CN121551906A - Lead-free tin-based solder alloy with high entropy phase, preparation method thereof and special smelting equipment - Google Patents

Lead-free tin-based solder alloy with high entropy phase, preparation method thereof and special smelting equipment

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Publication number
CN121551906A
CN121551906A CN202511987667.XA CN202511987667A CN121551906A CN 121551906 A CN121551906 A CN 121551906A CN 202511987667 A CN202511987667 A CN 202511987667A CN 121551906 A CN121551906 A CN 121551906A
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CN
China
Prior art keywords
lead
solder alloy
based solder
free tin
smelting
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202511987667.XA
Other languages
Chinese (zh)
Inventor
杭春进
李宣
关旗龙
王睿琦
白睿
孔硕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology Shenzhen
Original Assignee
Harbin Institute of Technology Shenzhen
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Filing date
Publication date
Application filed by Harbin Institute of Technology Shenzhen filed Critical Harbin Institute of Technology Shenzhen
Priority to CN202511987667.XA priority Critical patent/CN121551906A/en
Publication of CN121551906A publication Critical patent/CN121551906A/en
Pending legal-status Critical Current

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Classifications

    • 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°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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/06—Alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/08—Apparatus
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/003—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals by induction
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/006—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with use of an inert protective material including the use of an inert gas
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/04—Refining by applying a vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

The invention provides a lead-free tin-based solder alloy with a high entropy phase, a preparation method thereof and special smelting equipment, and belongs to the technical field of welding material preparation. The alloy comprises, by atomic percentage, 10% -25% of Zn, 15% -25% of Bi, 5% -20% of In, 5% -15% of Cu and the balance of Sn. The dedicated smelting plant includes a smelting vessel assembly and an auxiliary plant assembly. The preparation method comprises the steps of placing all the components into the special smelting equipment, vacuumizing, injecting inert gas for induction smelting, cooling to obtain an ingot, smelting the ingot again under the same condition, and rapidly cooling the obtained melt to obtain the brazing filler metal alloy. The solder alloy prepared by the invention not only has unique high entropy phase, but also has the advantages of low melting point, high toughness and good wettability, can inhibit the growth of interfacial intermetallic compounds, and is suitable for welding heat-sensitive materials and electronic devices.

Description

Lead-free tin-based solder alloy with high entropy phase, preparation method thereof and special smelting equipment
Technical Field
The invention belongs to the technical field of welding material preparation, and particularly relates to a lead-free tin-based solder alloy with a high entropy phase, a preparation method thereof and special smelting equipment.
Background
With the progress of global electronic packaging industry in green, the use of conventional lead-containing solders has been strictly limited by regulations such as the european union RoHS (directive on the use of certain harmful substances in electric and electronic devices) due to environmental toxicity problems. Although the current mainstream lead-free solder system such as Sn-Ag-Cu (SAC) alloy can meet the conventional packaging requirement, the conventional Sn-based alloy still has a remarkable technical bottleneck in the field of low-temperature micro-connection, and the conventional Sn-based alloy is easy to cause atom directional migration due to the thermal-electric coupling effect in the long-term service process, so that an intermetallic compound (IMC) layer of a welding spot interface is abnormally thickened and grows as whiskers, and the mechanical reliability and the conductive stability of a device are remarkably reduced. In the emerging low-temperature packaging scenes of flexible electronics, biomedical devices and the like, the existing solder is easy to damage a heat sensitive substrate due to the fact that the melting point is higher (180 ℃), so that the failure risk of the electronics is greatly improved.
Currently, low temperature solder development focuses on binary alloy systems (e.g., sn-Bi, sn-In, etc.), improving wettability by micro doping. However, the single main element solder cannot give consideration to the toughness of the material, and the breakthrough improvement of the comprehensive performance is restricted. In recent years, the design concept of multi-principal element alloy (including high-entropy alloy, medium-entropy alloy and the like) based on multi-principal element synergistic effect provides a new direction for solder innovation. The peculiar lattice distortion effect of the multi-principal element alloy can obviously prevent the migration and diffusion of atoms, improve the toughness of the brazing filler metal, and the cocktail effect is beneficial to optimizing the morphology regulation of interface IMC. However, since most of the elements have limited solid solubility in tin matrix, the phases (e.g., inSn 4, etc.) in the existing multi-principal element tin-based solders contain only 2 to 3 elements, and a high-entropy solid solution phase containing 5 elements cannot be formed in the solder to fully exert the characteristics of the high-entropy alloy. Therefore, the multi-principal element lead-free tin-based solder alloy which can realize excellent welding performance under the low-temperature condition and has high entropy strengthening effect is developed, and has important technical significance and application value for meeting urgent requirements of high-performance and low-temperature sensitive welding materials in the electronic packaging industry.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a lead-free tin-based solder alloy with a high entropy phase, a preparation method thereof and special smelting equipment. Aiming at the technical problems of high melting point, insufficient mechanical property of welding spots, difficult effective inhibition of interface diffusion, insufficient long-term stability of welding spots and the like of the existing low-temperature solder, the invention provides the multi-element low-temperature solder containing high entropy phase, which realizes the cooperative promotion of the strength and toughness of the solder through multi-principal element cooperative effect, inhibits the generation of brittle intermetallic compounds of a welding interface, reduces the diffusion rate of interface atoms and ensures the long-term service stability of a microelectronic packaging structure under the thermal-mechanical coupling load.
In order to achieve the above purpose, the present invention provides the following technical solutions:
one of the technical schemes of the invention is as follows:
the invention provides a lead-free tin-based solder alloy with a high entropy phase, which takes Sn, any one or two of Bi or In as main elements, and any two or three of Ni, mn, ag, cu and Zn as the rest elements.
Further, sn in the lead-free tin-based solder alloy is an essential element, and the lead-free tin-based solder alloy comprises five elements;
The mixing entropy of the lead-free tin-based solder alloy is more than or equal to 1.4R, R is an ideal gas constant, and the numerical value is 8.314J/(mol.K).
Further, the lead-free tin-based solder alloy takes Sn, bi and In as main elements, and the rest elements comprise Cu and Zn.
Further, the lead-free tin-based solder alloy comprises, by atomic percentage, 10% -25% of Zn, 15% -25% of Bi, 5% -20% of In, 5% -15% of Cu and the balance of Sn.
Further, the atomic percentage of Sn is more than or equal to 30%;
The total atomic percentage of the main elements is more than or equal to 60 percent.
Still more preferably, the lead-free tin-based solder alloy comprises, in atomic percent, 16% Zn, 24% Bi, 10% In, 10% Cu, 40% Sn;
the lead-free tin-based solder alloy comprises 18 atomic percent of Zn, 25 atomic percent of Bi, 12 atomic percent of In, 10 atomic percent of Cu and 35 atomic percent of Sn;
The lead-free tin-based solder alloy comprises 20 atomic percent of Zn, 25 atomic percent of Bi, 15 atomic percent of In, 10 atomic percent of Cu and 30 atomic percent of Sn;
the lead-free tin-based solder alloy comprises 10% of Zn, 25% of Bi, 15% of In, 10% of Cu and 40% of Sn In atomic percentage.
The invention also provides special smelting equipment for the lead-free tin-based solder alloy with the high entropy phase, wherein the special smelting equipment comprises a smelting container assembly and an auxiliary equipment assembly;
The smelting container assembly comprises a special container, the top of the special container is connected with a sealing device, the top of the sealing device is connected with a stirring rod, the stirring rod penetrates through the sealing device to extend into the special container, and the stirring rod is connected with a miniature motor;
The auxiliary equipment assembly comprises a motor fixing frame, a quick lifting device, a vacuum air channel, an exhaust pipeline and an inert gas input air channel, wherein one end of the motor fixing frame is connected with the quick lifting device, the other end of the motor fixing frame is connected with the miniature motor, the vacuum air channel, the exhaust pipeline and the inert gas input air channel are connected with the sealing device through quick connecting flanges, and the other end of the vacuum air channel is connected with an external 20-40L oil-free negative pressure vacuum pump.
Further, the quick lifting device comprises a main body support, a connecting sliding rail, a hand wheel operating part and a test tube fixing frame, wherein the motor fixing frame is connected with the main body support, the hand wheel operating part is fixedly connected to the main body support, the main body support is in transmission connection with the connecting sliding rail through gear meshing, the hand wheel operating part is in transmission connection with the connecting sliding rail, the test tube fixing frame is fixedly connected to the connecting sliding rail and is in sliding connection with the main body support through the connecting sliding rail, and a screw rod in the connecting sliding rail is driven to rotate through rotating the hand wheel operating part, so that the test tube fixing frame is driven to move up and down, and quick and accurate lifting of a smelting container assembly is realized.
Further, the stirring rod is a special ceramic stirring rod.
The sealing device adopts a double sealing structure, wherein the lower sealing is realized by matching a quick-connection flange joint with a high-temperature-resistant rubber ring, and the upper sealing adopts a high-elasticity sealing rubber plug;
The auxiliary equipment assembly further comprises an induction coil, a cooling liquid container, a pressure relief valve and a switching valve, wherein the induction coil is sleeved on the periphery of the special container, the cooling liquid container is arranged below the special container, an ice water mixture/liquid nitrogen is filled as a cooling medium, the pressure relief valve is arranged on the exhaust pipeline, and the switching valve is arranged on the vacuum gas circuit, the exhaust pipeline and the inert gas input pipeline.
Further, the high-temperature resistant rubber ring is resistant to high temperature of 100-150 ℃;
The induction coil is connected with an external intermediate frequency induction heater, and the power of the intermediate frequency induction heater is 10-35 kw;
the pressure relief valve is preferably a 0.1-0.6 MPa pressure relief valve;
The trait container is preferably a quartz container.
Further, the working method of the special smelting equipment comprises the steps of closing a switch valve before smelting, vacuumizing the special container to 0.03 MPa by using an external vacuum pump, opening an external gas cylinder filled with inert gas, injecting the inert gas from an inert gas input gas channel, opening an exhaust gas channel switch valve, and filling the cavity of the special container with the inert gas through the adjustment of a pressure release valve; and when cooling is needed, the special container is quickly lowered by the quick lifting device, so that the stirring rod is separated from the alloy solution on the one hand, and the special container is quickly immersed into a cooling medium on the other hand, thereby realizing quick cooling.
The invention also provides a preparation method of the lead-free tin-based solder alloy with high entropy phase, which comprises the following steps:
(1) Placing the components into special smelting equipment according to claim 5, vacuumizing, injecting inert gas for induction smelting, and standing and cooling to obtain cast ingots;
(2) Placing the cast ingot into the special smelting equipment according to claim 5, vacuumizing, injecting inert gas for remelting, and rapidly cooling the obtained melt to obtain the lead-free tin-based solder alloy.
Further, in the induction smelting process in step (1), a micro-positive pressure environment in the special container needs to be maintained, so as to avoid rapid evaporation of part of metal due to great reduction of vapor pressure in a vacuum environment.
Further, the temperature of the induction smelting in the step (1) is 600-700 ℃ and the time is 6-9 min. Ensure that various metals are thoroughly melted, and obtain cast ingots after standing and cooling at room temperature, if the temperature is higher than 700 ℃, a large amount of evaporation loss of Zn element can be caused in the smelting process.
Further, the remelting temperature in the step (2) is 300-600 ℃ and the time is 8-10 min, the melting point of the alloy in the secondary smelting is greatly lower than that of the initial raw material, the alloy can be melted at a lower temperature, and the lower smelting temperature is used for avoiding the evaporation loss of part of elements in the heating process and reducing the energy loss.
The remelting is carried out under high-speed stirring, the rotating speed of the high-speed stirring is 300 rpm, and a motor is started to stir in the heating process, so that the melt in the container is fully and uniformly mixed;
the rapid cooling is performed by immersing the trait container containing the melt in an ice-water mixture or liquid nitrogen, preferably an ice-water mixture.
Further, when the ice-water mixture is adopted for cooling, the temperature of the cooling liquid is 0 ℃, the cooling liquid is separated from the container after the alloy is contracted, the alloy is conveniently taken out, and the method is preferred;
when the liquid nitrogen is adopted for cooling, the temperature of the cooling liquid is-196 ℃, and the cooling liquid is separated from the special container after the alloy is shrunk, so that the alloy is conveniently taken out.
Further, the inert gases are nitrogen or argon;
vacuumizing to 0.03 MPa;
the components in the step (1) are solid particles or solid powder.
Compared with the prior art, the invention has the beneficial effects that:
The invention provides a lead-free and nontoxic high-entropy solder alloy, which can meet the welding requirement of daily electronic products and completely meet the RoHS environmental protection regulations. According to the invention, by precisely controlling the components of the brazing filler metal and combining uniform stirring and ultra-high-speed cooling processes, the brazing filler metal with a high-entropy solid solution phase, which mainly contains Sn, bi, in and other low-melting-point elements and is assisted by Cu, ni, ag and other high-melting-point elements, is obtained. Compared with other high-entropy alloy solders, the design strategy of the invention selects elements without lead and toxicity, meets RoHS requirements, and obtains specific five-membered high-entropy phases in the solders on the premise of ensuring high mixed entropy by precisely controlling the proportion of main elements and optimizing the preparation method, thereby realizing multiphase coupling of intermetallic compounds, traditional solid solution phases and high-entropy solid solution phases and improving the toughness of the solders. Compared with the traditional SnBi or SnAgCu solder, the invention adopts low-melting-point elements such as Sn, bi, in and the like to form a eutectic structure, thereby effectively reducing the melting point of the solder and being more suitable for a low-temperature welding scene. Meanwhile, the strengthening phases with different sizes and hardness are formed by the synergistic effect of multiple principal components, so that the toughness of the brazing filler metal is remarkably improved.
The multi-element system of the brazing alloy has remarkable inhibition effect on Cu element diffusion and interface nucleation in the brazing process, reduces the interface diffusion speed, effectively inhibits excessive growth of interface IMC, reduces the thickness of the IMC, keeps the high-entropy solid solution phase stable in the use process, improves the bearing capacity of the brazing alloy, comprehensively realizes low melting point, high strength and good interface stability of the brazing alloy, and remarkably improves the high-temperature performance and long-term service reliability of a brazing joint.
The lead-free tin-based solder alloy with the high entropy phase has remarkable advantages in the aspect of industrialized application, the selected Sn, bi, in, zn and other elements are all conventional metal raw materials in the field of electronic packaging, the supply chain is mature and stable, the cost is controllable, and the designed preparation device has the characteristics of low cost, rich functions and the like, so that the large equipment investment required by the traditional vacuum melting is avoided. The prepared solder has very low melting point and good wettability, can realize good connection with a substrate after reflow at a lower temperature, and is particularly suitable for welding application of heat-sensitive materials and electronic devices.
The special smelting equipment has the advantages of simple structure, convenient operation and low cost, and can realize good smelting effect without using a complicated and expensive vacuum smelting furnace. The equipment can effectively solve the technical problem that a common smelting device cannot realize full stirring by being matched with an accurate sealing system through a unique quick lifting mechanism, is particularly suitable for smelting various low-melting-point alloys, and has good universality.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of the overall structure of a special melting apparatus for a lead-free tin-based solder alloy according to example 1 of the present invention;
Fig. 2 is a schematic structural diagram of a rapid lifting device of a special smelting apparatus for a lead-free tin-based solder alloy according to embodiment 1 of the present invention;
FIG. 3 is a schematic view of the structure of the melting vessel assembly of the special melting apparatus for the lead-free tin-based solder alloy of example 1 of the present invention;
In the figures 1-3, 1, a motor fixing frame, 2, a quick lifting device, 3, a cooling liquid container, 4, an exhaust pipeline, 5, a pressure release valve, 6, a switching valve, 7, a vacuum gas passage, 8, an inert gas input gas passage, 9, a hand wheel operation part, 10, a main body bracket, 11, a test tube fixing frame, 12, a connecting sliding rail, 13, a micro motor, 14, an induction coil, 15, a special container, 16, a quick connection flange, 17, a high temperature resistant rubber ring, 18, a sealing rubber plug, 19 and a stirring rod;
FIG. 4 is a Differential Scanning Calorimeter (DSC) graph of a lead-free tin-based solder alloy prepared in example 2 of the present invention;
FIG. 5 is a weld interface microstructure of a lead-free tin-based solder alloy joint prepared in example 2 of the present invention, where a is a weld interface microstructure of weld 2 min at 180℃and b is a weld interface microstructure of weld 3min at 180 ℃;
FIG. 6 is a microstructure of the solder alloy joints of the lead-free tin-based solder prepared in example 2 of the present invention after heat aging of 0h, 50 h, and 100 h;
FIG. 7 is a line graph of the interface EDS of the solder alloy solder joint of the lead-free tin-based solder prepared in example 2 of the present invention when heat aged by 100 h, wherein a is the position of the welding interface where the line scan is located, b is the enlarged view of the line scan area, and c is the element content change graph of the line scan;
FIG. 8 is a graph (a) showing the point scan of the interfacial EDS and a graph (b) showing the analysis of the EDS component of the interfacial structure of the lead-free tin-based solder alloy prepared in example 2 according to the present invention when the solder is heat aged by 100 h;
FIG. 9 is a BSE diagram of the lead-free tin-based solder alloy prepared in example 2 of the present invention, wherein a is the BSE diagram of the whole alloy and b is the enlarged diagram at the high entropy phase position;
FIG. 10 is a high entropy phase internal point EDS diagram (a) and a composition analysis diagram (b) of the lead-free tin-based solder alloy prepared in example 2 of the present invention;
FIG. 11 is an XRD pattern of the lead-free tin-based solder alloy prepared in example 2 of the present invention;
FIG. 12 is a drawing showing the tensile properties of the lead-free tin-based solder alloy prepared in example 2 of the present invention;
Fig. 13 is a SEM image of a welded cross-section of the lead-free tin-based solder alloy prepared in example 2 of the present invention under the condition that the welding temperature is 180 ℃ and the welding time is 150 s.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The room temperature in the examples of the invention below is 23.+ -. 2 ℃.
Example 1
A special smelting apparatus for a lead-free tin-based solder alloy having a high entropy phase, as shown in fig. 1-3, includes a smelting vessel assembly and an auxiliary equipment assembly;
Wherein, the smelting container assembly comprises a special container (15), the top of the special container (15) is connected with a sealing device, the top of the sealing device is connected with a stirring rod (19), the stirring rod (19) penetrates through the sealing device to extend into the special container (15), and the stirring rod (19) is connected with a miniature motor (13);
The sealing device adopts a double sealing structure, wherein the lower sealing is realized by matching a joint of a quick-connection flange (16) with a high-temperature-resistant rubber ring (17), the upper sealing adopts a high-elasticity sealing rubber plug (18), a stirring rod inserting hole, an exhaust pipeline hole, a vacuum gas pipeline hole and an inert gas input gas pipeline hole are arranged on the sealing rubber plug (18), and corresponding pipelines and stirring rods (19) are inserted through corresponding hole positions, and the pipelines adopt hoses with steel wire supports;
the auxiliary equipment assembly comprises a motor fixing frame (1), a quick lifting device (2), a vacuum gas circuit (7), an exhaust pipeline (4), an inert gas input gas circuit (8), an induction coil (14), a cooling liquid container (3), a pressure release valve (5) and a switch valve (6);
The quick lifting device comprises a main body support (10), a connecting sliding rail (12), a hand wheel operating part (9) and a test tube fixing frame (11), wherein one end of a motor fixing frame (1) is connected with the main body support (10), the other end of the motor fixing frame is connected with a miniature motor (13), the hand wheel operating part (9) is fixedly connected to the main body support (10), the main body support (10) is in transmission connection with the connecting sliding rail (12) through gear engagement, the hand wheel operating part (9) is in transmission connection with the connecting sliding rail (12), the test tube fixing frame (11) is fixedly connected to the connecting sliding rail (12) and is in sliding connection with the main body support (10) through the connecting sliding rail (12), and a screw rod in the connecting sliding rail (12) is driven to rotate through rotating the hand wheel operating part (9), so that the test tube fixing frame (11) is driven to move up and down, and quick and accurate lifting of a smelting container assembly is realized;
One end of the vacuum gas path (7) is connected with a vacuum gas path hole on the sealing rubber plug (18) through a quick connection flange (16), the other end of the vacuum gas path (7) is connected with an external 20-40L oil-free negative pressure vacuum pump, the vacuum gas path (7) is also provided with a switch valve (6), the exhaust pipeline (4) is also connected with an exhaust pipeline hole on the sealing rubber plug (18) through the quick connection flange (16), the exhaust pipeline (4) is also provided with a pressure release valve (5) and a switch valve (6), the inert gas input gas path (8) is also connected with an inert gas input gas path hole on the sealing rubber plug (18) through the quick connection flange (16), and the inert gas input gas path (8) is also provided with the switch valve (6);
The induction coil (14) is sleeved on the periphery of the special container (15) and is connected with an external medium-frequency induction heater, the cooling liquid container (3) is arranged below the special container (15), and an ice-water mixture is filled as a cooling medium.
Example 2
A preparation method of a lead-free tin-based solder alloy with a high entropy phase comprises the following steps:
(1) The components of 10 atomic percent of Zn, 25 atomic percent of Bi, 15 atomic percent of In, 10 atomic percent of Cu and 40 atomic percent of Sn are respectively weighed.
(2) Placing the solid particles of the components into special smelting equipment in the embodiment 1, vacuumizing a quartz container to 0.03 MPa, injecting nitrogen, maintaining a micro-positive pressure environment in the quartz container, performing induction smelting under the protection of nitrogen gas, wherein the smelting temperature is 650 ℃, the smelting time is 8 min, and cooling to obtain an ingot.
(3) Placing the cast ingot into special smelting equipment in the embodiment 1, vacuumizing a quartz container to 0.03 MPa, injecting nitrogen, maintaining a micro-positive pressure environment in the quartz container, smelting again under the protection of nitrogen gas, wherein the smelting temperature is 400 ℃ and the time is 10min, fully melting, inserting a ceramic stirring rod into the melt during smelting, and rotating and stirring at a high speed of 300 rpm to realize the fully and uniform mixing of the melt in the quartz container.
(4) And (3) pulling out the ceramic stirring rod, immersing the quartz container into cooling liquid in an ice-water mixture, rapidly cooling the solder alloy at 0 ℃, separating the solder alloy from the container after cooling and shrinking, and taking out the solder alloy from the container when the temperature is restored to room temperature, thereby obtaining the lead-free tin-based solder alloy, wherein the overall mixing entropy of the alloy is 1.46R. The thermal effect of the melt with temperature change was analyzed by Differential Scanning Calorimetry (DSC) during melting, and the thermal analysis graph is shown in fig. 4, and it can be seen from fig. 4 that the melting peak temperatures of the components of the solder alloy in the present invention are 81.5 ℃ and 92.3 ℃, so that the melting point of the solder alloy in the present invention is low.
Example 3
A preparation method of a lead-free tin-based solder alloy with a high entropy phase comprises the following steps:
(1) The components of 16% of Zn, 24% of Bi, 10% of In, 10% of Cu and 40% of Sn are respectively weighed.
(2) Placing the solid particles of the components into special smelting equipment in the embodiment 1, vacuumizing a quartz container to 0.03 MPa, injecting nitrogen, maintaining a micro-positive pressure environment in the quartz container, performing induction smelting under the protection of nitrogen gas, wherein the smelting temperature is 600 ℃, the time is 8 min, and cooling to obtain an ingot.
(3) Placing the cast ingot into special smelting equipment in the embodiment 1, vacuumizing a quartz container to 0.03 MPa, injecting nitrogen, maintaining a micro-positive pressure environment in the quartz container, smelting again under the protection of nitrogen gas, wherein the smelting temperature is 500 ℃ and the time is 10min, fully melting, inserting a ceramic stirring rod into the melt during smelting, and rotating and stirring at a high speed of 300 rpm to realize the fully and uniform mixing of the melt in the quartz container.
(4) And (3) pulling out the ceramic stirring rod, immersing the quartz container into cooling liquid of an ice-water mixture, rapidly cooling the solder alloy at 0 ℃, separating the solder alloy from the container after cooling and shrinking, and taking out the solder alloy from the container when the temperature is restored to room temperature, thereby obtaining the lead-free tin-based solder alloy, wherein the overall mixing entropy of the alloy is 1.46R.
Example 4
A preparation method of a lead-free tin-based solder alloy with a high entropy phase comprises the following steps:
(1) The components of 18% of Zn, 25% of Bi, 12% of In, 10% of Cu and 35% of Sn are respectively weighed.
(2) Placing the solid powder of the components into special smelting equipment in the embodiment 1, vacuumizing a quartz container to 0.03 MPa, injecting argon, maintaining a micro-positive pressure environment in the quartz container, performing induction smelting under the protection of argon gas, wherein the smelting temperature is 700 ℃, the smelting time is 8 min, and cooling to obtain an ingot.
(3) Placing the cast ingot into special smelting equipment in the embodiment 1, vacuumizing a quartz container to 0.03 MPa, injecting argon, keeping a micro-positive pressure environment in the quartz container, smelting again under the protection of argon gas, wherein the smelting temperature is 400 ℃ and the time is 10min, fully melting the cast ingot, inserting a ceramic stirring rod into a melt during smelting, and rotating and stirring at a high speed of 300 rpm to realize fully and uniformly mixing of the melt in the quartz container.
(4) And (3) pulling out the ceramic stirring rod, immersing the quartz container into cooling liquid of an ice-water mixture, rapidly cooling the solder alloy at 0 ℃, separating the solder alloy from the container after cooling and shrinking, and taking out the solder alloy from the container when the temperature is restored to room temperature, thereby obtaining the lead-free tin-based solder alloy, wherein the overall mixing entropy of the alloy is 1.51R.
Example 5
A preparation method of a lead-free tin-based solder alloy with a high entropy phase comprises the following steps:
(1) The components of 20% of Zn, 25% of Bi, 15% of In, 10% of Cu and 30% of Sn are respectively weighed.
(2) Placing the solid particles of the components into special smelting equipment in the embodiment 1, vacuumizing a quartz container to 0.03 MPa, injecting argon, maintaining a micro-positive pressure environment in the quartz container, performing induction smelting under the protection of argon gas, wherein the smelting temperature is 680 ℃ and the time is 7 min, and cooling to obtain an ingot.
(3) Placing the cast ingot into special smelting equipment in the embodiment 1, vacuumizing a quartz container to 0.03 MPa, injecting argon, keeping a micro-positive pressure environment in the quartz container, smelting again under the protection of argon gas, wherein the smelting temperature is 450 ℃ and the time is 10min, fully melting the cast ingot, inserting a ceramic stirring rod into the melt during smelting, and rotating and stirring at a high speed of 300 rpm to realize fully and uniformly mixing of the melt in the quartz container.
(4) And (3) pulling out the ceramic stirring rod, immersing the quartz container into liquid nitrogen, rapidly cooling the solder alloy at 0 ℃, separating the solder alloy from the container after cooling and shrinking, and taking out the solder alloy from the container when the temperature is restored to room temperature, thereby obtaining the lead-free tin-based solder alloy, wherein the overall mixing entropy of the alloy is 1.54R, and the melting peak temperature is 82.6 ℃.
Comparative example 1
A preparation method of a lead-free tin-based solder alloy is different from example 2 In that the atomic percentages of the components are 20% of Zn, 25% of Bi, 20% of In, 10% of Cu and 25% of Sn;
the other preparation methods and raw material compositions are the same as in example 2, and the prepared solder alloy has a melting peak temperature of 81.2 ℃, toughness of 82.6%, tensile strength of 42.6 MPa and a tensile strength far lower than that of example 2.
Comparative example 2
A preparation method of a lead-free tin-based solder alloy is different from example 2 In that the atomic percentages of the components are 20% of Zn, 20% of Bi, 7% of In, 23% of Cu and 30% of Sn;
the other preparation methods and raw material compositions are the same as in example 2, and the prepared solder alloy has a melting peak temperature of 140.6 ℃, an elongation of 18.2% and an elongation far lower than that of example 2.
Performance testing
The lead-free tin-based solder alloy prepared in example 2 was cut into pieces and the surface was polished, a small amount of halogen flux was uniformly applied to the surface, sandwiched between polished copper blocks, placed in a reflow oven, and welded at 180 ℃ with a microstructure of 2 min as shown in a diagram in fig. 5, and welded at 180 ℃ with a microstructure of 3 min as shown in b diagram in fig. 5, and it was seen from fig. 3 that the IMC thickness at the time of welding 3 min was 0.76 μm, which was almost the same as the thickness at the time of welding 2 min IMC, indicating that the diffusion rate at the time of welding the solder prepared in the present invention was slow. After the initial welding condition of 180 ℃ and welding of 5 min ℃, the microstructure after heat aging of 0h, 50 h and 100 h is shown in fig. 6, and it can be observed from fig. 6 that the interface IMC gradually increases in thickness with the heat aging time, however, the growth dynamics process is slower than that of the conventional SnBi solder. The interface scan is performed during the heat aging of 100 h, the scan results of the interface line scan and the dot scan are shown in fig. 7 and 8, and it can be known from fig. 7 and 8 that the interface IMC is a five-membered complex compound. Under the influence of the high entropy effect, the interface diffusion and the interface IMC growth process are obviously inhibited.
The lead-free tin-based solder alloy prepared in example 2 was cut into small pieces, sequentially polished with 600 mesh, 1000 mesh, 1500 mesh and 2000 mesh sand paper, polished with 1 μm silica polishing solution, and subjected to BSE observation, wherein a BSE (back scattering electron image) diagram is shown in fig. 9, wherein a diagram a is a BSE diagram of the whole alloy, red frames and blue frames marked with high entropy phases are enlarged diagrams of the red frames marked with high entropy phases, fig. 9 shows that the alloy consists of five phases corresponding to parts of different lining degrees of the picture respectively, gray corresponds to a tin-rich phase (tin content exceeds 90%), white phase is a bismuth-rich phase (bismuth content exceeds 90%), gray color is an InBi phase, dark black is a CuZn phase, and gray phases with black spots are five-membered high entropy phases containing five elements, and the phases are uniformly distributed.
The BSE (back-scattered electron imaging) and EDS (‌ energy spectrum point and surface scanning) images of the lead-free tin-based solder alloy prepared In example 2 are shown In fig. 10, and it can be known from fig. 10 that the high-entropy phase consists of five different elements, and the atomic percentages of Cu, zn, in, sn and Bi In the high-entropy phase are 16.0%,16.4%,16.8%,35.6% and 15.2%, respectively. The calculated entropy value of the high-entropy phase is 1.54R, which is far higher than the entropy (1.0R-1.2R) of the phase in the traditional brazing filler metal and the high-entropy brazing filler metal, and belongs to the high-entropy category. ‌ A
The lead-free tin-based solder alloy prepared in example 2 was subjected to ‌ X-ray diffraction (XRD) analysis of the phase composition of the alloy material, the XRD pattern of which is shown in fig. 11, and it can be seen from fig. 11 that the main peak positions of Sn of the alloy in the upper pattern are 31.03 degrees and 32.44 degrees, and the main peak positions of Sn in the standard PDF card in the lower pattern are 30.631 degrees and 32.014 degrees, and the shift of the peaks can be seen by comparing the main peak positions of Sn in the two patterns, indicating that the matrix phase in the lead-free tin-based solder alloy material is solid solution phase, and the existence of solid solution strengthening of the matrix of the solder alloy prepared in the invention occurs to some extent, which is favorable for improving the load carrying capacity of the solder.
The lead-free tin-based solder alloy prepared in example 2 was tested according to ISO 6892-1/ASTM E8, and the test results are shown in fig. 12, and it can be seen from fig. 12 that the solder alloy prepared by the method of the present invention has higher tensile properties than the conventional Sn 58 Bi low temperature solder, and the elongation exceeds 40% while the tensile strength exceeds 60 MPa, and the elongation is 12% -20% that of the far super Sn 58 Bi solder, which contributes to improvement of solder welding reliability.
The wetting angle of example 2 of the present invention was tested, and the wetting angle was 46.9 ° as shown in fig. 13, which shows SEM images of welded cross sections under the condition that the welding time was 150 s at 180 ℃.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1.一种具有高熵相的无铅锡基钎料合金，其特征在于，所述无铅锡基钎料合金以Sn，及Bi或In中的任意一种或两种组合为主元素，其余元素包括Ni、Mn、Ag、Cu和Zn中的任意两种或三种组合。1. A lead-free tin-based solder alloy with a high-entropy phase, characterized in that the lead-free tin-based solder alloy is based on Sn and any one or a combination of two of Bi or In as the main elements, and the remaining elements include any two or a combination of three of Ni, Mn, Ag, Cu and Zn. 2.根据权利要求1所述的具有高熵相的无铅锡基钎料合金，其特征在于，所述无铅锡基钎料合金中Sn为必需元素，所述无铅锡基钎料合金中包括五种元素；2. The lead-free tin-based solder alloy with a high-entropy phase according to claim 1, characterized in that Sn is an essential element in the lead-free tin-based solder alloy, and the lead-free tin-based solder alloy includes five elements; 所述无铅锡基钎料合金的混合熵≥1.4R。The mixing entropy of the lead-free tin-based solder alloy is ≥1.4R. 3.根据权利要求1所述的具有高熵相的无铅锡基钎料合金，其特征在于，所述无铅锡基钎料合金以Sn、Bi和In为主元素，其余元素包括Cu和Zn。3. The lead-free tin-based solder alloy with a high-entropy phase according to claim 1, characterized in that the lead-free tin-based solder alloy is mainly composed of Sn, Bi and In, and the remaining elements include Cu and Zn. 4.根据权利要求3所述的具有高熵相的无铅锡基钎料合金，其特征在于，所述无铅锡基钎料合金各元素按原子百分比计，Zn：10%-25%、Bi：15%-25%、In：5%-20%、Cu：5%-15%、余量为Sn。4. The lead-free tin-based solder alloy with a high-entropy phase according to claim 3, characterized in that, by atomic percentage, each element of the lead-free tin-based solder alloy is: Zn: 10%-25%, Bi: 15%-25%, In: 5%-20%, Cu: 5%-15%, with the balance being Sn. 5.一种如权利要求1-4任一项所述的具有高熵相的无铅锡基钎料合金的专用熔炼设备，其特征在于，所述专用熔炼设备包括熔炼容器组件和辅助设备组件；5. A dedicated melting equipment for lead-free tin-based solder alloys with a high-entropy phase as described in any one of claims 1-4, characterized in that the dedicated melting equipment comprises a melting container assembly and an auxiliary equipment assembly; 所述熔炼容器组件包括特质容器，所述特质容器的顶部连接有密封装置，所述密封装置的顶部连接有搅拌棒，所述搅拌棒穿过所述密封装置伸入所述特质容器的内部，所述搅拌棒上连接有微型电机；The melting container assembly includes a special container, the top of which is connected to a sealing device, the top of which is connected to a stirring rod, the stirring rod extending through the sealing device into the interior of the special container, and a micro motor connected to the stirring rod; 所述辅助设备组件包括电机固定架、快速升降装置、真空气路、排气管路和惰性气体输入气路，所述电机固定架一端与所述快速升降装置连接，另一端与所述微型电机连接，所述真空气路、所述排气管路和惰性气体输入气路均通过快接法兰与所述密封装置连接。The auxiliary equipment components include a motor mounting bracket, a quick-lifting device, a vacuum passage, an exhaust pipe, and an inert gas input passage. One end of the motor mounting bracket is connected to the quick-lifting device, and the other end is connected to the micro motor. The vacuum passage, the exhaust pipe, and the inert gas input passage are all connected to the sealing device via quick-connect flanges. 6.根据权利要求5所述的具有高熵相的无铅锡基钎料合金的专用熔炼设备，其特征在于，所述快速升降装置包括主体支架、连接滑轨、手轮操作部件和试管固定架，所述电机固定架与所述主体支架连接，所述手轮操作部件固定连接在所述主体支架上，所述手轮操作部件与所述连接滑轨传动连接；所述试管固定架固定连接在所述连接滑轨上，并通过所述连接滑轨与所述主体支架形成滑动连接，通过转动所述手轮操作部件，带动所述连接滑轨内的丝杠旋转，从而驱动所述试管固定架上下移动。6. The special smelting equipment for lead-free tin-based solder alloys with a high-entropy phase according to claim 5, characterized in that the rapid lifting device includes a main support, a connecting slide rail, a handwheel operating component, and a test tube holder; the motor holder is connected to the main support; the handwheel operating component is fixedly connected to the main support; the handwheel operating component is drivenly connected to the connecting slide rail; the test tube holder is fixedly connected to the connecting slide rail and forms a sliding connection with the main support through the connecting slide rail; by rotating the handwheel operating component, the lead screw in the connecting slide rail is driven to rotate, thereby driving the test tube holder to move up and down. 7.根据权利要求5所述的具有高熵相的无铅锡基钎料合金的专用熔炼设备，其特征在于，所述密封装置采用双重密封结构：下部密封通过快接法兰接头配合耐高温橡胶圈实现，上部密封采用高弹性密封胶塞。7. The special smelting equipment for lead-free tin-based solder alloys with high entropy phase according to claim 5, characterized in that the sealing device adopts a double sealing structure: the lower sealing is achieved by a quick-connect flange joint in conjunction with a high-temperature resistant rubber ring, and the upper sealing adopts a high-elasticity sealing plug. 8.一种如权利要求1-4任一项所述的具有高熵相的无铅锡基钎料合金的制备方法，其特征在于，包括以下步骤：8. A method for preparing a lead-free tin-based solder alloy with a high-entropy phase as described in any one of claims 1-4, characterized in that it comprises the following steps: （1）将各组成成分置于权利要求5所述的专用熔炼设备中，抽真空后注入惰性气体进行感应熔炼，静置冷却后得到铸锭；(1) Place each component in the special melting equipment described in claim 5, evacuate and inject inert gas for induction melting, and then let it stand and cool to obtain an ingot; （2）将所述铸锭置于权利要求5所述的专用熔炼设备中，抽真空后注入惰性气体进行再次熔炼，将得到的熔体经冷却后，即得到所述无铅锡基钎料合金。(2) The ingot is placed in the special melting equipment described in claim 5, and after vacuuming, inert gas is injected for remelting. After cooling the resulting melt, the lead-free tin-based solder alloy is obtained. 9.根据权利要求8所述的具有高熵相的无铅锡基钎料合金的制备方法，其特征在于，步骤（1）中所述感应熔炼的温度为600-700 ℃，时间为6-9 min。9. The method for preparing lead-free tin-based solder alloy with high entropy phase according to claim 8, characterized in that the induction melting temperature in step (1) is 600-700 ℃ and the time is 6-9 min. 10.根据权利要求8所述的具有高熵相的无铅锡基钎料合金的制备方法，其特征在于，步骤（2）中所述再次熔炼的温度为300-600 ℃，时间为8-10 min；10. The method for preparing lead-free tin-based solder alloy with high entropy phase according to claim 8, characterized in that the remelting temperature in step (2) is 300-600 ℃ and the time is 8-10 min; 所述再次熔炼在高速搅拌下进行，所述高速搅拌的转速为300 rpm；The remelting is carried out under high-speed stirring at a speed of 300 rpm; 所述冷却的方式为将盛有熔体的容器浸入冰水混合物或液氮中。The cooling method involves immersing the container holding the melt in an ice-water mixture or liquid nitrogen.
CN202511987667.XA 2025-12-26 2025-12-26 Lead-free tin-based solder alloy with high entropy phase, preparation method thereof and special smelting equipment Pending CN121551906A (en)

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