CN1330455C - Zirconium oxide nano grain reinforced composite Sn-Ag welding material and its prepn process - Google Patents
Zirconium oxide nano grain reinforced composite Sn-Ag welding material and its prepn process Download PDFInfo
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- CN1330455C CN1330455C CNB2005100134308A CN200510013430A CN1330455C CN 1330455 C CN1330455 C CN 1330455C CN B2005100134308 A CNB2005100134308 A CN B2005100134308A CN 200510013430 A CN200510013430 A CN 200510013430A CN 1330455 C CN1330455 C CN 1330455C
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Abstract
本发明公开了一种氧化锆纳米颗粒增强型锡银复合焊料及其制备方法，属于复合无铅焊料技术。所述的氧化锆纳米颗粒增强型锡银复合焊料，是在质量比为96.5∶3.5的纯度为99.99%的锡和银的共晶无铅焊料中，含有质量比为1%-2%的粒径为20-30nm的氧化锆颗粒。该焊料制备方法于包括以下过程：质量比为96.5∶3的纯度为99.99%的锡和银的共晶无铅焊料熔炼；然后将质量比为1%-2%的粒径为20-30nm氧化锆与熔配而成的锡银共晶无铅焊料热混，再通过水冷就得到复合氧化锆纳米颗粒增强型锡银复合焊料。所制得的复合焊料硬度提高15%-30%。并且能抑制锡银无铅焊料在慢速冷却状态下易生成的对焊接不利的大块金属间化合物Ag3Sn的形成写生长。
The invention discloses a zirconia nanoparticle-reinforced tin-silver composite solder and a preparation method thereof, belonging to the technology of composite lead-free solder. The zirconia nanoparticle-reinforced tin-silver composite solder is composed of eutectic lead-free solder of tin and silver with a mass ratio of 96.5:3.5 and a purity of 99.99%, containing particles with a mass ratio of 1%-2%. Zirconia particles with a diameter of 20-30nm. The solder preparation method includes the following processes: the eutectic lead-free solder of tin and silver with a mass ratio of 96.5:3 and a purity of 99.99% is melted; Zirconium is mixed with tin-silver eutectic lead-free solder formed by melting, and then water-cooled to obtain composite zirconia nanoparticle-reinforced tin-silver composite solder. The hardness of the prepared composite solder is increased by 15%-30%. And it can inhibit the formation and writing growth of bulk intermetallic compound Ag 3 Sn which is easy to form in the slow cooling state of tin-silver lead-free solder, which is unfavorable to soldering.
Description
Technical field
The present invention relates to a kind of Zirconium oxide nano grain reinforced composite Sn-Ag welding material and preparation method thereof, belong to compound lead-free solder technology.
Background technology
Pay attention to environmental protection, advocate the main trend that green product is the current world economy development.The use bimillennial history of having had an appointment of tradition plumber's solder, and in the hyundai electronics assembly industry, be used widely especially.But owing to plumbous infringement to nerve system of human body brings very important harm to human health, the lead contamination problem is subject to people's attention day by day, to such an extent as to realize in the world that at present the unleaded cry of electronic product is very high.The discarded tissue of electronic electric equipment under the leader of European Union (WEEE) requirement stopped in the electronic assemblies industry in 2006 uses lead-containing materials.American National electronics manufacturing association (NEMI) specially for carrying out one " the unleaded plan of the welding of NEMI " by name for this reason comes the unleaded use problem that is assemblied in the electronics industry of system research; The main consumer electronics manufacturing enterprise of Japan also promises to undertake round Realization leadless electronic assembling as early as possible one after another, and everything makes the research of lead-free solder extremely urgent.For meeting the unleaded tide of global synchronization welding, the lead-free solder patent barrier of avoiding having developed is in the world formulated the task of top priority that the lead-free solder development strategy that is fit to China's actual conditions has become China Electronics's assembly industry.It is estimated that the China's electronics and IT industry income from sales reached 2.73 trillion yuan in 2004, its middle outlet accounts for about half.The enforcement of relevant decree rules has been related to the outlet of the relevant plumbous product of China in the world, also is directly connected to the protection of China's ecological environment and health.Domestic electronic product is unleaded imperative.The Chinese government pays much attention to the electronic product problem of environmental pollution, has put into effect " electronics and IT products prevention and cure of pollution management method ", to guarantee China's electronics and information industry sustainable and healthy development for this reason.But the unleaded Study on Technology of China's electronic product is started late, there is the commercialization leadless electronic product of independent intellectual property right very few especially, therefore, material science worker is faced with the challenge of using lead-free solder to replace traditional plumber's solder, and the research and development of novel lead-free scolder have become one of advanced subject of material science.
In order to obtain having the welding material of very good mechanical properties, adopt composite methods to add to strengthen particle in existing ripe welding material is the direction that many researchers make great efforts with the performance that improves scolder always.The researcher of U.S. Akron university is that 1% to 5% copper nano particles generates composite solder by add mass ratio in tin-lead solder, finds that it can improve the scolder institutional framework, makes that micro-hardness is the highest to have improved 40%.And add mass ratio therein is that 1% to 2% TiOx nano particle generates composite solder and makes also that its microhardness is the highest to have improved 50%.IBM Corporation is improved the overlap joint performance of scolder and metallic matrix by add molybdenum and tantalum nano particle generation composite solder in tin-lead solder.But these study limitations are not generalized to lead-free solder with compound in traditional tin-lead solder.
Summary of the invention
The object of the invention provides a kind of Zirconium oxide nano grain reinforced composite Sn-Ag welding material and preparation method thereof, and this scolder can improve the hardness of traditional composite Sn-Ag welding material and can suppress wherein compd A g between bulk metal
3The generation of Sn.Its preparation method is simple.
The present invention is realized by following technical proposals, a kind of Zirconium oxide nano grain reinforced composite Sn-Ag welding material, it is characterized in that, at mass ratio is that 96.5: 3.5 purity is in the eutectic lead-free solder of 99.99% tin and silver, and the particle diameter that contains the mass ratio that accounts for tin and silver components and be 1%-2% is the zirconia particles of 20-30nm.
Above-mentioned Zirconium oxide nano grain reinforced composite Sn-Ag welding material preparation method is characterized in that comprising following process:
Be 99.99% tin and silver by mass ratio with purity be in vacuum melting furnace argon shield under to be heated to 1200 ℃ of-1500 ℃ of fusings at 96.5: 3.5, in addition magnetic stirs simultaneously, so that alloying component is even.Water-cooled is solidified then, again will alloy reheat 1200 ℃ of-1500 ℃ of fusings after the upset, and in addition magnetic stirs and water-cooled simultaneously.At least five times so repeatedly, obtaining diameter is the tin silver eutectic lead-free solder of the button shape of 3.0-3.5cm.Then; with the mass ratio that accounts for tin and silver components be the particle diameter of 1%-2% to be the 20-30nm zirconia put into crucible under the vacuum protection and be heated to 250-300 ℃ and stir with the molten tin silver eutectic lead-free solder that forms of joining, just obtain the compound zirconia nano grain reinforced composite Sn-Ag welding material by water-cooled again.
Advantage of the present invention be by Zirconium oxide nano grain adding significantly refinement tin silver lead-free solder at the tissue of as cast condition, Webster micro-hardness test result shows that the composite solder microhardness of generation improves 15%-30% than the microhardness of the tin silver lead-free solder that does not add Zirconium oxide nano grain.And can suppress that the tin silver lead-free solder easily generates under the state of cooling at a slow speed to welding compd A g between disadvantageous bulk metal
3The formation of Sn and growth are improved the welding performance of scolder.
Description of drawings
Fig. 1 is the micro-metallograph of as-cast structure that does not add the tin silver eutectic lead-free solder of Zirconium oxide nano grain, and wherein white portion is Fu Xixiang, and its average grain size is 20-50 μ m.
Fig. 2 is the micro-metallograph of as-cast structure that adds the tin silver eutectic lead-free solder of 1% Zirconium oxide nano grain, and wherein white portion is Fu Xixiang, and its average grain size is 5-10 μ m, and tissue obtains refinement.
Fig. 3 is the micro-metallograph of as-cast structure that adds the tin silver eutectic lead-free solder of 2% Zirconium oxide nano grain, and wherein white portion is Fu Xixiang, and its average grain size is 1-2 μ m, and tissue obtains refinement more.
Fig. 4 is the micro-metallograph that does not add the equilibrium state tissue of tin silver eutectic lead-free solder after solidifying under the 5 ℃/min cooling velocity of Zirconium oxide nano grain, and wherein white bar is compd A g between bulk metal
3Sn, its average length is 120-180 μ m.
Fig. 5 is the micro-metallograph that adds the equilibrium state tissue of tin silver eutectic lead-free solder after solidifying under the 5 ℃/min cooling velocity of 1% Zirconium oxide nano grain, and wherein white bar is compd A g between bulk metal
3Sn, its average length is 30-50 μ m, compd A g between bulk metal
3Formation and the growth of Sn are inhibited.
Fig. 6 is the micro-metallograph that adds the equilibrium state tissue of tin silver eutectic lead-free solder after solidifying under the 5 ℃/min cooling velocity of 2% Zirconium oxide nano grain, does not have compd A g between bulk metal
3The generation of Sn.
Fig. 7 is an as cast condition tin silver eutectic lead-free solder and the Webster micro-hardness testing that adds 1% and 2% Zirconium oxide nano grain composite solder comparison diagram as a result.Can see that along with the increase of Zirconium oxide nano grain addition, the microhardness of composite solder obtains the raising of 15%-30%.
The specific embodiment
Example 1
Be 99.99% tin and silver by mass ratio with purity be in vacuum melting furnace argon shield under to be heated to 1200 ℃ of fusings at 96.5: 3.5, in addition magnetic stirs simultaneously, so that alloying component is even.Water-cooled is solidified then.In order to make alloy full and uniform, will reheat 1200 ℃ of fusings after the alloy upset, in addition magnetic stirs and water-cooled simultaneously.Five times so repeatedly, obtaining diameter is the tin silver eutectic lead-free solder of the button shape of 3.0-3.5cm.Then; being 1% Zirconium oxide nano grain (big or small 20-30 nanometer) with mass ratio puts into crucible under the vacuum protection and is heated to 250 ℃ and stir with the molten tin silver eutectic lead-free solder that forms of joining, and just obtains the nano grain reinforced sn-ag alloy scolder of compound zirconia by water-cooled again.
Example 2
Be 99.99% tin and silver by mass ratio with purity be in vacuum melting furnace argon shield under to be heated to 1300 ℃ of fusings at 96.5: 3.5, in addition magnetic stirs simultaneously, so that alloying component is even.Water-cooled is solidified then.In order to make alloy full and uniform, will reheat 1300 ℃ of fusings after the alloy upset, in addition magnetic stirs and water-cooled simultaneously.Five times so repeatedly, obtaining diameter is the tin silver eutectic lead-free solder of the button shape of 3.0-3.5cm.Then; being 1.5% Zirconium oxide nano grain (big or small 20-30 nanometer) with mass ratio puts into crucible under the vacuum protection and is heated to 270 ℃ and stir with the molten tin silver eutectic lead-free solder that forms of joining, and just obtains the nano grain reinforced sn-ag alloy scolder of compound zirconia by water-cooled again.
Example 3
Be 99.99% tin and silver by mass ratio with purity be in vacuum melting furnace argon shield under to be heated to 1500 ℃ of fusings at 96.5: 3.5, in addition magnetic stirs simultaneously, so that alloying component is even.Water-cooled is solidified then.In order to make alloy full and uniform, will reheat 1500 ℃ of fusings after the alloy upset, in addition magnetic stirs and water-cooled simultaneously.Five times so repeatedly, obtaining diameter is the tin silver eutectic lead-free solder of the button shape of 3.0-3.5cm.Then; being 2% Zirconium oxide nano grain (big or small 20-30 nanometer) with mass ratio puts into crucible under the vacuum protection and is heated to 300 ℃ and stir with the molten tin silver eutectic lead-free solder that forms of joining, and just obtains the nano grain reinforced sn-ag alloy scolder of compound zirconia by water-cooled again.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100134308A CN1330455C (en) | 2005-05-09 | 2005-05-09 | Zirconium oxide nano grain reinforced composite Sn-Ag welding material and its prepn process |
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| CNB2005100134308A CN1330455C (en) | 2005-05-09 | 2005-05-09 | Zirconium oxide nano grain reinforced composite Sn-Ag welding material and its prepn process |
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| Publication Number | Publication Date |
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| CN1672859A CN1672859A (en) | 2005-09-28 |
| CN1330455C true CN1330455C (en) | 2007-08-08 |
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| CNB2005100134308A Expired - Fee Related CN1330455C (en) | 2005-05-09 | 2005-05-09 | Zirconium oxide nano grain reinforced composite Sn-Ag welding material and its prepn process |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745752B (en) * | 2009-12-17 | 2011-12-14 | 北京有色金属研究总院 | Nanometer reinforced bismuth base lead-free high-temperature solder and preparation method thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323062B (en) * | 2008-07-16 | 2010-06-02 | 太仓市南仓金属材料有限公司 | Silicon carbide granule enhancement type tin-silver-zinc compound solder manufacture method |
| CN103056545B (en) * | 2013-01-18 | 2014-12-17 | 江苏师范大学 | A lead-free solder for high reliability WLCSP device soldering |
| CN104476006B (en) * | 2014-11-18 | 2016-08-24 | 南京航空航天大学 | A kind of high wetting resistance to oxidation lead-free solder used for submerged arc welding and preparation for processing thereof |
| JP6540869B1 (en) * | 2018-03-30 | 2019-07-10 | 千住金属工業株式会社 | Solder paste |
| JP7778343B2 (en) * | 2021-08-31 | 2025-12-02 | 国立大学法人大阪大学 | High strength, high ductility, and high reliability solder and its manufacturing method |
| CN116652319A (en) * | 2023-06-08 | 2023-08-29 | 扬州大学 | A kind of tin dioxide nanoparticle reinforced lead-free composite paste and solder joint formed therefrom |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040303C (en) * | 1995-06-30 | 1998-10-21 | 三星电机株式会社 | Universal non-lead solder |
| CN1087994C (en) * | 1995-09-29 | 2002-07-24 | 松下电器产业株式会社 | Lead-free solder |
| CN1392817A (en) * | 2000-09-18 | 2003-01-22 | 松下电器产业株式会社 | Brazing materials and electrical or electronic equipment using the same |
-
2005
- 2005-05-09 CN CNB2005100134308A patent/CN1330455C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040303C (en) * | 1995-06-30 | 1998-10-21 | 三星电机株式会社 | Universal non-lead solder |
| CN1087994C (en) * | 1995-09-29 | 2002-07-24 | 松下电器产业株式会社 | Lead-free solder |
| CN1392817A (en) * | 2000-09-18 | 2003-01-22 | 松下电器产业株式会社 | Brazing materials and electrical or electronic equipment using the same |
Non-Patent Citations (1)
| Title |
|---|
| 铜铟铋硫对Sn-Ag基无铅焊料性能的影响 林培豪，刘心宇，成钧，电子元件与材料，第22卷第10期 2003 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745752B (en) * | 2009-12-17 | 2011-12-14 | 北京有色金属研究总院 | Nanometer reinforced bismuth base lead-free high-temperature solder and preparation method thereof |
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| CN1672859A (en) | 2005-09-28 |
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Assignee: Nancang Metal Materials Co., Ltd., Taicang City Assignor: Tianjin University Contract record no.: 2011320000712 Denomination of invention: Zirconium oxide nano grain reinforced composite Sn-Ag welding material and its prepn process Granted publication date: 20070808 License type: Exclusive License Open date: 20050928 Record date: 20110512 |
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