CN108994480A - A kind of SnBiAgCu high-reliability lead-free solder alloy - Google Patents
A kind of SnBiAgCu high-reliability lead-free solder alloy Download PDFInfo
- Publication number
- CN108994480A CN108994480A CN201811177450.2A CN201811177450A CN108994480A CN 108994480 A CN108994480 A CN 108994480A CN 201811177450 A CN201811177450 A CN 201811177450A CN 108994480 A CN108994480 A CN 108994480A
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- Prior art keywords
- snbiagcu
- free solder
- solder alloy
- lead
- alloy
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—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
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3601—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
Abstract
A kind of SnBiAgCu high-reliability lead-free solder alloy, by weight percentage, include: the Ni of Bi, 0.01-0.5% of Sb, 0.5-10% of In, 0.1-10% of Cu, 0.5-10% of Ag, 0.4-4% of 0.1-5%, total amount are in P, Ge or Ga of 0-0.1%, the Sn of surplus and inevitable impurity.For the present invention by the addition of the alloying elements such as Ag, Sb, Ni, In, the enrichment of Bi can be hindered in interface by being formed after solder joint, prevent SnBi eutectic structure from being formed, reduce the damage of Welded Joints mechanical performance, weld strength is improved, while under different technological temperatures, there is preferable inoxidizability.
Description
Technical field
The present invention relates to leadless welding alloy technical fields.
Background technique
Since electronic solder is unleaded, widely used is SnCu system, SnAgCu system, the conjunction of SnBi system solder
Gold.SnAgCu system wetability is good, has preferable soldering reliability and process yields, but that there is also fusing points is higher, at high cost, with
Silver content increase anti-drop reduce the disadvantages of.Cost is relatively low for Sn-Cu system, but fusing point is high, wetability is poor.Sn-Bi system is molten
Point is low, wetability is preferable, but due to containing poor reliability after Bi higher welding.Publication No. CN1927525 and CN101380700B
Chinese patent individually disclose a series of solders, these solders are due to being added to rare earth element, and Rare-Earth Element Chemistry property
It is very active, it is easy to aoxidize, solder surface tension can be made to increase, reduce the wetability of solder, is unfavorable for welding.The addition meeting of Zn
The defects of making welding point rough surface, tarnish, and the oxidizable influence mobility of Zn, leading to bridging and draw point increase, and
And corrosion etc. easily occurs for welding point.The addition of Fe can be such that glutinous slag increases, and form the defects of drawing point, bridging.The addition of Al can make
There is sand shape in welding point, reduces the reliability of welding point.In order to guarantee welding quality and postwelding reliability, Zn,
The elements such as Fe, Al, rare earth element all must be strictly controlled its ingredient in microalloying, simultaneously because the content of Bi is very high, crisp
Property larger and with " pyrocondensation cold expanding " characteristic, therefore there are still wetability is poor, melting range big (poor fluidity), weld after can
The disadvantages of poor by property.
Summary of the invention
Present invention seek to address that the deficiencies in the prior art, provide a kind of segregation that can inhibit Bi element, improving welding property,
The SnBiAgCu high-reliability lead-free solder alloy of comprehensive good welding performance.
The technical solution adopted by the present invention is as follows:
A kind of SnBiAgCu high-reliability lead-free solder alloy, the weight percent composition of the leadless welding alloy are as follows:
The Ag of 0.1-5%；
The Cu of 0.4-4%；
The In of 0.5-10%；
The Sb of 0.1-10%；
The Bi of 0.5-10%；
The Ni of 0.01-0.5%；
With any one in following element, two or three of compound addition, total amount is within the scope of 0-0.1%:
The P of 0-200ppm；
The Ga of 0-200ppm；
The Ge of 0-200ppm；
And the Sn and inevitable impurity of surplus.
During the preparation process, Ag, Cu, Sb, In, Ni, Ge, P are prepared among SnX and close leadless welding alloy of the present invention
Golden form addition, remaining Bi, Ga are added with pure material, and insufficient Sn is added with pure Sn.
The intermediate alloy of Ag, Cu, Ge, P, Sb, In, Ni of the present invention using vacuum melting furnace prepare, preparation ratio and
Smelting temperature is respectively:
Ag:Sn-3%Ag, 500 DEG C；
Cu:Sn-10%Cu, 650 DEG C；
Sb:Sn-10%Sb, 500 DEG C；
In:Sn-52%In, 350 DEG C；
Ni:Sn-4%Ni, 700 DEG C
Ge:Sn-1%Ge, 400 DEG C；
P:Sn-1%P, 450 DEG C.
Lead-free solder form of the present invention be powdery, paste, BGA soldered ball, centreless or have core welding wire shape, rodlike, strip,
Any one of ingot shape, foil-like.
A small amount of Bi, In and Ni that SnBiAgCu leadless welding alloy of the present invention contains, improves the wetting of solder alloy
Property and welding performance.Bi member can be effectively suppressed under " pinning " effect of the elements such as Sb by the compound addition of Ag, Sb element
The segregation and the brittleness in the welding street corner of enrichment and generation of element, improve weld strength, can also improve the surface characteristic of fusion welding,
The surface tension for reducing fusion welding, promotes the wetting of solder, improves the welding performance of solder alloy.When In content is lower,
In can be solid-solubilized in Sn, and the In atom of solid solution can hinder the movement of dislocation；Weldering is improved by the compound addition of P, Ge, Ga
The inoxidizability of material, in wave-soldering and solder dip process, solder is in molten state for a long time, and melt is in higher temperature at this time
Under degree, and contacted with air, to generate various metal oxides, metal oxide and melted metal are adhered to, thus
One layer of grume mixture is formed on surface, not only causes the loss of a large amount of solder metals, but also influence the flowing of solder melt
Property, it is easy to produce the technological problems such as failure welding, slag inclusion.P, bath surface metal can be effectively reduced in the compound addition of Ge, Ga
Oxidation, especially under higher technological temperature, the inoxidizability rate of exchange of alloy are lasting, stablize, and anti-oxidizing elements consume
It is slow；Simultaneously in the welding process, the adherency in the oxide and metal bath of Surface Creation, the flowing of solder melt are prevented
Property is preferably kept, and welding quality is more stable.
Detailed description of the invention
Fig. 1 is the DSC curve of the solder alloy SnAg3Cu3In1Sb1.5Bi0.6Ni0.01Ga of embodiment 3；
Fig. 2 is the solder alloy SnAg2Cu0.7In0.5Sb3.0Bi2.0Ni0.01PGa sample tensile test of embodiment 8
The load-displacement curves obtained afterwards.
Specific embodiment
Invention is further described in detail With reference to embodiment, but protection scope of the present invention and unlimited
In the content.
The weight percent of SnBiAgCu high-reliability lead-free solder of the invention forms are as follows:
The Ag of 0.1-5%；
The Cu of 0.4-4%；
The In of 0.5-10%；
The Sb of 0.1-10%；
The Bi of 0.5-10%；
The Ni of 0.01-0.5%；
With any one in following element, two or three of compound addition, total amount is within the scope of 0-0.1%:
The P of 0-200ppm；
The Ga of 0-200ppm；
The Ge of 0-200ppm；
And the Sn and inevitable impurity of surplus.
During the preparation process, Ag, Cu, Sb, In, Ni, Ge, P are prepared into SnX intermediate alloy form and add the lead-free solder
Add, remaining Bi, Ga are added with pure material, and insufficient Sn is added with pure Sn.
The intermediate alloy of above-mentioned Ag, Cu, Ge, P, Sb, In, Ni are prepared using vacuum melting furnace, prepare ratio and melting temperature
Degree is respectively:
Ag:Sn-3%Ag, 500 DEG C；
Cu:Sn-10%Cu, 650 DEG C；
Sb:Sn-10%Sb, 500 DEG C；
In:Sn-52%In, 350 DEG C；
Ni:Sn-4%Ni, 700 DEG C
Ge:Sn-1%Ge, 400 DEG C；
P:Sn-1%P, 450 DEG C.
The lead-free solder form being prepared be powdery, paste, BGA soldered ball, centreless or have core welding wire shape, rodlike, strip,
Any one of ingot shape, foil-like, there is no limit for solder form.
The present invention lists specific 8 lead-free solder embodiments.Comparative example SAC3005 solder is used simultaneously to carry out pair
Than.
The alloy formula of 8 embodiments is as shown in table 1 (being calculated in mass percent).
Fusing point, heating rate 5K/min are tested using DSC131evo type differential scanning calorimetric analysis instrument；Using
MUSTSYSTEM II type Weldability detector measures the wetting power of solder, and base material isFine copper silk, help weldering
Agent is KESTER 985-M, 270 DEG C of experimental temperature, immersion depth 3mm, immerses speed 10mm/s, immerses time 3s；Using
REGER type mechanics machine tested for tensile strength, tensile speed 2mm/min.
The fusing point of 8 embodiments and comparative example is as shown in table 1, and the results are shown in Table 2 for wetability, mechanical property result such as table
Shown in 3.Alloy number 1~8 in 1~table of table 3 respectively refers to the solder alloy number of Examples 1 to 8.
1 fusing point of table
2 wetability of table
| Alloy number | Ta(s) | Tb(s) | T2/3Fmax | Fmax |
| Embodiment 1 | 0.4681 | 0.4808 | 0.5653 | 0.9746 |
| Embodiment 2 | 0.4498 | 0.4647 | 0.5520 | 0.9889 |
| Embodiment 3 | 0.4481 | 0.4613 | 0.5460 | 0.9387 |
| Embodiment 4 | 0.4673 | 0.4821 | 0.5693 | 0.9438 |
| Embodiment 5 | 0.4630 | 0.4730 | 0.5550 | 0.9104 |
| Embodiment 6 | 0.4542 | 0.4606 | 0.5406 | 0.9732 |
| Embodiment 7 | 0.4363 | 0.4498 | 0.5315 | 0.9581 |
| Embodiment 8 | 0.4780 | 0.4920 | 0.5780 | 0.9593 |
| SAC305 | 0.4441 | 0.4566 | 0.5463 | 1.0884 |
3 tensile strength of table
| Alloy number | Tensile strength (MPa) | Elongation at break (%) |
| Embodiment 1 | 74.01 | 39.19 |
| Embodiment 2 | 87.51 | 36.52 |
| Embodiment 3 | 65.12 | 40.43 |
| Embodiment 4 | 43.43 | 61.78 |
| Embodiment 5 | 50.8 | 45.6 |
| Embodiment 6 | 93.95 | 15.64 |
| Embodiment 7 | 71.03 | 28.11 |
| Embodiment 8 | 76.53 | 44.48 |
| SAC305 | 53.7 | 42.17 |
From table 1,2,3 as can be seen that the fusion temperature of any leadless welding alloy of the embodiment of the present invention 1~8 is below
SAC305, and compared with SAC305, the wetability of alloy is suitable with SAC305, and mechanical property all increases.
Claims (4)
1. a kind of SnBiAgCu high-reliability lead-free solder alloy, which is characterized in that the weight percent of the leadless welding alloy
Composition are as follows:
The Ag of 0.1-5%；
The Cu of 0.4-4%；
The In of 0.5-10%；
The Sb of 0.1-10%；
The Bi of 0.5-10%；
The Ni of 0.01-0.5%；
With any one in following element, two or three of compound addition, total amount is within the scope of 0-0.1%:
The P of 0-200ppm；
The Ga of 0-200ppm；
The Ge of 0-200ppm；
And the Sn and inevitable impurity of surplus.
2. a kind of SnBiAgCu high-reliability lead-free solder alloy according to claim 1, which is characterized in that described unleaded
Solder alloy during the preparation process, Ag, Cu, Sb, In, Ni, Ge, P be prepared into SnX intermediate alloy form addition, remaining Bi, Ga with
Pure material addition, insufficient Sn are added with pure Sn.
3. a kind of SnBiAgCu high-reliability lead-free solder alloy according to claim 2, which is characterized in that the Ag,
The intermediate alloy of Cu, Ge, P, Sb, In, Ni are prepared using vacuum melting furnace, and preparation ratio and smelting temperature are respectively:
Ag:Sn-3%Ag, 500 DEG C；
Cu:Sn-10%Cu, 650 DEG C；
Sb:Sn-10%Sb, 500 DEG C；
In:Sn-52%In, 350 DEG C；
Ni:Sn-4%Ni, 700 DEG C
Ge:Sn-1%Ge, 400 DEG C；
P:Sn-1%P, 450 DEG C.
4. a kind of SnBiAgCu high-reliability lead-free solder alloy according to any one of claims 1 to 4, feature exist
In, the lead-free solder form be powdery, paste, BGA soldered ball, centreless or have core welding wire shape, rodlike, strip, ingot shape, in foil-like
It is any.
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| CN201811177450.2A CN108994480A (en) | 2018-10-10 | 2018-10-10 | A kind of SnBiAgCu high-reliability lead-free solder alloy |
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| CN201811177450.2A CN108994480A (en) | 2018-10-10 | 2018-10-10 | A kind of SnBiAgCu high-reliability lead-free solder alloy |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109732237A (en) * | 2019-01-02 | 2019-05-10 | 昆明理工大学 | A kind of SnBiCuAgNiCe low temperature lead-free solder alloy |
| CN111390424A (en) * | 2020-04-21 | 2020-07-10 | 深圳市唯特偶新材料股份有限公司 | Tin-plated copper strip coating anti-oxidation solder alloy and preparation method thereof |
| 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 |
| CN112643241A (en) * | 2020-12-10 | 2021-04-13 | 昆明理工大学 | Sn-Bi-Cu-Ag-Ni-Sb low-temperature high-mechanical-property lead-free solder alloy |
| CN113070606A (en) * | 2021-04-15 | 2021-07-06 | 云南锡业锡材有限公司 | Sn-Ag-Cu high-performance lead-free solder and preparation method thereof |
| CN114559178A (en) * | 2021-12-21 | 2022-05-31 | 西安理工大学 | Sn-Bi-Ag series lead-free solder and preparation method thereof |
| 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 |
| EP3903993A4 (en) * | 2018-12-25 | 2022-09-07 | Tamura Corporation | Lead-free solder alloy, solder joining material, electronic circuit mounting board, and electronic control device |
| JP7161133B1 (en) | 2021-09-30 | 2022-10-26 | 千住金属工業株式会社 | Solder alloys, solder balls, solder preforms, solder pastes and solder joints |
| JP7161134B1 (en) | 2021-09-30 | 2022-10-26 | 千住金属工業株式会社 | Solder alloys, solder balls, solder preforms, solder pastes and solder joints |
| JP2022546078A (en) * | 2019-09-02 | 2022-11-02 | アルファ・アセンブリー・ソリューションズ・インコーポレイテッド | High temperature ultra-reliable alloy |
| CN115430949A (en) * | 2022-10-09 | 2022-12-06 | 云南锡业集团（控股）有限责任公司研发中心 | Five-membered eutectic high-toughness low-temperature tin-bismuth series solder and preparation method thereof |
| CN115476069A (en) * | 2022-10-28 | 2022-12-16 | 云南锡业集团（控股）有限责任公司研发中心 | Five-membered or six-membered lead-free tin-based solder with low Ag, high thermal stability and high toughness |
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| US11724341B2 (en) | 2018-12-25 | 2023-08-15 | Tamura Corporation | Lead-free solder alloy, solder joining material, electronic circuit mounting substrate, and electronic control device |
| EP3903993A4 (en) * | 2018-12-25 | 2022-09-07 | Tamura Corporation | Lead-free solder alloy, solder joining material, electronic circuit mounting board, and electronic control device |
| CN109732237A (en) * | 2019-01-02 | 2019-05-10 | 昆明理工大学 | A kind of SnBiCuAgNiCe low temperature lead-free solder alloy |
| JP2022546078A (en) * | 2019-09-02 | 2022-11-02 | アルファ・アセンブリー・ソリューションズ・インコーポレイテッド | High temperature ultra-reliable alloy |
| CN111390424A (en) * | 2020-04-21 | 2020-07-10 | 深圳市唯特偶新材料股份有限公司 | Tin-plated copper strip coating anti-oxidation solder alloy and preparation method thereof |
| 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 |
| CN112643241A (en) * | 2020-12-10 | 2021-04-13 | 昆明理工大学 | Sn-Bi-Cu-Ag-Ni-Sb low-temperature high-mechanical-property lead-free solder alloy |
| CN113070606A (en) * | 2021-04-15 | 2021-07-06 | 云南锡业锡材有限公司 | Sn-Ag-Cu high-performance lead-free solder and preparation method thereof |
| JP2023051074A (en) * | 2021-09-30 | 2023-04-11 | 千住金属工業株式会社 | Solder alloy, solder ball, solder preform, solder paste, and solder joint |
| JP7161134B1 (en) | 2021-09-30 | 2022-10-26 | 千住金属工業株式会社 | Solder alloys, solder balls, solder preforms, solder pastes and solder joints |
| JP7161133B1 (en) | 2021-09-30 | 2022-10-26 | 千住金属工業株式会社 | Solder alloys, solder balls, solder preforms, solder pastes and solder joints |
| WO2023054630A1 (en) * | 2021-09-30 | 2023-04-06 | 千住金属工業株式会社 | Solder alloy, solder ball, solder preform, solder paste, and solder joint |
| WO2023054629A1 (en) * | 2021-09-30 | 2023-04-06 | 千住金属工業株式会社 | Solder alloy, solder ball, solder preform, solder paste, and solder joint |
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| TWI818752B (en) * | 2021-09-30 | 2023-10-11 | 日商千住金屬工業股份有限公司 | Solder alloys, solder balls, solder preforms, solder pastes and solder joints |
| CN114559178A (en) * | 2021-12-21 | 2022-05-31 | 西安理工大学 | Sn-Bi-Ag series lead-free solder and preparation method thereof |
| 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 |
| CN115430949A (en) * | 2022-10-09 | 2022-12-06 | 云南锡业集团（控股）有限责任公司研发中心 | Five-membered eutectic high-toughness low-temperature tin-bismuth series solder and preparation method thereof |
| CN115430949B (en) * | 2022-10-09 | 2024-04-05 | 云南锡业集团（控股）有限责任公司研发中心 | Five-membered eutectic high-toughness low-Wen Xibi-series solder and preparation method thereof |
| CN115476069A (en) * | 2022-10-28 | 2022-12-16 | 云南锡业集团（控股）有限责任公司研发中心 | Five-membered or six-membered lead-free tin-based solder with low Ag, high thermal stability and high toughness |
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