CN101585119A - Oxidation resistant low silver lead-free solder alloy - Google Patents
Oxidation resistant low silver lead-free solder alloy Download PDFInfo
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- CN101585119A CN101585119A CNA2009100427716A CN200910042771A CN101585119A CN 101585119 A CN101585119 A CN 101585119A CN A2009100427716 A CNA2009100427716 A CN A2009100427716A CN 200910042771 A CN200910042771 A CN 200910042771A CN 101585119 A CN101585119 A CN 101585119A
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- alloy
- solder
- lead
- free solder
- solder alloy
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 100
- 239000000956 alloy Substances 0.000 title claims abstract description 100
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 63
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 26
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 22
- 239000004332 silver Substances 0.000 title claims abstract description 17
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 8
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 8
- 238000003466 welding Methods 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 238000005476 soldering Methods 0.000 abstract description 9
- 229910017944 Ag—Cu Inorganic materials 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000009413 insulation Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229910052738 indium Inorganic materials 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 238000005275 alloying Methods 0.000 description 6
- 230000004927 fusion Effects 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 230000003026 anti-oxygenic effect Effects 0.000 description 5
- 238000005282 brightening Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910020888 Sn-Cu Inorganic materials 0.000 description 3
- 229910019204 Sn—Cu Inorganic materials 0.000 description 3
- 238000004100 electronic packaging Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910020816 Sn Pb Inorganic materials 0.000 description 1
- 229910020922 Sn-Pb Inorganic materials 0.000 description 1
- 229910007116 SnPb Inorganic materials 0.000 description 1
- 229910008783 Sn—Pb Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006023 eutectic alloy Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Electric Connection Of Electric Components To Printed Circuits (AREA)
Abstract
An oxidation-resistant low-silver lead-free solder alloy relates to a lead-free solder for environment-friendly soldering, in particular to a lead-free solder for wave soldering. It comprises the following components in percentage by weight: ag: 0.10 to 0.55, Cu: 0.5 to 1.0, and the balance Sn. The lead-free solder alloy further contains P in an amount of 0.001 to 0.1 weight percent. The lead-free solder alloy further contains 0.005-0.1 wt% of In. The lead-free solder alloy further comprises Ge, Ga, Ce or a combination thereof in an amount of 0.0005-0.01 wt%. The solder pot can solve the problems of excessive metal oxides, solder joint bridging, insufficient wettability and the like on the surface of the solder pot in the use process of the existing Sn-Ag-Cu system lead-free solder with low Ag. The lead-free solder alloy can be processed into solder bars, solder rods and solder wires, can also be processed into solder balls, solder paste and other forms, and can meet the requirements of PCB assembly, SMT surface mounting and the like.
Description
Technical field:
The present invention relates to a kind of leadless welding alloy, the oxidation resistant lead-free solder alloy in low silver that particularly a kind of wave-soldering is used.
Background technology:
The Sn-Pb alloy is with characteristics such as its excellent wetability, weldability, electric conductivity, mechanical property, cost be lower, becomes the typical solder alloy of Electronic Packaging and assembling in the present electronics industry.But Pb and contain the poisonous and harmful substance that the Pb compound is the healthy and contaminated environment of harm humans.At present, Japan, European Union and the U.S. have all worked out the unleaded process of scolder of oneself in succession, WEEE (Waste Electricaland Electronic Equipment) and RoHS (Resbictionof Hazrdous Subsfances) instruct that mandatory requirement was from July 1st, 2006, and the electronic product of selling on European market should be unleaded electronic product.
The Sn-3.0Ag-0.7Cu series lead-free solder is existing wave-soldering best lead-free solder of combination property in the leadless welding alloy, but because of containing the Ag more than 3.0%, the cost height.The Sn0.7Cu eutectic alloy becomes wave-soldering at first one of alloy with lead-free solder with advantage such as its low price, raw material supply abundance, solder alloy element easily reclaim, favorable mechanical performance, machinability and more traditional SnPb scolder solder joint are high reliability.Yet, be solder alloy for Sn-Cu, solder alloy easily produces the microstructure segregation phenomenon in fusion process, and its spreadability is still inadequate.The Sn-Cu series lead-free solder alloy of high Sn content in use oxidation tendency also can increase.In addition, in the wave soldering process, the Sn0.7Cu leadless welding alloy also exists some than distinct issues, as the bridging and the easily dissolving of generation in fusion welding of the Cu in the printed substrate of solder joint.The former easily causes the short circuit phenomenon of solder joint, and the latter not only causes the change of fusion welding composition, and easily forms Cu
6Sn
5Intermetallic compound phase (this phase density is lower than the Sn0.7Cu alloy) causes molten braze alloy easily lamination to take place and has shortened service life of scolder.
The present invention discloses a kind of Sn-Ag-Cu series lead-free solder of oxidation resistant low silver, and its weight alloy composition is: Ag:0.10～0.55%; Cu:0.5～1.0%; X:0.0005～0.1% (wherein X refers to P, In and/or Ge or Ga or Ce), surplus is Sn.
The present invention has the close combination property of Sn-3.0Ag-0.7Cu series lead-free solder, cost is near the cost of existing wave-soldering with the Sn-0.7Cu-0.01Ni leadless welding alloy simultaneously, can be used for various lead-free solder products, as foundry alloy, welding rod piece, welding wire, miniature soldered ball, welding powder and soldering paste, be specially adapted to the Electronic Packaging technology in the microelectronics industry.With tin-lead solder alloy phase ratio, alloy of the present invention does not contain poisonous element lead, can be widely used in electronics industry and general engineering.)
Summary of the invention:
The object of the present invention is to provide a kind of oxidation resistant lead-free solder alloy in low silver, it can solve easy oxidation in scolder pot surface in use of Sn-Cu series lead-free solder alloy and problems such as solder joint bridging and wetability deficiency, and combination property is suitable with the Sn-3.0Ag-0.7Cu series lead-free solder again.
Technical scheme of the present invention is: a kind of oxidation resistant lead-free solder alloy in low silver, and it comprises the composition of following percentage by weight: Ag:0.10～0.55, Cu:0.5～1.0, surplus is Sn.
In the above-mentioned leadless welding alloy, further add the P of weight 0.001～0.1.
In the above-mentioned leadless welding alloy, further add percentage by weight and be 0.005～0.1 In.
In the above-mentioned leadless welding alloy, further add percentage by weight and be 0.0005～0.01 Ge or Ga or Ce or their combination.
Oxidation resistant lead-free solder alloy in low silver involved in the present invention has the brazing property better than Sn0.7Cu0.01Ni leadless welding alloy, and combination property is suitable with the Sn-3.0Ag-0.7Cu series lead-free solder.
The preferable range of copper content is 0.5～1.0%, and the preferable range of silver content is 0.10～0.55%.Because the tin content of Sn-0.3Ag-0.7Cu series lead-free solder alloy up to 99%, therefore, can increase the generation of scolder pot fusion welding surface metal oxide in the use.Add 0.001～0.10% element P and can stop the further oxidation of solder alloy effectively.In the use, molten braze alloy is by oxidation reaction (4P+5O in the scolder pot
2→ 2P
2O
5, SnO+P
2O
5→ SnOP
2O
5) can form one deck oxide-film as thin as a wafer on fusion welding surface, its can further hinder solder alloy directly and surrounding air be in contact with one another the generation oxidation reaction.To suppress oxidation effectiveness not obvious if the addition of element P is less than 0.001%, but surpass 0.10% when element P content, then the solderability that oxidative phenomena seriously will the deterioration solder alloy.P content preferable range is 0.005～0.10%.On the basis of adding element P, further add element Ge among the present invention, then can suppress Cu in printed circuit Cu substrate and the components and parts pin on the one hand, reduced Cu in the fusion welding to the dissolving of molten braze alloy
6Sn
5Growing amount, prolonged service life of scolder; But on the other hand since the Ge solid solution in Cu
6Sn
5Compound mutually in, thereby changed the form of this intermetallic compound, change into spherical by needle-like.And the spheroidizing compound is much smaller to the influence of fusion welding flowability, thereby reduces the possibility that bridging forms.When Ge content less than 0.001% the time, its effect is not obvious, surpasses at 0.01% o'clock if add Ge content, can make the solder performance variation, fusing point raises.The preferred addition of Ge is 0.001～0.005%.Also added micro-rare earth element ce among the present invention to improve the tissue of solder alloy.Because rare earth element can promote the forming core of solder alloy in process of setting, have rotten and homogenising effect, thereby improve the mechanical property of solder alloy, significantly improve the creep resistant fatigue behaviour of solder alloy.If ree content is less than 0.001%, its effect is just not obvious, if add the degradation that 0.01% above rare earth element can make solder alloy, fusing point raises.The preferred content of rare earth element is 0.005～0.01%.Add the wetting and spreading performance that rare earth element can also improve solder alloy among the present invention.Because rare earth element is a surface active element, adds the surface tension that suitable ree content can reduce molten braze alloy, improves the wettability of solder alloy.
Characteristics of the present invention:
Compared with prior art, the present invention has the following effect of having a mind to:
1, the present invention has added the alloying element (P, In, Ge, Ga, Ce) of a spot of silver and trace on the basis of Sn-0.7Cu leadless welding alloy, the key property of alloy is near the Sn-3.0Ag-0.7Cu lead-free solder alloy, good with existing welding procedure compatibility, alternative Sn-3.0Ag-0.7Cu lead-free solder alloy, and easily apply.
2, the present invention added micro-P and or Ge, Ga, Ce after, can make alloy in molten state and atmospheric environment, obtain high oxidation resistance.
3, the present invention can adopt prior art for preparing to become the lead-free solder product of various forms, as the lead-free solder ingot, and the welding rod piece, welding wire, miniature soldered ball, welding powder and soldering paste, the present invention is specially adapted to the Electronic Packaging technology in the microelectronics industry.
4, the present invention is easy to processing, and cost of manufacture is low.
The specific embodiment
Be described in further detail the present invention below in conjunction with embodiment.Certainly, the present invention is not limited to the concrete composition among the following embodiment.
Embodiment 1:
The tinbase intermediate alloy of configuration Sn-20wt%Ag, Sn-50wt%Cu, Sn-5wt%P, Sn-2wt%Ge, In, Sn all adopt the simple substance simple metal, by following percentage by weight configuration leadless welding alloy: Ag:0.30, Cu:0.70, P:0.005, In:0.01:Ge0.001, surplus Sn.Select for use common melting technique to carry out alloying smelting, obtain foundry alloy, foundry alloy is being placed an open pot, heat fused is until 260 ℃ under atmospheric environment, scrape off the liquid level scum silica frost, and insulation for a long time under this temperature, observe alloy melt liquid level change in color, to estimate the effect of resistance to high temperature oxidation.Found that insulation is after 8 hours down at 260 ℃, this alloy still can keep the brightness of liquid level.Alloy is after high temperature is cooled to room temperature, and surface-brightening is silvery white in color, and shows that this alloy has the good high-temperature antioxygenic property.
Embodiment 2:
The tinbase intermediate alloy of configuration Sn-20wt%Ag, Sn-50wt%Cu, Sn-5wt%P, In, Ga, Sn all adopt the simple substance simple metal, by following percentage by weight configuration leadless welding alloy: Ag:0.30, Cu:0.70, P:0.005, In:0.01:Ga:0.008, surplus Sn.Select for use common melting technique to carry out alloying smelting, obtain foundry alloy, foundry alloy is being placed an open pot, heat fused is until 260 ℃ under atmospheric environment, scrape off the liquid level scum silica frost, and insulation for a long time under this temperature, observe alloy melt liquid level change in color, to estimate the effect of resistance to high temperature oxidation.Found that insulation is after 8 hours down at 260 ℃, this alloy still can keep the brightness of liquid level.Alloy is after high temperature is cooled to room temperature, and surface-brightening is silvery white in color, and shows that this alloy has the good high-temperature antioxygenic property.
Embodiment 3:
The tinbase intermediate alloy of configuration Sn-20wt%Ag, Sn-50wt%Cu, Sn-5wt%P, Sn-2wt%Ce, In, Sn all adopt the simple substance simple metal, by following percentage by weight configuration leadless welding alloy: Ag:0.30, Cu:0.70, P:0.005, In:0.01:Ce:0.01, surplus Sn.Select for use common melting technique to carry out alloying smelting, obtain foundry alloy, foundry alloy is being placed an open pot, heat fused is until 260 ℃ under atmospheric environment, scrape off the liquid level scum silica frost, and insulation for a long time under this temperature, observe alloy melt liquid level change in color, to estimate the effect of resistance to high temperature oxidation.Found that insulation is after 8 hours down at 260 ℃, this alloy still can keep the brightness of liquid level.Alloy is after high temperature is cooled to room temperature, and surface-brightening is silvery white in color, and shows that this alloy has the good high-temperature antioxygenic property.
Embodiment 4:
The tinbase intermediate alloy of configuration Sn-20wt%Ag, Sn-50wt%Cu, Sn-5wt%P, Sn-2wt%Ge, Sn-2wt%Ce, In, Sn all adopt the simple substance simple metal, by following percentage by weight configuration leadless welding alloy: Ag:0.30, Cu:0.70, P:0.005, In:0.01:Ge:0.001, Ce:0.01, surplus Sn.Select for use common melting technique to carry out alloying smelting, obtain foundry alloy, foundry alloy is being placed an open pot, heat fused is until 260 ℃ under atmospheric environment, scrape off the liquid level scum silica frost, and insulation for a long time under this temperature, observe alloy melt liquid level change in color, to estimate the effect of resistance to high temperature oxidation.Found that insulation is after 8 hours down at 260 ℃, this alloy still can keep the brightness of liquid level.Alloy is after high temperature is cooled to room temperature, and surface-brightening is silvery white in color, and shows that this alloy has the good high-temperature antioxygenic property.
Embodiment 5:
The tinbase intermediate alloy of configuration Sn-20wt%Ag, Sn-50wt%Cu, Sn-5wt%P, Sn-2wt%Ce, In, Ga, Sn all adopt the simple substance simple metal, by following percentage by weight configuration leadless welding alloy: Ag:0.30, Cu:0.70, P:0.005, In:0.01:Ga:0.002, Ce:0.01, surplus Sn.Select for use common melting technique to carry out alloying smelting, obtain foundry alloy, foundry alloy is being placed an open pot, heat fused is until 260 ℃ under atmospheric environment, scrape off the liquid level scum silica frost, and insulation for a long time under this temperature, observe alloy melt liquid level change in color, to estimate the effect of resistance to high temperature oxidation.Found that insulation is after 8 hours down at 260 ℃, this alloy still can keep the brightness of liquid level.Alloy is after high temperature is cooled to room temperature, and surface-brightening is silvery white in color, and shows that this alloy has the good high-temperature antioxygenic property.
Claims (6)
1, oxidation resistant lead-free solder alloy in low silver is characterized in that it comprises the composition of following percentage by weight: Ag:0.10～0.55, Cu:0.5～1.0, and surplus is Sn.
2, oxidation resistant lead-free solder alloy in low silver according to claim 1 is characterized in that the silver content percentage by weight is 0.10～0.55.
3, oxidation resistant lead-free solder alloy in low silver according to claim 1 is characterized in that copper content percentage by weight is 0.5～1.0.
4, according to claim 1 or 2 or 3 described oxidation resistant lead-free solder alloy in low silver, it is characterized in that in the above-mentioned leadless welding alloy, further add percentage by weight and be 0.001～0.1 P.
5, according to claim 1 or 2 or 3 described oxidation resistant lead-free solder alloy in low silver, it is characterized in that in the above-mentioned leadless welding alloy, further add percentage by weight and be 0.005～0.1 In.
6, according to claim 1 or 2 or 3 described oxidation resistant lead-free solder alloy in low silver, it is characterized in that in the above-mentioned leadless welding alloy, further add percentage by weight and be 0.0005～0.01 Ge, Ga or Ce or their combination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100427716A CN101585119A (en) | 2009-02-26 | 2009-02-26 | Oxidation resistant low silver lead-free solder alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100427716A CN101585119A (en) | 2009-02-26 | 2009-02-26 | Oxidation resistant low silver lead-free solder alloy |
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| Publication Number | Publication Date |
|---|---|
| CN101585119A true CN101585119A (en) | 2009-11-25 |
Family
ID=41369647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100427716A Pending CN101585119A (en) | 2009-02-26 | 2009-02-26 | Oxidation resistant low silver lead-free solder alloy |
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| CN (1) | CN101585119A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102862001A (en) * | 2012-10-10 | 2013-01-09 | 浙江高博焊接材料有限公司 | Sn-Ag-Cu lead-free solder containing Nd, Te and Ga |
| CN103978323A (en) * | 2014-05-27 | 2014-08-13 | 北京理工大学 | Lead-free solder |
| CN105345305A (en) * | 2015-10-28 | 2016-02-24 | 仲恺农业工程学院 | Sn-Ag-Cu-Tc low-silver lead-free solder |
| CN109082559A (en) * | 2018-09-03 | 2018-12-25 | 云南锡业锡材有限公司 | A kind of low silver-colored high-reliability lead-free solder alloy of SnAgCuNiGeCe |
| CN112322929A (en) * | 2020-10-28 | 2021-02-05 | 云南锡业集团（控股）有限责任公司研发中心 | Intermediate alloy for improving oxidation resistance of solder |
| 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 |
| CN113857713A (en) * | 2021-09-15 | 2021-12-31 | 昆明理工大学 | Low-silver Sn-Ag-Cu lead-free solder and preparation method thereof |
| CN114161023A (en) * | 2014-04-30 | 2022-03-11 | 日本斯倍利亚股份有限公司 | Lead-free solder alloy |
-
2009
- 2009-02-26 CN CNA2009100427716A patent/CN101585119A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102862001A (en) * | 2012-10-10 | 2013-01-09 | 浙江高博焊接材料有限公司 | Sn-Ag-Cu lead-free solder containing Nd, Te and Ga |
| CN102862001B (en) * | 2012-10-10 | 2015-04-01 | 浙江高博焊接材料有限公司 | Sn-Ag-Cu lead-free solder containing Nd, Te and Ga |
| CN114161023A (en) * | 2014-04-30 | 2022-03-11 | 日本斯倍利亚股份有限公司 | Lead-free solder alloy |
| CN103978323A (en) * | 2014-05-27 | 2014-08-13 | 北京理工大学 | Lead-free solder |
| CN105345305A (en) * | 2015-10-28 | 2016-02-24 | 仲恺农业工程学院 | Sn-Ag-Cu-Tc low-silver lead-free solder |
| CN109082559A (en) * | 2018-09-03 | 2018-12-25 | 云南锡业锡材有限公司 | A kind of low silver-colored high-reliability lead-free solder alloy of SnAgCuNiGeCe |
| CN109082559B (en) * | 2018-09-03 | 2021-09-28 | 云南锡业锡材有限公司 | SnAgCuNiGeCe low-silver high-reliability lead-free solder alloy |
| CN112322929A (en) * | 2020-10-28 | 2021-02-05 | 云南锡业集团（控股）有限责任公司研发中心 | Intermediate alloy for improving oxidation resistance of solder |
| 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 |
| CN113857713A (en) * | 2021-09-15 | 2021-12-31 | 昆明理工大学 | Low-silver Sn-Ag-Cu lead-free solder and preparation method thereof |
| CN113857713B (en) * | 2021-09-15 | 2023-02-28 | 昆明理工大学 | Low-silver Sn-Ag-Cu lead-free solder and preparation method thereof |
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