CN112372177B - High-wettability brazing filler metal and preparation method thereof - Google Patents
High-wettability brazing filler metal and preparation method thereof Download PDFInfo
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- CN112372177B CN112372177B CN202011211060.XA CN202011211060A CN112372177B CN 112372177 B CN112372177 B CN 112372177B CN 202011211060 A CN202011211060 A CN 202011211060A CN 112372177 B CN112372177 B CN 112372177B
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- wettability
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Classifications
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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
- B23K35/264—Bi 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
Abstract
The invention relates to the technical field of brazing materials, in particular to a high-wettability brazing filler metal and a preparation method thereof. The high-wettability brazing filler metal consists of the following components in percentage by mass: 0.2 to 1 percent of Ag, 0.8 to 1.5 percent of Sb, 41 to 43 percent of Sn and the balance of Bi. The invention can ensure that the performance of other aspects of the solder system is not influenced by strictly limiting the addition amount of Sb and matching the content of other elements, and simultaneously improves the spreading coefficient and the wettability of the solder.
Description
Technical Field
The invention relates to the technical field of brazing materials, in particular to a high-wettability brazing filler metal and a preparation method thereof.
Background
The filler metal is a filler added in or beside the gap of the filler metal to realize the combination of two materials (or parts). The melting point of the solder must be lower than the melting point of the material to be soldered. The solder is divided into soft solder and hard solder according to the melting point, wherein the soft solder is the solder with the melting point lower than 450 ℃, and the hard solder is the solder with the melting point higher than 450 ℃. Generally, solder includes tin-based, lead-based, zinc-based, and the like solders; the hard solder comprises aluminum-based, silver-based, copper-based, nickel-based and the like.
The traditional tin-lead alloy solder is a widely used soft solder, the melting point can be reduced by adding lead, eutectic with the tin with the melting point of 183 ℃ is formed, the structure is totally eutectic, and the tin-lead alloy solder is widely applied to electricians. However, lead and lead compounds are toxic substances, and thus lead-free solders are the focus of research in the field.
The Sn-Bi lead-free solder has the advantages of low melting point, energy conservation, environmental protection and the like, has low melting point, can reduce the thermal damage of electronic components and substrates in the packaging process, and has important application value in the field of low-temperature lead-free soldering. When the Sn58Bi eutectic brazing filler metal is used for brazing, the connection process of a welding layer is good in air tightness, and the alloy of a linking area is uniform and has no gap.
However, the conventional Sn58 Bi-based solder has poor fluidity and poor wettability after melting, and is not favorable for production and test.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the present invention is to provide a solder with high wettability, which solves the problem of poor wettability of the Sn58 Bi-based solder in the prior art.
A second object of the present invention is to provide a method for preparing a solder with high wettability.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the high-wettability brazing filler metal consists of the following components in percentage by mass:
0.2 to 1 percent of Ag, 0.8 to 1.5 percent of Sb, 41 to 43 percent of Sn and the balance of Bi.
The invention changes the original alloy system by adding Sb into the Sn-Bi-Ag solder, and increases the wettability of the solder while ensuring the performances of other aspects of the solder system.
The invention can ensure that the performance of other aspects of the solder system is not influenced by strictly limiting the addition amount of Sb and matching the content of other elements, and simultaneously improves the spreading coefficient and the wettability of the solder.
As in the different embodiments, the mass fraction of Ag in the high wettability solder may be 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc.;
the mass fraction of Sb may be 0.8%, 0.85%, 0.9%, 0.95%, 1%, 1.05%, 1.1%, 1.15%, 1.2%, 1.25%, 1.3%, 1.35%, 1.4%, 1.45%, 1.5%, etc.;
the mass fraction of Sn may be 41%, 41.5%, 42%, 42.5%, 43%, etc.
In the high-wettability solder, the mass fraction of Bi can be 54.5-58%.
As in the different embodiments, the mass fraction of Bi in the high wettability solder may be 54.5%, 55%, 55.5%, 56%, 56.5%, 57%, 57.5%, 58%, and so on.
In a specific embodiment of the invention, the high-wettability solder consists of the following components in percentage by mass:
0.5 to 1 percent of Ag, 1 to 1.5 percent of Sb, 41.5 to 42.5 percent of Sn and the balance of Bi.
In a specific embodiment of the invention, the high-wettability solder consists of the following components in percentage by mass:
0.8 to 0.95 percent of Ag, 1.1 to 1.45 percent of Sb, 41.5 to 42.5 percent of Sn and the balance of Bi.
In a specific embodiment of the present invention, the mass percentage of Sb is 1.1% to 1.25%, more preferably 1.15% to 1.18%.
The invention also provides a preparation method of the high-wettability brazing filler metal, which comprises the following steps:
mixing and smelting Sn58Bi, an Ag simple substance and an Sb simple substance according to a proportion.
In a specific embodiment of the present invention, the method of hybrid smelting comprises: and mixing the mixture of Sn58Bi, the simple substance Ag and the simple substance Sb with molten salt, and putting the mixture into a container for smelting treatment.
In a specific embodiment of the invention, the smelting temperature is 170-190 ℃; the smelting time is 45-120 s.
In a specific embodiment of the present invention, the amount of the simple substance Sb is 0.5% to 3%, preferably 1% to 2%, such as 1.1% to 1.45%, of the sum of the masses of the simple substance Sn58Bi, ag and the simple substance Sb. The amount of the simple substance Ag accounts for 0.2-1% of the sum of the masses of the simple substances Sn58Bi, ag and Sb, preferably 0.5-1%, such as 0.8-0.95%.
Compared with the prior art, the invention has the beneficial effects that:
(1) The Sb is added into the Sn-Bi-Ag brazing filler metal, so that the original alloy system is changed, the performances of other aspects of the brazing filler metal system are ensured, and the wettability of the brazing filler metal system is improved;
(2) The preparation method of the high-wettability brazing filler metal is simple and is beneficial to industrial production.
Detailed Description
While the technical solutions of the present invention will be described clearly and completely with reference to the specific embodiments, those skilled in the art will understand that the following described examples are some, but not all, examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The high-wettability brazing filler metal consists of the following components in percentage by mass:
0.2 to 1 percent of Ag, 0.8 to 1.5 percent of Sb, 41 to 43 percent of Sn and the balance of Bi.
The invention changes the original alloy system by adding Sb into the Sn-Bi-Ag solder, and increases the wettability of the solder while ensuring the performances of other aspects of the solder system.
The invention can ensure that the performance of other aspects of the solder system is not influenced by strictly limiting the addition amount of Sb and matching the content of other elements, and simultaneously improves the spreading coefficient and the wettability of the solder.
In research, the high-wettability brazing filler metal disclosed by the invention has the advantage that as the Sb content is increased, the spreading factor of the prepared brazing filler metal tends to be increased, then reduced and finally stabilized. The reason for the increase of the spreading coefficient of the brazing filler metal is that the addition of Sb improves the fluidity of the brazing filler metal, but Ag and Sb in the liquid brazing filler metal move towards the surface along with the increase of the Sb content, and uneven areas rich in Ag and Sb are formed on the surface, so that the surface tension is increased, and the wetting capacity of the brazing filler metal is reduced. The invention adopts a specific amount of Sb and matches with other elements, thereby improving the wettability of the brazing filler metal while ensuring the other properties of the brazing filler metal.
As in the different embodiments, the mass fraction of Ag in the high wettability solder may be 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc.; the mass fraction of Sb may be 0.8%, 0.85%, 0.9%, 0.95%, 1%, 1.05%, 1.1%, 1.15%, 1.2%, 1.25%, 1.3%, 1.35%, 1.4%, 1.45%, 1.5%, etc.; the mass fraction of Sn may be 41%, 41.5%, 42%, 42.5%, 43%, etc. In the high-wettability solder, the mass fraction of Bi can be 54.5-58%. As in the different embodiments, the mass fraction of Bi in the high wettability solder may be 54.5%, 55%, 55.5%, 56%, 56.5%, 57%, 57.5%, 58%, and so on.
In a specific embodiment of the invention, the high-wettability solder consists of the following components in percentage by mass:
0.5 to 1 percent of Ag, 1 to 1.5 percent of Sb, 41.5 to 42.5 percent of Sn and the balance of Bi.
In a specific embodiment of the invention, the high-wettability solder consists of the following components in percentage by mass:
0.8 to 0.95 percent of Ag, 1.1 to 1.45 percent of Sb, 41.5 to 42.5 percent of Sn and the balance of Bi.
The invention also provides a preparation method of the high-wettability brazing filler metal, which comprises the following steps:
mixing and smelting Sn58Bi, ag simple substance and Sb simple substance according to a proportion. The proportion refers to that the high-wettability brazing filler metal is prepared according to the preset components of the high-wettability brazing filler metal, and the components are prepared according to the mass percentage of 0.2% -1% of Ag, 0.8% -1.5% of Sb, 41% -43% of Sn and the balance of Bi.
In practical operation, the purity of the Ag simple substance and the Sb simple substance is preferably more than or equal to 99.99wt%.
In a specific embodiment of the present invention, the method of hybrid smelting comprises: and mixing the mixture of Sn58Bi, the simple substance Ag and the simple substance Sb with molten salt, and putting the mixture into a container for smelting treatment.
In a specific embodiment of the invention, the smelting temperature is 170-190 ℃; the smelting time is 45-120 s.
As in various embodiments, the temperature of the melting may be 170 ℃, 175 ℃,180 ℃, 185 ℃, 190 ℃, etc.; the time of the melting may be 45s, 50s, 55s, 60s, 65s, 70s, 75s, 80s, 85s, 90s, 95s, 100s, 105s, 110s, 115s, 120s, and the like.
In a preferred embodiment of the invention, the temperature of the smelting is 180 ℃, and the holding time of the smelting is 60s.
In actual operation, a mixture of Sn58Bi, ag and Sb can be uniformly mixed with molten salt and placed in a crucible, the crucible is heated, for example, placed on an aluminum plate for heating and smelting, and the temperature is kept at 180 ℃ for 60s; and pouring the smelted material into a stainless steel mold, and performing air cooling treatment to obtain the high-wettability brazing filler metal. The molten salt is inorganic molten salt.
In a specific embodiment of the present invention, the mass ratio of the mixture of the Sn58Bi, the simple substance Ag, and the simple substance Sb to the inorganic molten salt may be 8: 2. The inorganic molten salt can be conventional inorganic molten salt.
In a specific embodiment of the invention, the amount of the simple substance Sb is 0.8% to 1.5%, preferably 1% to 1.5%, of the sum of the masses of the simple substance Sn58Bi, ag and the simple substance Sb. The dosage of the Ag simple substance accounts for 0.2-1 percent of the mass sum of the Sn58Bi, the Ag simple substance and the Sb simple substance, and is preferably 0.5-1 percent.
As in various embodiments, the amount of elemental Sb may comprise 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, etc. of the sum of the masses of elemental Sn58Bi, ag, and elemental Sb.
As in various embodiments, the amount of the simple substance Ag may account for 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1% of the mass sum of the Sn58Bi, the simple substance Ag, and the simple substance Sb.
In the specific embodiment of the invention, the smelting components of the high-wettability solder comprise, by mass, 0.80-0.95% of Ag, 1.10-1.45% of Sb, 42.0-42.5% of Sn and 55.0-56.0% of Bi, and preferably comprise 0.81-0.93% of Ag, 1.16-1.45% of Sb, 42.28-42.35% of Sn and 55.34-55.68% of Bi.
Examples 1 to 2
The formulation information of the high wettability solders of examples 1-2 is shown in table 1.
TABLE 1 raw materials for solder with different high wettability
The preparation method of the high-wettability brazing filler metal in the embodiment 1 comprises the following steps: weighing Sn58Bi, an Ag simple substance and an Sb simple substance, and mixing to obtain a mixture, wherein the using amount of the Ag simple substance accounts for 1% of the mass of the mixture, and the using amount of the Sb simple substance accounts for 1% of the mass of the mixture;
the compounding method of the high-wettability solder of example 2 includes: weighing Sn58Bi, an Ag simple substance and an Sb simple substance, and mixing to obtain a mixture, wherein the using amount of the Ag simple substance accounts for 1% of the mass of the mixture, and the using amount of the Sb simple substance accounts for 1.5% of the mass of the mixture.
The method for preparing the high wettability solder of example 1-2 includes the steps of:
(1) Preparing materials according to the respective proportion of the above embodiment;
(2) Mixing the raw material mixture obtained by batching in the step (1) with inorganic molten salt (potassium chloride and lithium chloride are mixed according to the mass ratio of 1.3: 1) according to the mass ratio of 8: 2, placing the mixture in a crucible, placing the crucible on an aluminum plate, heating and smelting the mixture to 180 ℃, and keeping the temperature for 60s; and then pouring the smelted materials into a stainless steel mold, and air-cooling to obtain the high-wettability brazing filler metal.
The melting compositions of the solder having high wettability in examples 1 to 2 are shown in Table 2.
TABLE 2 melting composition of solder with different high wettability
Comparative examples 1 to 2
The brazing filler metals of comparative examples 1-2 were Sn58Bi-1Ag and Sn58Bi-1Ag2Sb, respectively, and the melting compositions thereof are shown in Table 3. Preparation method of solder of comparative examples 1-2 reference is made to the preparation method of examples 1-2.
TABLE 3 melting composition of solder of comparative example 1
Experimental example 1
The solder of examples 1-2 and comparative examples 1-2 were subjected to spreading test in accordance with GB/T11364-2008 solder wettability test method. The base material is 99.99% pure Cu plate with size of 10.0 × 10.0 × 1.0mm. Firstly, polishing a copper sheet by 1000# and 3000# abrasive paper until the surface processing trace and oxide skin disappear and the trace is uniform, and then soaking the copper sheet in alcohol, cleaning in ultrasonic waves and drying. Solder balls made of the solders of examples 1 to 2 and comparative examples 1 to 2 were placed in the center of a Cu sheet, and a rosin-based solder was coated on the solder balls using a needleless syringe, to obtain samples corresponding to examples 1 to 3 and comparative example 1.
Selecting the brazing temperature of 180 ℃, heating the sample by using a 202-OAB type electrothermal constant-temperature drying oven, firstly heating the drying oven to 180 ℃, opening the oven door to quickly place the sample after the temperature is stabilized, keeping the temperature for 30s after the temperature is raised to 180 ℃ again, taking out the sample and cooling the sample by air. And after cooling the sample, soaking the sample in alcohol for ultrasonic cleaning to remove residual soldering flux on the surface. The thickness of the solder was measured using a micrometer and the spreading factor was calculated, the results are shown in table 4.
TABLE 4 spreading factor of different solders
| Numbering | Solder numbering | Spreading factor (%) |
| Example 1 | SBA-1Sb | 57 |
| Example 2 | SBA-1.5Sb | 55.63 |
| Comparative example 1 | SB-1Ag | 55.89 |
| Comparative example 2 | SBA-2Sb | 55.24 |
Through analysis of test data, when the using amount of the Sb element is controlled within a certain mass fraction range, the wettability of the original brazing filler metal is improved, and when the mass fraction of the added Sb element is about 1% and less than 1.5%, the effect of improving the wettability is optimal.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. The high-wettability brazing filler metal is characterized by comprising the following components in percentage by mass:
0.8-0.95% of Ag, 1.15-1.18% of Sb, 41.5-42.5% of Sn and the balance of Bi.
2. The method for preparing a solder with high wettability according to claim 1, comprising the steps of:
mixing and smelting Sn58Bi, an Ag simple substance and an Sb simple substance according to a proportion.
3. The method for preparing the high-wettability solder according to claim 2, wherein the hybrid melting method comprises: and mixing the mixture of Sn58Bi, the simple substance Ag and the simple substance Sb with molten salt, and putting the mixture into a container for smelting treatment.
4. The method for preparing the high-wettability solder according to claim 3, wherein the melting temperature is 170 to 190 ℃; the smelting time is 45 to 120s.
5. The preparation method of the high-wettability solder according to claim 3, wherein the material after the mixed melting is poured into a mold and subjected to air cooling treatment to obtain the high-wettability solder.
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| CN114012303A (en) * | 2021-10-28 | 2022-02-08 | 宁波佳明金属制品有限公司 | Low-temperature solder and preparation method thereof |
| CN114850725B (en) * | 2022-05-24 | 2024-04-26 | 雅拓莱焊接科技（惠州）有限公司 | Ultrathin tin-bismuth system preformed welding ring and preparation process thereof |
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| CN101844280A (en) * | 2010-02-08 | 2010-09-29 | 岳阳金正电子材料有限公司 | Tin-bismuth solder with low melting point and preparation method thereof |
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| CN106216872B (en) * | 2016-08-11 | 2019-03-12 | 北京康普锡威科技有限公司 | A kind of SnBiSb series low-temperature leadless solder and preparation method thereof |
| CN107825005A (en) * | 2017-12-12 | 2018-03-23 | 云南锡业锡材有限公司 | A kind of low temperature solder(ing) paste and preparation method thereof |
| CN107999995A (en) * | 2017-12-12 | 2018-05-08 | 云南锡业锡材有限公司 | Solder stick and its preparation process for low-temperature welding |
| CN108526748A (en) * | 2018-03-28 | 2018-09-14 | 云南锡业锡材有限公司 | A kind of SnBiAgSbIn low temperature lead-free solder alloys |
| WO2020047481A1 (en) * | 2018-08-31 | 2020-03-05 | Indium Corporation | Snbi and snin solder alloys |
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| CN101844280A (en) * | 2010-02-08 | 2010-09-29 | 岳阳金正电子材料有限公司 | Tin-bismuth solder with low melting point and preparation method thereof |
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| Sn-0.3Ag-0.7Cu-xSb无铅钎料润湿性;张亮等;《焊接学报》;20150125(第01期);第60页右栏2.1 Sb元素部分第1段 * |
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