CN104289824A - Stannum, argentum and copper lead-free solder and production method thereof - Google Patents
Stannum, argentum and copper lead-free solder and production method thereof Download PDFInfo
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- CN104289824A CN104289824A CN201410520684.8A CN201410520684A CN104289824A CN 104289824 A CN104289824 A CN 104289824A CN 201410520684 A CN201410520684 A CN 201410520684A CN 104289824 A CN104289824 A CN 104289824A
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- copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
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- Electric Connection Of Electric Components To Printed Circuits (AREA)
Abstract
The invention discloses a stannum, argentum and copper lead-free solder and a production method thereof. The stannum, argentum and copper lead-free solder is formed by, by weight, 1.0 to 5.0 % of argentum, 0.1 to 1.0 % of copper, 0.1 to 0.5% of yttrium, 0.1 to 0.5% of cerium and the balance stannum. The production method comprises adjusting the vacuum degree of a vacuum furnace into 1 to 5 MPa at the room temperature; mixing the copper with the yttrium and smelting in the vacuum furnace for 5 to 8 minutes to obtain the copper and yttrium intermediate alloy; mixing the copper with the cerium and smelting in the vacuum furnace for 5 to 8 minutes to obtain the copper and cerium intermediate alloy; placing the mass fraction of stannum and argentum into the molten copper and microelement intermediate alloy, performing full stirring after the smelting and performing cooling. According to the stannum, argentum and copper lead-free solder and the production method thereof, the trace rare earth elements yttrium and cerium are added into the stannum and copper alloy to produce the solder alloy which is good in welding performance and mechanical property and accordingly the lead-free purpose can be achieved; meanwhile precious metal elements such as gold is not contained and accordingly the cost is significantly reduced; meanwhile the organization and mechanical property of the solder alloy is improved through the trace rare earth elements and accordingly the high reliability of a solder point can be ensured and the new requirements for the solder alloy due to the rapid development of electronic products can be met.
Description
Technical field
The present invention relates to a kind of lead-free solder and preparation method thereof, especially a kind of Sn-Ag-Cu lead-free solder and preparation method thereof.
Background technology
" light, thin, short, little " change of electronic product is had higher requirement to the microminiaturization of components and parts and packing density, and for all components and parts, the reliability of device solder joint is the key factor affecting its life-span, because solder joint is the position that whole stresses of parts is concentrated, therefore solder joint optimal design and how to ensure that quality of welding spot is an important problem.As the direct result of welding, the quality and reliability of solder joint determines the quality of electronic product.That is, in process of production, the quality of assembling finally shows as the quality of welding.The nineties in last century rises, more and more higher to the requirement that electronic product is unleaded in the world, and European Union formally clearly proposed to forbid from 1 day July in 2006 at the leaded electronic product of EU member country's production and selling on February 13rd, 2003.Through the research of more than ten years, existing tens kinds of lead-free solders are developed.These leadless welding alloy systems have soldering processes performance, excellent welding spot reliability relatively preferably, are acknowledged as the alloy system having application prospect in lead-free solder most gradually.But substantially all containing, for example precious metal elements such as Au, Ag in these alloys, cause the cost of alloy higher, especially in recent years, the rise in price of noble metal is very fast, the rise of noble metal price limits a large amount of uses of noble metal in solder alloy, therefore researches and develops and is not of great significance containing the new solder alloy of noble metal.
Summary of the invention
The object of the invention is for overcoming above-mentioned the deficiencies in the prior art, a kind of Sn-Ag-Cu lead-free solder and preparation method thereof is provided, the solder welding performance of preparation is good, good mechanical performance, not containing precious metal elements such as Au while of unleaded, significantly reduce cost, utilize the rare earth element of trace to improve the microstructure and mechanical property of solder alloy simultaneously.
For achieving the above object, the present invention adopts following technical proposals:
Sn-Ag-Cu lead-free solder, the composition of this solder and content percentage, Ag:1.0 ~ 5.0%, Cu:0.1 ~ 1.0%, Y:0.1 ~ 0.5%, Ce:0.1 ~ 0.5%, surplus is Sn.
Preferably, the composition of this solder and content percentage, Ag:2.8%, Cu:0.5%, Y:0.2%, Ce:0.1%, surplus is Sn.
A preparation method for Sn-Ag-Cu lead-free solder, is realized by following steps:
(1) preparation of intermediate alloy Cu-Y and Cu-Ce
At 15 ~ 30 DEG C, the vacuum of vacuum drying oven is adjusted to 1-5MPa, Cu and Y is mixed, melting 5 ~ 8min in a vacuum furnace, obtain Cu-Y intermediate alloy; Cu and Ce is mixed, melting 5 ~ 8min in a vacuum furnace, obtain Cu-Ce intermediate alloy; Mix after the Cu-Y intermediate alloy of preparation and the melting of Cu-Ce intermediate alloy;
(2) preparation of Sn-Ag-Cu-Y-Ce alloy
At 15 ~ 30 DEG C, Cu-Y and the Cu-Ce intermediate alloy putting into melting according to Sn, Ag of above-mentioned mass fraction, fully stirs, is cooled to room temperature after all melting.
In step (1), the mass ratio of described Cu and Y is 6.5 ~ 7.5:2.5 ~ 3.5, and the mass ratio of described Cu and Ce is 6.0 ~ 7.0:3.0 ~ 4.0.
In step (1), described Cu-Y intermediate alloy and Cu-Ce intermediate alloy bed blending quality ratio are 5.5 ~ 6.5:3.5 ~ 4.5.
The invention has the beneficial effects as follows, the Y element of trace can the tissue of refining alloy, improve form and the distribution of the intermetallic compound in solder alloy, avoid producing thick intermetallic compound, thus put forward heavy alloyed mechanical property, the Ce element of trace is except except the tissue of refining alloy, can putting forward heavy alloyed mechanical behavior under high temperature, especially can put forward heavy alloyed croop property.Trace rare-earth element Y and Ce is added based in Sn-Cu alloy, preparation has the solder alloy of good welds performance, mechanical property, both unleaded object can be reached, simultaneously not containing precious metal elements such as Au, significantly reduce cost, utilize the rare earth element of trace to improve the microstructure and mechanical property of solder alloy simultaneously, thus can ensure that solder joint has higher reliability, can meet the fast-developing new demand proposed solder alloy of electronic product, therefore this research has significant actual application value.
Accompanying drawing explanation
Fig. 1 is the different yttrium content Sn-Ag-Cu-Y-Ce alloy creep life-spans;
Fig. 2 is Sn-Ag-Cu-0.2Y-0.1Ce and Cu substrate weld interface pattern.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is further described.
Embodiment 1:
Sn-Ag-Cu lead-free solder, the composition of this solder and content percentage, Ag:1.0%, Cu:0.1%, Y:0.1%, Ce:0.2%, surplus is Sn.
The preparation method of above-mentioned Sn-Ag-Cu lead-free solder, is realized by following steps:
(1) intermediate alloy Cu-Y, Cu-Ce
At 15 DEG C, the vacuum of vacuum drying oven is adjusted to 1MPa, be Cu and the Y mixing of 6.5:2.5 by mass ratio, melting 5min in a vacuum furnace, obtains Cu-Y intermediate alloy; Be Cu and the Ce mixing of 6.0:4.0 by mass ratio, melting 5 ~ 8min in a vacuum furnace, obtains Cu-Ce intermediate alloy; Be mix the Cu-Y intermediate alloy of preparation and Cu-Ce intermediate alloy after 5.5:3.5 melting according to mass ratio;
(2) preparation of Sn-Ag-Cu-Y-Ce
Put into Cu-Y, Cu-Ce intermediate alloy of melting according to Sn, Ag of above-mentioned mass fraction, fully stir after all melting.
Embodiment 2:
Sn-Ag-Cu lead-free solder, the composition of this solder and content percentage, Ag:5.0%, Cu:1.0%, Y:0.5%, Ce:0.1%, surplus is Sn.
The preparation method of above-mentioned Sn-Ag-Cu lead-free solder, is realized by following steps:
(1) preparation of intermediate alloy Cu-Y, Cu-Ce
At 30 DEG C, the vacuum of vacuum drying oven is adjusted to 5MPa, be Cu and the Y mixing of 7.5:3.5 by mass ratio, melting 8min in a vacuum furnace, obtains Cu-Y intermediate alloy; Be Cu and the Ce mixing of 6.5:3.5 by mass ratio, melting 5 ~ 8min in a vacuum furnace, obtains Cu-Ce intermediate alloy; Be mix the Cu-Y intermediate alloy of preparation and Cu-Ce intermediate alloy after 6:4 melting according to mass ratio;
(2) preparation of Sn-Ag-Cu-Y-Ce
Put into the Cu-Y intermediate alloy of melting according to Sn, Ag of above-mentioned mass fraction, fully stir after all melting.
Embodiment 3:
Sn-Ag-Cu lead-free solder, the composition of this solder and content percentage, Ag:2.8%, Cu:0.5%, Y:0.3%, Ce:0.5%, surplus is Sn.
The preparation method of above-mentioned Sn-Ag-Cu lead-free solder, is realized by following steps:
(1) preparation of intermediate alloy Cu-Y, Cu-Ce
At 23 DEG C, the vacuum of vacuum drying oven is adjusted to 3MPa, be Cu and the Y mixing of 7:3 by mass ratio, melting 5min in a vacuum furnace, obtains Cu-Y intermediate alloy; Be Cu and the Ce mixing of 6:3 by mass ratio, melting 5 ~ 8min in a vacuum furnace, obtains Cu-Ce intermediate alloy; Be mix the Cu-Y intermediate alloy of preparation and Cu-Ce intermediate alloy after 6.5:4.5 melting according to mass ratio;
(2) preparation of Sn-Ag-Cu-Y-Ce
Put into the Cu-Y intermediate alloy of melting according to Sn, Ag of above-mentioned mass fraction, fully stir after all melting.
Embodiment 4:
Sn-Ag-Cu lead-free solder, the composition of this solder and content percentage, Ag:2.8%, Cu:0.5%, Y:0.2%, Ce:0.1%, surplus is Sn.
The preparation method of above-mentioned Sn-Ag-Cu lead-free solder, is realized by following steps:
(1) preparation of intermediate alloy Cu-Y, Cu-Ce
At 23 DEG C, the vacuum of vacuum drying oven is adjusted to 3MPa, be Cu and the Y mixing of 7:3 by mass ratio, melting 5min in a vacuum furnace, obtains Cu-Y intermediate alloy; Be Cu and the Ce mixing of 6.5:3.5 by mass ratio, melting 5 ~ 8min in a vacuum furnace, obtains Cu-Ce intermediate alloy; Be mix the Cu-Y intermediate alloy of preparation and Cu-Ce intermediate alloy after 6:4 melting according to mass ratio;
(2) preparation of Sn-Ag-Cu-Y-Ce
Put into the Cu-Y intermediate alloy of melting according to Sn, Ag of above-mentioned mass fraction, fully stir after all melting.
The solder refuse first will prepared in the embodiment of the present invention 4, pours in the stainless steel molding jig of 450 DEG C, then, mould is cooled to room temperature with the speed of 2 DEG C/s; The inner surface of mould, through sanding and polishing process, ensure that the smooth surface of casting sample; Finally, take out sample, the burr removing mould bound fraction is to be measured.
Stretching experiment adopt microcomputer control tensile testing machine: sample at room temperature with the speed tensile of 10mm/min until fracture.The calculating of ultimate tensile strength, elongation after fracture and 0.2% disproportional elongation stress is all carried out according to National Standard of the People's Republic of China GB228-87, and test result shows, ultimate tensile strength is 20MPa, and elongation after fracture is 12%.
Alloy creep test result is for shown in Fig. 1, and creep life, test showed, the life-span of creep rupture of SnAgCu plumb joint under room temperature can be improved 90% ~ 150% by the interpolation of minipool Rare Earth Y and Ce.At ambient temperature, when content of rare earth Y is 0.2wt.%, life-span of creep rupture is the highest.
The interface formed after Sn-Ag-Cu-0.2Y-0.1Ce solder alloy welds with copper dish, as shown in Figure 2, figure middle and upper part light color metal is Sn-Ag-Cu-0.2Y-0.1Ce alloy, bottom dark parts is Cu dish, carry out research to the microscopic structure after solder alloy and the welding of Cu dish to find, Sn-Ag-Cu-0.2Y-0.1Ce alloy and Cu dish solder interconnections interface dense, not significantly cavity, simultaneously at the intermetallic compound Ag that solder alloy and linkage interface exist
3sn is tiny, and is evenly dispersed in Sn, morphology of intermetallic compound and being evenly distributed, and this is highly beneficial to the mechanical property improving solder alloy.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (5)
1. a Sn-Ag-Cu lead-free solder, is characterized in that, the composition of this solder and content percentage, Ag:1.0 ~ 5.0%, Cu:0.1 ~ 1.0%, Y:0.1 ~ 0.5%, Ce:0.1 ~ 0.5%, surplus is Sn, and its medium trace element is Y and Ce.
2. a kind of Sn-Ag-Cu lead-free solder as claimed in claim 1, is characterized in that, the composition of this solder and content percentage, Ag:2.8%, Cu:0.5%, Y:0.2%, Ce:0.1%, and surplus is Sn.
3. the preparation method of Sn-Ag-Cu lead-free solder as claimed in claim 1, is realized by following steps:
(1) preparation of intermediate alloy Cu-Y and Cu-Ce
At 15 ~ 30 DEG C, the vacuum of vacuum drying oven is adjusted to 1 ~ 5MPa, Cu and Y is mixed, melting 5 ~ 8min in a vacuum furnace, obtain Cu-Y intermediate alloy; Cu and Ce is mixed, melting 5 ~ 8min in a vacuum furnace, obtain Cu-Ce intermediate alloy; Mix after the Cu-Y intermediate alloy of preparation and the melting of Cu-Ce intermediate alloy;
(2) preparation of Sn-Ag-Cu-Y-Ce alloy
At 15 ~ 30 DEG C, Cu-Y and the Cu-Ce intermediate alloy putting into melting according to Sn, Ag of above-mentioned mass fraction, fully stirs, is cooled to room temperature after all melting.
4. the preparation method of a kind of Sn-Ag-Cu lead-free solder as claimed in claim 3, is characterized in that, in step (1), the mass ratio of described Cu and Y is 6.5 ~ 7.5:2.5 ~ 3.5, and the mass ratio of described Cu and Ce is 6.0 ~ 7.0:3.0 ~ 4.0.
5. the preparation method of a kind of Sn-Ag-Cu lead-free solder as claimed in claim 3, is characterized in that, in step (1), described Cu-Y intermediate alloy and Cu-Ce intermediate alloy bed blending quality ratio are 5.5 ~ 6.5:3.5 ~ 4.5.
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| CN201410520684.8A CN104289824B (en) | 2014-09-30 | 2014-09-30 | Stannum, argentum and copper lead-free solder and production method thereof |
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| CN201410520684.8A CN104289824B (en) | 2014-09-30 | 2014-09-30 | Stannum, argentum and copper lead-free solder and production method thereof |
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| CN104289824B CN104289824B (en) | 2017-05-24 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113458650A (en) * | 2021-07-05 | 2021-10-01 | 云南锡业锡材有限公司 | Sn-Ag-Cu-Ce high-reliability lead-free solder |
| CN114289927A (en) * | 2021-12-28 | 2022-04-08 | 上海大学 | Lead-free solder |
| CN114888481A (en) * | 2022-05-31 | 2022-08-12 | 杭州华光焊接新材料股份有限公司 | High-reliability lead-free solder alloy |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113458650A (en) * | 2021-07-05 | 2021-10-01 | 云南锡业锡材有限公司 | Sn-Ag-Cu-Ce high-reliability lead-free solder |
| CN114289927A (en) * | 2021-12-28 | 2022-04-08 | 上海大学 | Lead-free solder |
| CN114888481A (en) * | 2022-05-31 | 2022-08-12 | 杭州华光焊接新材料股份有限公司 | High-reliability lead-free solder alloy |
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| CN104289824B (en) | 2017-05-24 |
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