the nano Co particles and the nano Mn particles, the heat preservation stirring is continued for 20min after the nano particles are all melted into the melt, the nano particles are uniformly distributed in the melt A, and the alloy melt containing the high-dispersity nano particles is obtained. The alloy melt is cooled along with the furnace to obtain the Sn-0.1Cu-0.03Bi-0.03Ni-1Co-1Mn silver-free solder alloy. And in the whole preparation process, the nitrogen is always introduced into the furnace, the air pressure in the furnace is kept slightly higher than the atmospheric pressure, and redundant gas is discharged through a constant pressure valve of the vacuum intermediate frequency furnace.
The brazing filler metal alloy prepared through the steps comprises 0.1% of Cu, 0.03% of Bi, 0.03% of Ni, 1.0% of Co1.0%, 1.0% of Mn and the balance of Sn.
Example 4
The Sn-1Cu-1Bi-1Ni-0.6Co-0.7Mn silver-free solder alloy is prepared by the following method:
(1) preparing Sn-1Cu-1Bi-1Ni alloy by using pure Sn, SnCu10, SnBi58, SnCuBiNi and SnNi4 by adopting a method in the prior art;
(2) putting the alloy prepared in the step (1) into a crucible of a vacuum intermediate frequency furnace, vacuumizing until the air pressure in the furnace is slightly larger than atmospheric pressure, heating to 600 ℃, and preserving heat for 5min to obtain Sn-1Cu-1Bi-1Ni melt A;
(3) carrying out reduction treatment on nano Co particles and nano Mn particles with the particle size of 80-100 nm, wherein the reduction treatment method comprises the steps of putting the nano Co particles and the nano Mn particles into a tube furnace, introducing nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 20: 1), and carrying out heat preservation for 30min at 120 ℃;
(4) and (3) filling nitrogen into the vacuum intermediate frequency furnace, and blowing the reduced nano Co particles with the weight percent of 0.7 and the nano Mn particles with the weight percent of 0.8 into the melt A through a thin tube, wherein the gas pressure is 0.3MPa, and the nano particles are added into the melt at the speed of 0.5 g/s. When the nano Co particles and the nano Mn particles are blown into the melt A, the outlet of the thin tube is arranged at the bottom of a crucible of the vacuum intermediate frequency furnace, the mechanical stirring device is positioned in the melt, the mechanical stirring device is started from the blowing of the nano Co particles and the nano Mn particles, the heat preservation stirring is continued for 25min after the nano particles are all melted into the melt, the nano particles are uniformly distributed in the melt A, and the alloy melt containing the high-dispersity nano particles is obtained. And cooling the alloy melt along with the furnace to obtain the Sn-1Cu-1Bi-1Ni-0.6Co-0.7Mn silver-free solder alloy. And in the whole preparation process, the nitrogen is always introduced into the furnace, the air pressure in the furnace is kept slightly higher than the atmospheric pressure, and redundant gas is discharged through a constant pressure valve of the vacuum intermediate frequency furnace.
The brazing filler metal alloy prepared through the steps comprises 1.0% of Cu, 1.0% of Bi, 1.0% of Ni, 0.6% of Co0.7% of Mn and the balance of Sn.
The invention utilizes the characteristic that nano particles are easy to float upwards and adopts a specific smelting method to finally obtain the high-reliability SnCuBiCoMnNi lead-free solder alloy with high dispersibility and high adding efficiency, and the product has stable quality and low preparation cost.
Claims (10)
1. The high-reliability silver-free tin-based solder is characterized by being a silver-free SnCuBiNiCoMn lead-free solder, and comprising the following components in percentage by weight: 0.1 to 1.0 wt% of Cu, 0.03 to 1.0 wt% of Bi, 0.03 to 1.0 wt% of Ni, 0.5 to 1.0 wt% of nano Co particles, 0.5 to 1.0 wt% of nano Mn particles, and the balance of Sn; wherein, part of the nanometer Co particles and the nanometer Mn particles are uniformly distributed in the lead-free solder melt in a dispersion mode.
2. The high-reliability silver-free tin-based solder according to claim 1, wherein the particle size of the Co nanoparticles and the Mn nanoparticles is 20-100 nm.
3. The method for preparing a highly reliable silver-free tin-based solder according to claim 1 or 2, comprising the steps of:
(1) putting the prepared SnCuBiNi alloy into a vacuum intermediate frequency furnace;
(2) the vacuum intermediate frequency furnace is vacuumized and then filled with nitrogen, so that the pressure in the furnace is slightly higher than the atmospheric pressure, the nitrogen is always filled in the furnace and the pressure in the furnace is kept slightly higher than the atmospheric pressure in the subsequent whole preparation process, and the redundant gas is discharged through a constant pressure valve of the vacuum intermediate frequency furnace;
(3) heating the vacuum intermediate frequency furnace to 500-600 ℃, and preserving heat for 5min to obtain a SnCuBiNi melt A;
(4) uniformly blowing the Co nanoparticles and the Mn nanoparticles into the melt A through a thin tube by using nitrogen;
keeping the electromagnetic stirring of the vacuum intermediate frequency furnace in 20min from the beginning of the step (2) to the end of blowing the nano Co particles and the nano Mn particles into the melt A, and mechanically stirring the alloy in the furnace by adopting a mechanical stirring device while keeping the electromagnetic stirring of the alloy in the furnace in the vacuum intermediate frequency furnace so as to uniformly distribute the nano particles in the melt A;
(5) and after the preparation process is finished, the alloy in the furnace is cooled along with the furnace to obtain the high-reliability silver-free tin-based solder.
4. The method for preparing a highly reliable silver-free tin-based solder according to claim 3, wherein the mechanical stirring device is inserted into the furnace from the top of the vacuum intermediate frequency furnace, and the mechanical stirring device is provided with one or more than two layers of stirring blades.
5. The preparation method of the highly reliable silver-free tin-based solder according to claim 3 or 4, characterized in that in the preparation process of the silver-free tin-based solder, a thin tube outlet for blowing in nano Co particles and nano Mn particles is arranged at the bottom of a crucible of a vacuum intermediate frequency furnace, a mechanical stirring device is arranged at the upper part of the thin tube outlet, and in the floating process of bubbles from the thin tube outlet, the nano particles are continuously stirred by the mechanical stirring action and finally melted into the melt, so that an alloy melt containing the highly dispersible nano particles is obtained.
6. The method for preparing the highly reliable silver-free tin-based solder according to claim 3 or 4, wherein when the Co nanoparticles and Mn nanoparticles are uniformly blown into the melt A through the tubules by nitrogen, the inner diameter of the tubules is 1-3 mm, the gas pressure is 0.1-0.3 MPa, and the nanoparticles are added into the melt at a speed of 0.3-0.5 g/s.
7. The method for preparing the highly reliable silver-free tin-based solder according to claim 5, wherein when the Co nanoparticles and Mn nanoparticles are uniformly blown into the melt A through a narrow tube by nitrogen, the inner diameter of the narrow tube is 1-3 mm, the gas pressure is 0.1-0.3 MPa, and the nanoparticles are added into the melt at a speed of 0.3-0.5 g/s.
8. The method for preparing the high-reliability silver-free tin-based solder according to the claim 3 or 4, wherein the raw materials for preparing the SnCuBiNi alloy are pure Sn, SnCu10, SnBi58, SnCuBiNi, SnNi4, Sn in the SnCuBiNi melt A is realized by adding pure Sn, Cu is realized by adding SnCu10, Bi is realized by adding SnBi58, and Ni is realized by adding SnNi 4.
9. The preparation method of the high-reliability silver-free tin-based solder according to claim 3 or 4, characterized in that the nanometer Co particles and the nanometer Mn particles are subjected to reduction treatment and then blown into the melt A; the reduction treatment method comprises the steps of putting the nanometer Co particles and the nanometer Mn particles into a tube furnace, introducing reducing gas, and preserving heat for a period of time.
10. The method for preparing the highly reliable silver-free tin-based solder according to claim 9, wherein the reducing gas is a mixed gas of nitrogen and hydrogen, and the volume ratio of the nitrogen to the hydrogen is (10-20): 1, the heat preservation temperature of the tube furnace is 120 ℃, and the heat preservation time is 30 min.
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| CN201911388186.1A CN111085798A (en) | 2019-12-30 | 2019-12-30 | High-reliability silver-free tin-based solder and preparation method thereof |
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| CN201911388186.1A CN111085798A (en) | 2019-12-30 | 2019-12-30 | High-reliability silver-free tin-based solder and preparation method thereof |
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| CN112453753A (en) * | 2020-11-13 | 2021-03-09 | 华北水利水电大学 | Flexible deformation brazing filler metal and automatic preparation device and preparation method thereof |
| CN116604221A (en) * | 2023-07-19 | 2023-08-18 | 长春理工大学 | Infrared detection window solder material and preparation method thereof |
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