CN103341699A - Unleaded Sn-In-Ag brazing filler metal replacing tin-lead brazing filler metal - Google Patents
Unleaded Sn-In-Ag brazing filler metal replacing tin-lead brazing filler metal Download PDFInfo
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- CN103341699A CN103341699A CN2013102803664A CN201310280366A CN103341699A CN 103341699 A CN103341699 A CN 103341699A CN 2013102803664 A CN2013102803664 A CN 2013102803664A CN 201310280366 A CN201310280366 A CN 201310280366A CN 103341699 A CN103341699 A CN 103341699A
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Abstract
Unleaded Sn-In-Ag brazing filler metal replacing tin-lead brazing filler metal is low in welding point and good in welding technology performance and mechanical performance. The unleaded Sn-In-Ag brazing filler metal replacing the tin-lead brazing filler metal is composed of 8%-35% of In, 0.1%-5% of Ag, 0.01%-3% of Bi, 0.01%-3% of Sb, 0-1% of Cu, 0.01%-0.2% of Ni, 0.0005%-0.1% of P, 0.0005%-0.1% of X and the balance of Sn with the total weight of brazing filler metal as a benchmark, wherein the X is one or any mixture of Ga, Ge and mixed rare earth. The unleaded Sn-In-Ag brazing filler metal replacing the tin-lead brazing filler metal is suitable for being used as the brazing filler metal.
Description
Technical field
The present invention relates to a kind of lead-free brazing, it can be applicable to wave-soldering, Reflow Soldering and the manual welding in electronics and microelectronics Packaging field, and this solder can directly replace traditional tin-lead solder.
Background technology
All the time, tin-lead solder is widely used.Along with the raising of environmental requirement, countries in the world begin to advocate the employing lead-free brazing.On July 1st, 2006, European Union implements WEEE and ROHS rule simultaneously, and restriction is carried out in the use of solder containing lead.China begins restriction in March, 2007 and uses solder containing lead.In the lead-free brazing class that substitutes the Sn-37Pb solder, Sn-Ag-Cu (SAC) brazing filler metal is recognized the world over.Yet the fusing point of Sn-Ag-Cu brazing filler metal is than high more than 30 degree of traditional Sn-37Pb solder, and therefore, technological temperature also rises thereupon, and this is that industry is undesirable.
In the electronics industry, need the surface element of lower temperature assembling to become the unleaded obstacle of implementation solder, for solving this problem, must exploitation lead-free brazing technology and the material suitable even lower with traditional Sn-37Pb solder fusing point.The welding material that can realize low-temperature mounting has Sn-Zn system, Sn-In system and Sn-Bi system etc.In various candidate's lead-free alloys, tin (Sn) all is used as base metal basically, and other metals common and that tin is used comprise silver (Ag), indium (In), zinc (Zn), antimony (Sb), copper (Cu) and bismuth (Bi).Why selecting these materials, is because generally can reduce fusing point when they and tin component alloy, obtains desirable machinery, electric and hot property.Wherein, indium is the active ingredient that reduces the ashbury metal fusing point.The solder alloy series that contains indium, it is low because of fusing point, antifatigue and ductility is good, electric conductivity is high, Joint Strength is high, good reliability, especially have a good wetability to pottery, glass etc. are nonmetal, become one of main solder of microelectronics assembling at present.
US 5938862 discloses the SAC soft solder that has the 8-10wt% indium under the situation that contains 2.3wt% silver and 1wt% copper, and its fusing point declines to a great extent and toughness strengthens.
WO 03/051572Al discloses the SAC lead-free solder that contains indium 0.8-1.2wt%, can avoid the smooth and homogeneous that forms the dendrite of tin and can guarantee the solder surface after fusion, and solder has higher alternation load intensity.
WO 97/43456 is at the fatigue of materials problem that causes owing to temperature inversion at automotive field, the lead-free solder of exploitation, and it contains 68.2-91.8wt% tin, 3.2-3.8% silver and 5-5.5% indium.
Although above three kinds of solders have excellent performance, fusing point still is higher than the Sn-37Pb solder.
Summary of the invention
The invention reside in Sn-Ag-Cu (SAC) the series leadless solder fusing point height that will solve alternative traditional Sn-37Pb solder of generally acknowledging the world today, be unfavorable for the assembling of electronic component low temperature, and the problem of the technology of common lead-free brazing soldering, poor mechanical property, a kind of Sn-In-Ag lead-free brazing that replaces tin-lead solder is provided for this reason, this solder fusing point and Sn-37Pb's is suitable, and have good soldering processes performance and mechanical property, nontoxic pollution-free.
For addressing the above problem, its special character of technical scheme that lead-free brazing of the present invention adopts is to be that benchmark is made of following component with described solder gross weight: In 8 ~ 35%, Ag 0.1 ~ 5%, and Bi 0.01 ~ 3%, and Sb 0.01 ~ 3%, Cu 0 ~ 1%, Ni 0.01 ~ 0.2%, P 0.0005-0.1 %, X 0.0005-0.1 %, the Sn surplus, X is a kind of or several combination arbitrarily in Ga, Ge, the mishmetal.
The present invention is preferably: In 10-20%, Ag 2-4 %, Bi 0.5-2.5%, Sb 0.5-2%, Ni 0.02-0.2 %, P 0.001-0.02 %, X 0.001-0.02 %.
The preparation method of Sn-In-Ag lead-free solder of the present invention: in proportion with the Sn-Ag intermediate alloy, the Sn-Ni intermediate alloy, the Sn-Bi intermediate alloy, Sn-Sb intermediate alloy and In ingot, Sn ingot are put into vacuum melting furnace or non-vacuum melting stove, at 400-500 ℃ of melting 0.5-1h, then with the Sn-P intermediate alloy, the Sn-X intermediate alloy joins in the smelting furnace, fully stirs before coming out of the stove, and prepares required brazing filler metal alloy.
Sn-In-Ag lead-free solder alloy melting point of the present invention and Sn37Pb approach, and its tensile strength is not less than 40MPa.
Be made into any or multiple in solder foundry alloy or solder piece, welding rod, welding wire, soldered ball, welding powder, the soldering paste when the present invention prepares, be applied to electronics and microelectronics assembling field.
A kind of Sn-In-Ag lead-free solder alloy of the present invention is nontoxic, pollution-free, and cost is low, and non-oxidizability is strong, and good combination property satisfies welding requirements such as wave-soldering, Reflow Soldering and manual welding.
Compared with prior art, the present invention has following remarkable result:
1. the fusing point of novel alloy of the present invention is lower, can utilize splicer's skill equipment to carry out the electronics assembling.
2. add Cu in the Sn-In-Ag lead-free solder of the present invention, reduced fusing point, improved the intensity of solder, reduced molten copper rate.
3. add the P of trace in the Sn-In-Ag lead-free solder of the present invention as the antioxidant of solder, the non-oxidizability of solder is significantly improved.
4. add Bi in the Sn-In-Ag lead-free solder of the present invention, reduced the fusing point of solder, improved the wetting behavior of solder, improved the tensile strength of solder.
5. add Sb in the Sn-In-Ag lead-free solder of the present invention, improved the mechanical property of solder, improved the reliability of solder.
6. add Ni in the Sn-In-Ag lead-free solder of the present invention, reduced the corrode to copper base when having reduced the brazing filler metal alloy soldering; Refinement simultaneously compound pattern between interface metal, improved the reliability of solder joint.
7. added Ga in the Sn-In-Ag lead-free solder of the present invention, a kind of or any several combination in Ge and the mishmetal can make alloy have oxidation resistance and wettability preferably under molten condition.
The specific embodiment
Lead-free solder of the present invention is benchmark with its weight, and contained component and content thereof are provided by the embodiment of table 1, and has tested tensile strength, fusing point, the rate of spread and the antioxygenic property of embodiment and comparative example.
The component of the percentage composition among the embodiment is fed intake with the intermediate alloy form, in proportion with the Sn-Ag intermediate alloy, the Sn-Ni intermediate alloy, the Sn-Bi intermediate alloy, Sn-Sb intermediate alloy and In ingot, the Sn ingot is put into vacuum melting furnace or non-vacuum melting stove, at 400-500 ℃ of melting 0.5-1h, then with the Sn-P intermediate alloy, the Sn-X intermediate alloy joins in the smelting furnace, fully stir before coming out of the stove, casting solidification obtains brazing filler metal alloy, also can be processed into solder piece, solder bar, welding wire, weld tabs, soldered ball, welding powder or soldering paste.
Be that example prepares alloy process and states three kinds of modes as follows with embodiment 3:
Mode one: with Sn-Ag intermediate alloy 2.8kg, Sn-Ni intermediate alloy 0.05kg, Sn-Bi intermediate alloy 0.0017kg, Sn-Sb intermediate alloy 1kg and In ingot 2kg, Sn ingot 3.94kg puts into vacuum melting furnace or non-vacuum melting stove, at 450 ℃ of melting 45min, then with Sn-P intermediate alloy 0.2kg, Sn-X intermediate alloy 0.007kg joins in the smelting furnace, fully stirs before coming out of the stove, and casting solidification obtains brazing filler metal alloy.
Mode two: the smelting temperature that is that is different from mode one is 400 ℃, and smelting time is 1h, and other are identical with mode one.
Mode three: the smelting temperature that is that is different from mode one is 500 ℃, and smelting time is 0.5h, and other are identical with mode one.
Table 1 embodiment and Comparative Examples component and technical indicator
Annotate: 1. table 1 result all finishes under same test conditions.
2. the liquid film flavescence time is an index of scalar oxidation (anti-oxidant).
Lead-free solder fusing point of the present invention is moderate, have good cold and hot working performance, and advantage such as good in oxidation resistance, good mechanical properties, wetability are good is suitable for wave-soldering, Reflow Soldering and the manual welding in electronics and microelectronics Packaging field, is worth of widely use.
Although describe the present invention with embodiment, these embodiment explain not limit the present invention.For a person skilled in the art, should be understood that, in not deviating from claim of the present invention, under the situation of claimed scope, can carry out various improvement and variation to above-mentioned embodiment.
Claims (4)
1. Sn-In-Ag lead-free solder, it is characterized in that with described solder gross weight being that benchmark is made of following component: In 8 ~ 35%, and Ag 0.1 ~ 5%, and Bi 0.01 ~ 3%, and Sb 0.01 ~ 3%, and Cu 0 ~ 1%
Ni 0.01 ~ 0.2%, P 0.0005-0.1 %, and X 0.0005-0.1 %, the Sn surplus, X is a kind of or several combination arbitrarily in Ga, Ge, the mishmetal.
2. lead-free brazing as claimed in claim 1 is characterized in that: In 10-20%, Ag 2-4 %, Bi 0.5-2.5%, Sb 0.5-2%, Ni 0.02-0.2 %, P 0.001-0.02 %, X 0.001-0.02 %.
3. the preparation method of solder as claimed in claim 1 or 2, it is characterized in that: in proportion with the Sn-Ag intermediate alloy, the Sn-Ni intermediate alloy, the Sn-Bi intermediate alloy, Sn-Sb intermediate alloy and In ingot, Sn ingot are put into vacuum melting furnace or non-vacuum melting stove, at 400-500 ℃ of melting 0.5-1h, then with the Sn-P intermediate alloy, the Sn-X intermediate alloy joins in the smelting furnace, fully stirs before coming out of the stove, and casting solidification obtains brazing filler metal alloy.
4. the preparation method of solder as claimed in claim 3 is characterized in that described solder is made at least a in solder piece, solder bar, welding wire, weld tabs, soldered ball, welding powder or the soldering paste.
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| CN2013102803664A CN103341699A (en) | 2013-07-04 | 2013-07-04 | Unleaded Sn-In-Ag brazing filler metal replacing tin-lead brazing filler metal |
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| CN2013102803664A CN103341699A (en) | 2013-07-04 | 2013-07-04 | Unleaded Sn-In-Ag brazing filler metal replacing tin-lead brazing filler metal |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104625464A (en) * | 2014-12-23 | 2015-05-20 | 苏州龙腾万里化工科技有限公司 | Novel lead-free tin bar |
| CN104858564A (en) * | 2015-06-01 | 2015-08-26 | 谷华 | Soldering tin capable of not dissolving copper |
| CN105665956A (en) * | 2016-03-23 | 2016-06-15 | 徐宏达 | Soft solder alloy used for brazing aluminum and brazing aluminum alloy |
| EP2979807A4 (en) * | 2014-06-24 | 2016-12-07 | Harima Chemicals Inc | Solder alloy, solder composition, solder paste and electronic circuit board |
| CN108672979A (en) * | 2018-06-06 | 2018-10-19 | 上海莜玮汽车零部件有限公司 | A kind of leadless welding alloy and its application, glass assembly |
| CN108714749A (en) * | 2018-05-30 | 2018-10-30 | 江苏恒加机械工程有限公司 | A kind of preparation method of high brittle alloy weld tabs |
| CN108994480A (en) * | 2018-10-10 | 2018-12-14 | 云南锡业锡材有限公司 | A kind of SnBiAgCu high-reliability lead-free solder alloy |
| CN109175770A (en) * | 2018-09-30 | 2019-01-11 | 苏州优诺电子材料科技有限公司 | A kind of high intensity low-temperature lead-free solder and preparation method thereof |
| CN109894768A (en) * | 2019-03-29 | 2019-06-18 | 东莞市千岛金属锡品有限公司 | A kind of low temperature leadless alloy solder and preparation method thereof |
| CN111590235A (en) * | 2020-06-11 | 2020-08-28 | 中山翰华锡业有限公司 | Low-dielectric-loss high-reliability soldering paste and preparation method thereof |
| TWI744907B (en) * | 2019-05-27 | 2021-11-01 | 日商千住金屬工業股份有限公司 | Solder alloy, solder paste, preform solder, solder ball, wire solder, grease-filled solder, solder joint, electronic circuit board and multilayer electronic circuit board |
| CN115041799A (en) * | 2022-05-25 | 2022-09-13 | 云南前沿液态金属研究院有限公司 | Alloy material for low-temperature welding of indium tin oxide film and welding method |
| CN115139008A (en) * | 2015-05-15 | 2022-10-04 | 安波福技术有限公司 | Lead-free solder based on indium-tin-silver |
| 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 |
| CN115502604A (en) * | 2022-09-29 | 2022-12-23 | 安徽科技学院 | Brazing filler metal for magnesium alloy, using method and soldering flux thereof |
| 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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Cited By (26)
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| US9931716B2 (en) | 2014-06-24 | 2018-04-03 | Harima Chemicals, Incorporated | Solder alloy, solder composition, solder paste, and electronic circuit board |
| US9956649B2 (en) | 2014-06-24 | 2018-05-01 | Harima Chemicals, Incorporated | Solder alloy, solder paste, and electronic circuit board |
| EP2979807A4 (en) * | 2014-06-24 | 2016-12-07 | Harima Chemicals Inc | Solder alloy, solder composition, solder paste and electronic circuit board |
| EP3093098A4 (en) * | 2014-06-24 | 2017-12-13 | Harima Chemicals, Inc. | Solder alloy, solder paste and electronic circuit board |
| CN104625464A (en) * | 2014-12-23 | 2015-05-20 | 苏州龙腾万里化工科技有限公司 | Novel lead-free tin bar |
| CN115139008A (en) * | 2015-05-15 | 2022-10-04 | 安波福技术有限公司 | Lead-free solder based on indium-tin-silver |
| CN115139008B (en) * | 2015-05-15 | 2023-05-23 | 安波福技术有限公司 | Lead-free solder based on indium-tin-silver |
| CN104858564A (en) * | 2015-06-01 | 2015-08-26 | 谷华 | Soldering tin capable of not dissolving copper |
| CN105665956A (en) * | 2016-03-23 | 2016-06-15 | 徐宏达 | Soft solder alloy used for brazing aluminum and brazing aluminum alloy |
| CN108714749A (en) * | 2018-05-30 | 2018-10-30 | 江苏恒加机械工程有限公司 | A kind of preparation method of high brittle alloy weld tabs |
| CN108672979A (en) * | 2018-06-06 | 2018-10-19 | 上海莜玮汽车零部件有限公司 | A kind of leadless welding alloy and its application, glass assembly |
| CN109175770A (en) * | 2018-09-30 | 2019-01-11 | 苏州优诺电子材料科技有限公司 | A kind of high intensity low-temperature lead-free solder and preparation method thereof |
| CN108994480A (en) * | 2018-10-10 | 2018-12-14 | 云南锡业锡材有限公司 | A kind of SnBiAgCu high-reliability lead-free solder alloy |
| CN109894768A (en) * | 2019-03-29 | 2019-06-18 | 东莞市千岛金属锡品有限公司 | A kind of low temperature leadless alloy solder and preparation method thereof |
| TWI744907B (en) * | 2019-05-27 | 2021-11-01 | 日商千住金屬工業股份有限公司 | Solder alloy, solder paste, preform solder, solder ball, wire solder, grease-filled solder, solder joint, electronic circuit board and multilayer electronic circuit board |
| EP3888840A4 (en) * | 2019-05-27 | 2022-09-21 | Senju Metal Industry Co., Ltd. | Soldering alloy, soldering paste, preform solder, soldering ball, wire solder, resin flux cored solder, solder joint, electronic circuit board, and multilayer electronic circuit board |
| CN111590235A (en) * | 2020-06-11 | 2020-08-28 | 中山翰华锡业有限公司 | Low-dielectric-loss high-reliability soldering paste and preparation method thereof |
| CN114367762A (en) * | 2020-06-11 | 2022-04-19 | 中山翰华锡业有限公司 | Solder alloy powder, low dielectric loss high reliability soldering paste and preparation method thereof |
| CN111590235B (en) * | 2020-06-11 | 2022-04-01 | 中山翰华锡业有限公司 | Low-dielectric-loss high-reliability soldering paste and preparation method thereof |
| CN114367762B (en) * | 2020-06-11 | 2023-08-18 | 中山翰华锡业有限公司 | Solder alloy powder, low dielectric loss and high reliability solder paste and preparation method thereof |
| 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 |
| CN115041799A (en) * | 2022-05-25 | 2022-09-13 | 云南前沿液态金属研究院有限公司 | Alloy material for low-temperature welding of indium tin oxide film and welding method |
| CN115041799B (en) * | 2022-05-25 | 2023-01-24 | 云南前沿液态金属研究院有限公司 | Alloy material for low-temperature welding of indium tin oxide film and welding method |
| CN115502604A (en) * | 2022-09-29 | 2022-12-23 | 安徽科技学院 | Brazing filler metal for magnesium alloy, using method and soldering flux thereof |
| CN115502604B (en) * | 2022-09-29 | 2023-07-18 | 安徽科技学院 | Solder for magnesium alloy, using method and soldering flux 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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Application publication date: 20131009 |