CN108866364B - Method for adding easily-oxidizable elements into Sn-based brazing filler metal - Google Patents
Method for adding easily-oxidizable elements into Sn-based brazing filler metal Download PDFInfo
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- CN108866364B CN108866364B CN201810563985.7A CN201810563985A CN108866364B CN 108866364 B CN108866364 B CN 108866364B CN 201810563985 A CN201810563985 A CN 201810563985A CN 108866364 B CN108866364 B CN 108866364B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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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
- B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
- B23K20/002—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating specially adapted for particular articles or work
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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
- B23K35/40—Making wire or rods for soldering or welding
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- 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
Abstract
The invention provides a method for adding an easily-oxidized element into Sn-based brazing filler metal, which comprises the steps of coating the easily-oxidized element additive in parent metal by utilizing the cold pressure welding principle under the protection of inert gas, then immersing the parent metal of a coating structure into molten parent metal, dissolving an alloy outside the coating structure, and contacting and dissolving an internal additive with the molten metal. Because the outer layer of the coating structure immersed in the parent metal is the parent metal and only contains inert gas and easily-oxidizable element additives, and no oxygen is generated in the processes of melting the external metal and dissolving the easily-oxidizable element, the easily-oxidizable element cannot be oxidized, and a better element addition effect is achieved; the method has simple preparation process, realizes the purpose of directly adding the easily-oxidized elements in the atmospheric environment, and can greatly reduce the cost of solder production enterprises.
Description
Technical Field
The invention belongs to the technical field of solder preparation, and particularly relates to a method for adding an easily-oxidized element into a Sn-based solder.
Background
Alloying is always one of effective methods for improving the performance of the alloy, and is widely used for preparing various alloys. The addition of trace elements is one of the important methods for improving the performance of Sn-based solder. In Sn-based solder alloys, some alloying elements or trace elements are achieved by direct addition or by making an intermediate alloy first and then adding it twice. However, in the case of the easily oxidizable additive, it is difficult to directly add the easily oxidizable element to the molten metal, both in the case of direct addition and in the case of production of an intermediate alloy, because the easily oxidizable element is oxidized or even burned at room temperature or at the moment of contact with the molten metal. Secondly, the oxides on the surface of the additive prevent the additive from dissolving or reacting with the molten metal. Therefore, many elements easy to oxidize are prepared by vacuum melting, which greatly increases the cost of enterprises.
For easily oxidized and flammable trace elements (such as P, Ce, Al and the like), the trace elements are directly added under the protection of inert gas, so that the cost for preparing the alloy is greatly increased. In actual production, many solder manufacturers directly add trace elements to the molten Sn-based metal in the atmospheric environment, so that the disadvantages of great loss of trace elements, toxic gas generation and the like are inevitably generated. Taking trace element P as an example, P is commonly used as an antioxidant trace element of Sn-based solder. In the production process, if white phosphorus is directly added to the molten Sn-based alloy, the Sn-based alloy temperature needs to be around 600 ℃, and the ignition point of the white phosphorus is 40 ℃, so that oxidation and combustion inevitably occur during the direct addition process, and toxic phosphorus pentoxide is generated. If the catalyst is added in an inert atmosphere, the manufacturing cost of enterprises is greatly increased.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a method for adding an easily-oxidizable element into a Sn-based brazing filler metal, which is not contacted with oxygen all the time in the preparation process, realizes the purpose of directly adding the easily-oxidizable element in an atmospheric environment and has a better element addition effect.
In contrast, the technical scheme adopted by the invention is as follows:
a method of adding an easily oxidizable element to a Sn-based solder, comprising the steps of:
step S1, making the matrix Sn-based brazing filler metal into a lamellar structure to obtain lamellar metal;
step S2, folding the sheet metal, and performing cold pressing welding on two sides to prepare a pocket structure with an opening at one end;
step S3, under the protection of inert gas, the additive of the easily oxidized element is put into the middle of the metal interlayer from the opening of the pocket type structure;
step S4, under the protection of inert gas, cold-pressing and welding the opening of the pocket type structure to manufacture a cladding structure of the base metal cladding additive;
step S5, the base metal coating additive is immersed into the molten parent metal, the external metal of the coating layer is dissolved, and the internal additive is contacted with the molten metal and dissolved or reacted; wherein the temperature of the molten parent metal is not lower than the melting temperature of the additive. Further, step S5 is performed in the atmospheric environment.
By adopting the technical scheme, under the protection of inert gas, the easily-oxidized element additive is coated in the parent metal by utilizing the principle of cold pressure welding; the cladding structure may then be immersed in the molten parent metal using a robotic arm in an atmospheric environment without the need for an inert gas environment, with the outer alloy of the cladding structure dissolving and the inner additive contacting and dissolving the molten metal. The outer layer of the cladding structure immersed in the parent metal is the parent metal and only contains inert gas and easily-oxidizable element additives, and oxygen is not generated in the melting process of the external metal and the dissolving process of the easily-oxidizable element, so that the easily-oxidizable element cannot be oxidized.
Further, after step S5, the additive-added base metal obtained in step S5 may be further mixed in a proportion to prepare a solder alloy.
As a further improvement of the invention, the thickness D of the sheet metal is 500 μm to 10 mm. The sheet side is preferably such that it completely covers the additive and leaves a 5-10mm peripheral margin. The thickness D of the sheet metal is less than 500 mu m, the sheet metal is easy to damage, and waste is caused when the sheet metal is too thick. More preferably, the thickness D of the sheet metal is 500 μm to 8 mm.
As a further improvement of the invention, in step S2, the sheet metal is folded in half and then both sides are sent to a roller press for cold press welding; distance D between two extrusion rollers of roller pressgThe relation with the thickness D of the sheet metal is that D × 2 is more than or equal to D2%g2D × 20% or less, if the distance D between two extrusion rollers of the roller press is less than or equal togMore than 2D × 20%, the two layers of metal can not be welded completely, and the sealing effect can not be achieved, further, the ratio of 2D × 5% to D is more than or equal to Dg≤2D×20％。
As a further improvement of the present invention, in step S4, a spacing D is usedgThe opening of the roller press is welded in a cold pressing way, and the distance D between two extrusion rollers of the roller pressgThe relation with the thickness D of the sheet metal is that D × 5 is more than or equal to D5%g≤2D× 20％。
As a further improvement of the invention, in the step S2 and the step S4, the welding width is 2-10 mm.
As a further improvement of the present invention, in step S5, the base metal cladding additive is immersed in the molten parent metal using a robot arm.
As a further improvement of the present invention, the temperature of the molten parent metal in step S5 is identical to the temperature of the Sn-based solder conventionally used to prepare the additive.
As a further improvement of the invention, the Sn-based solder is a solder alloy used in the field of electronic packaging of Sn-Ag-Cu, Sn-Ag, Sn-Cu, Sn-Bi or Sn-Zn.
As a further improvement of the invention, the additive of the easily-oxidizable element is P, Ce or Al. Further, the additive accounts for 0.05-3% of the matrix metal by mass.
The method can be used for adding trace elements or preparing intermediate alloy.
Compared with the prior art, the invention has the beneficial effects that:
by adopting the technical scheme of the invention, a new method for adding the easily-oxidized elements is provided by utilizing the principle of cold pressure welding, the utilization rate of the additives is greatly improved, more elements in the additives can react with the parent metal and are fused into the parent metal, and a better element addition effect is achieved; and the method has simple preparation process and low cost, and can be used for adding easily-oxidized and combustible easily-oxidized elements. The brazing filler metal is not contacted with oxygen all the time in the preparation process, and finally the base metal cladding additive is immersed into the molten parent metal in the atmospheric environment, so that the aim of directly adding the easily-oxidized element in the atmospheric environment is fulfilled, and the cost of brazing filler metal production enterprises can be greatly reduced.
Drawings
FIG. 1 is a schematic view of the cold-welded seal of the present invention.
FIG. 2 is a schematic view of the alloy cladding process of the present invention.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
Example 1
The method comprises the steps of adding 2% of white phosphorus into pure Sn to prepare Sn-P intermediate alloy, selecting 10kg of pure Sn as a parent alloy, taking a part of pure Sn at a ratio of P: 200g, and preparing a 200 × 300 × 4mm lamellar structure through cold pressing deformation, folding the pure Sn of the lamellar layer in a long side manner, and then carrying out cold pressing welding on two side edges by using a roller press to prepare a pocket structure, wherein the distance between extrusion rollers is 1.2mm, and the welding width is 5 mm.
As shown in FIG. 2, the Sn alloy with both sides bonded was put into a glove box in Ar atmosphere, and 200g of P was put into the glove box from the opening. And (4) carrying out cold pressing and welding on the opening by using a manual roller press to prepare the Sn-coated P block structure. The distance between the squeeze rollers is 1.2mm, and the welding width is 5 mm.
Heating pure Sn in a graphite crucible to 580 ℃ in an atmospheric environment, pressing a block structure of Sn coated P into Sn metal by using a mechanical arm, stirring, taking out the mechanical arm after stirring for 20min, and casting molten metal into ingots.
Example 2
In the embodiment, 0.1% of Ce. added into Sn-3Ag-0.5Cu is used for selecting 965g of pure Sn as a parent alloy, 30g of Ag, 5g of Cu and 1g of Ce, a part of pure Sn is prepared into a 100 × 100 × 2mm lamellar structure through cold pressing deformation, the lamellar Sn is folded in half, a roll press is used for cold pressing and welding the side edges, the distance between extrusion rolls is 0.6mm, and the welding width is 5 mm.
The side-welded Sn alloy was put into a glove box in an Ar atmosphere, and 10g of Ce grains were charged from the opening. And (4) carrying out cold pressing and welding on the opening by using a manual roller press to prepare the Sn-coated Ce block structure. The squeeze roll pitch was 0.6 mm. The width of the weld is 5 mm.
And heating Sn in a graphite crucible to 1000 ℃, pressing the block structure of Sn coated with Ce into Sn metal by using a mechanical arm, stirring, taking out the mechanical arm after 30min, adding 30gAg and 5gCu when the furnace temperature is up to 300 ℃, stirring for 20min, and then casting molten metal into ingots.
Comparative example 1
This comparative example is compared to example 1. The preparation process comprises the following steps: in this comparative example, 2% white phosphorus was added to pure Sn to prepare an Sn-P master alloy. 10kg of pure tin is selected as a parent alloy, and 200g of white phosphorus is selected. Heating pure Sn in a graphite crucible to 580 ℃ in an atmospheric environment, rapidly pressing white phosphorus into Sn metal by using a mechanical arm, stirring, taking out the mechanical arm after stirring for 20min, and casting molten metal into ingots.
Comparative example 2
This comparative example is compared to example two. The preparation process comprises the following steps: in this example, 0.1% Ce was added to Sn-3Ag-0.5 Cu. Selecting pure Sn: 965g as parent alloy, Ag: 30g, Cu: 5g, Ce: 1g of the total weight of the composition. Heating pure Sn in a graphite crucible to 1000 ℃, rapidly pressing Ce powder into Sn metal by using a mechanical arm and stirring, taking out the mechanical arm after 30min, adding 30gAg and 5gCu when the furnace temperature is up to 300 ℃, stirring for 20min, and then casting molten metal into ingots.
The alloys prepared in the above examples and comparative examples were subjected to elemental analysis (chemical analysis method) to analyze the component ratio of the added elements in the final alloy, and the analysis results are shown in table 1. As can be seen from the table, the alloy prepared by the method of the present invention has a better effect of adding elements than the alloy prepared by directly adding an easily oxidizable substance to the molten metal.
TABLE 1 results of measuring additive components of examples and comparative examples
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (4)
1. A method for adding an easily-oxidized element into Sn-based solder is characterized in that: which comprises the following steps:
step S1, making the matrix Sn-based brazing filler metal into a lamellar structure to obtain lamellar metal;
step S2, folding the sheet metal, and performing cold pressing welding on two sides to prepare a pocket structure with an opening at one end;
step S3, under the protection of inert gas, the additive of the easily oxidized element is put into the middle of the metal interlayer from the opening of the pocket type structure;
step S4, under the protection of inert gas, cold-pressing and welding the opening of the pocket type structure to manufacture a cladding structure of the base metal cladding additive;
step S5, the base metal coating additive is immersed into the molten parent metal, the external metal of the coating layer is dissolved, and the internal additive is contacted with the molten metal and dissolved or reacted; wherein the temperature of the molten parent metal is not lower than the melting temperature of the additive;
the thickness D of the sheet metal is 500 mu m-10 mm;
in the step S2, folding the sheet metal, and sending the two sides into a roller press for cold pressing and welding; distance D between two extrusion rollers of roller pressgThe relation with the thickness D of the sheet metal is that D × 2 is more than or equal to D2%g≤2D×20%；
In step S4, the use distance is DgThe opening of the roller press is welded in a cold pressing way, and the distance D between two extrusion rollers of the roller pressgThe relation with the thickness D of the sheet metal is that D × 5 is more than or equal to D5%g≤2D×20%；
The Sn-based brazing filler metal is Sn-Ag-Cu, Sn-Ag, Sn-Cu, Sn-Bi or Sn-Zn brazing filler metal alloy;
the additive of the easily-oxidized element is P, Ce or Al.
2. The method of adding an easily oxidizable element to a Sn-based solder according to claim 1, characterized in that: in steps S2 and S4, the bonding width is 2 to 10 mm.
3. The method of adding an easily oxidizable element to a Sn-based solder according to claim 1, characterized in that: in step S5, the base metal coating additive is immersed in the molten parent metal using a robot arm.
4. The method of adding an easily oxidizable element to a Sn-based solder according to claim 1, characterized in that: the temperature of the molten parent metal in step S5 is identical to that of the Sn-based solder conventionally prepared with the additive.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810563985.7A CN108866364B (en) | 2018-06-04 | 2018-06-04 | Method for adding easily-oxidizable elements into Sn-based brazing filler metal |
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| CN201810563985.7A CN108866364B (en) | 2018-06-04 | 2018-06-04 | Method for adding easily-oxidizable elements into Sn-based brazing filler metal |
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| CN108866364A CN108866364A (en) | 2018-11-23 |
| CN108866364B true CN108866364B (en) | 2020-08-07 |
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| CN112775583A (en) * | 2021-01-14 | 2021-05-11 | 深圳市兴鸿泰锡业有限公司 | Solder alloy for automatic tin soldering machine and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1481970A (en) * | 2003-07-25 | 2004-03-17 | 南昌大学 | Tin-zinc base plumbum-free solder alloy and its preparing technology |
| CN104925744A (en) * | 2004-11-04 | 2015-09-23 | 微芯片生物技术公司 | Compression And Cold Weld Sealing Methods And Devices |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1481970A (en) * | 2003-07-25 | 2004-03-17 | 南昌大学 | Tin-zinc base plumbum-free solder alloy and its preparing technology |
| CN104925744A (en) * | 2004-11-04 | 2015-09-23 | 微芯片生物技术公司 | Compression And Cold Weld Sealing Methods And Devices |
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