CN100411804C - Self adaptive lead-free solder component and preparation method thereof - Google Patents
Self adaptive lead-free solder component and preparation method thereof Download PDFInfo
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- CN100411804C CN100411804C CNB2006101297839A CN200610129783A CN100411804C CN 100411804 C CN100411804 C CN 100411804C CN B2006101297839 A CNB2006101297839 A CN B2006101297839A CN 200610129783 A CN200610129783 A CN 200610129783A CN 100411804 C CN100411804 C CN 100411804C
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- free solder
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Abstract
The invention relates to a tin-silver-zinc self-adapt leadless solder with shape memory function and relative preparation, wherein in the tin-silver-zinc leadless solder whose purity is 99.99% and mass percentages are 96.5-93: 3.0-4.5: 0.5-2.5, there is silver-zinc metal phase with shape memory function; then it adds 0-2.5 gallium and 0-4 indium to improve humidity. The invention uses the silver-zinc thermoelasticity martensite of solder to obtain shape memory function. And it has compact combination and uniform distribution, compared with nickel-titanium alloy leadless solder.
Description
Technical field
The present invention relates to have the tin silver zinc self adaptive lead-free solder component and the preparation method of shape-memory properties, belong to the 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.2005, China's electronics and information industry economical operation in order, annual 38411 hundred million yuan of the incomes from sales that realize increase by 24.8% on a year-on-year basis, import and export 4,887 hundred million dollars, increase by 25.8% on a year-on-year basis.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.
As shown in Figure 1 silicon chip 1 is welded on the substrate 3, scolder combines with salient point on silicon chip and the substrate and forms solder bumps 2, and it is as the structure that plays connection, conduction and conductive force on the circuit board.During electronic device works, electric current causes the circuit board temperature to raise 4 through producing heat, because silicon chip is different with the baseplate material thermal coefficient of expansion, solder joint is bearing consequent most of shear stress 5; The electronic equipment outage, the circuit board temperature reduces, and expands to reply, and shear stress disappears.When electronic equipment moves repeatedly, be in the alternating action that solder joint in the thermal cycle will be subjected to shearing force, cause the solder joint cracking, the electronic system fault that makes, therefore, the United States Naval Postgraduate School researcher adopts niti-shaped memorial alloy particle after paddling process will bring out martensite and form by quenching to add SAC eutectic lead-free solder and makes composite solder.When reaching operating temperature, solder joint is subjected to the outer shear stress that causes owing to the coupling assembling thermal expansion coefficient difference, but simultaneously shape-memory material changes the restoring force that is produced by martensite to austenite and will cause that solder joint expands and offset the suffered outer shear stress of solder joint in the solder joint, the elasticity of scolder is improved, has reduced the different most of shear stresses that produce of scolder with the baseplate material thermal coefficient of expansion.But because the wetability between niti-shaped memorial alloy particle and scolder and substrate is very poor, success is compound in the matrix niti-shaped memorial alloy uniform particles very difficult, though take the copper facing of NiTi particle surface or add hydrofluoric acid base solder flux to improve its wetability, but produce little effect on the one hand, the cost increase also is a difficult problem on the other hand.
Summary of the invention
The object of the invention provides tin silver zinc self adaptive lead-free solder component and the preparation method with shape-memory properties, and this scolder has SME when temperature change, can improve the solder joint service life, and its preparation method is simple.
The present invention is realized by following technical proposals, tin silver zinc self adaptive lead-free solder with shape-memory properties, it is characterized in that, in purity is that 99.99% mass ratio is 96.5-93: 3.0-4.5: in the 0.5-2.5 tin silver zinc lead-free solder, exist to have the silver-colored zinc intermetallic compound phase of shape-memory properties, can add the gallium of 0-2.5 and the indium of 0-4 for improving wetability on this basis.
The preparation method of the above-mentioned tin silver zinc self adaptive lead-free solder with shape-memory properties is characterized in that comprising following process:
With purity is that 99.9% tin, silver, zinc and each alloying element gallium, indium are that 96.5-86.5: 3.0-4.5: 0.5-2.5: 0-2.5: 0-4 is heated to 1200 ℃ of-1500 ℃ of fusings in the vacuum melting furnace under the argon shield by mass ratio; simultaneously in addition magnetic stirs; so that alloy composition is even, water-cooled is solidified then.Again will alloy reheat 1200 ℃ of-1500 ℃ of fusings after the upset, in addition magnetic stirs and water-cooled simultaneously.At least five times so repeatedly, obtain the tin silver zinc lead-free solder buttony that diameter is about 3.0-3.5cm; The crucible that tin silver zinc lead-free solder is put under the vacuum protection is heated to 230-280 ℃; fast it is made by shrend and generate silver-colored zinc thermo elastic martensite in the scolder; make it between 20 ℃ and 120 ℃, have double process shape-memory effect; obtain having the tin silver zinc self adaptive lead-free solder of shape-memory properties; wherein the micro-metallograph of partial elements self adaptive lead-free solder is shown in Fig. 2,3; silver zinc intermetallic compound particle evenly distributes on matrix, and the silver-colored zinc intermetallic compound particle and the scolder matrix bond that self generate as can be seen are good.
Advantage of the present invention is to make scolder have SME by the silver-colored zinc thermo elastic martensite of separating out in the tin silver zinc self adaptive lead-free solder, can better under thermal shock environmental work condition, be on active service, compare simultaneously with niti-shaped memorial alloy granule enhancement type lead-free solder, its in conjunction with closely, be evenly distributed and do not have the wetability problem.
Description of drawings
Fig. 1: the suffered shear strain figure of solder joint in the thermal cycle process;
Fig. 2: the micro-metallograph of 95.4%Sn-3.7%Ag-0.9%Zn self adaptive lead-free solder;
Fig. 3: the micro-metallograph of 94.9%Sn-3.7%Ag-0.9%Zn-0.5%In self adaptive lead-free solder;
Fig. 4: the micro-metallograph of 96.1%Sn-3.4%Ag-0.5%Zn self adaptive lead-free solder.
1. silicon chip, 2. solder bumps, 3. substrate, 4. duty is heated, 5. the suffered shearing force of solder joint.
The specific embodiment
Embodiment 1:
Be 99.99% tin, silver, zinc by mass ratio with purity be in vacuum melting furnace argon shield under to be heated to 1200 ℃ of fusings at 95.4: 3.7: 0.9, in addition magnetic stirs simultaneously, so that alloy composition is even, water-cooled is solidified then.Again will alloy reheat 1200 ℃ of fusings after the upset, in addition magnetic stirs and water-cooled simultaneously.At least five times so repeatedly, obtain the tin silver zinc lead-free solder buttony that diameter is about 3.0-3.5cm; The crucible that tin silver zinc lead-free solder is put under the vacuum protection is heated to 230 ℃; fast it is made by shrend and generate silver-colored zinc thermo elastic martensite in the scolder; make it between 20 ℃ and 100 ℃, have double process shape-memory effect, obtain having the tin silver zinc self adaptive lead-free solder of shape-memory properties.The micro-metallographic of the resulting self adaptive lead-free solder in preparation back as shown in Figure 2.
Embodiment 2:
With purity is that 99.99% tin, silver, zinc, indium are 94.9: 3.7: 0.9 by mass ratio: 0.5 is heated to 1300 ℃ of fusings in the vacuum melting furnace under the argon shield, and in addition magnetic stirs simultaneously, so that alloy composition is even, water-cooled is solidified then.Again will alloy reheat 1300 ℃ of fusings after the upset, in addition magnetic stirs and water-cooled simultaneously.At least five times so repeatedly, obtain the tin silver zinc lead-free solder buttony that diameter is about 3.0-3.5cm; The crucible that tin silver zinc lead-free solder is put under the vacuum protection is heated to 250 ℃; fast it is made by shrend and generate silver-colored zinc thermo elastic martensite in the scolder; make it between 30 ℃ and 110 ℃, have double process shape-memory effect, obtain having the tin silver zinc self adaptive lead-free solder of shape-memory properties.The micro-metallographic of the resulting self adaptive lead-free solder in preparation back as shown in Figure 3.
Embodiment 3:
Be 99.99% tin, silver, zinc by mass ratio with purity be in vacuum melting furnace argon shield under to be heated to 1350 ℃ of fusings at 96.1: 3.4: 0.5, in addition magnetic stirs simultaneously, so that alloy composition is even, water-cooled is solidified then.Again will alloy reheat 1350 ℃ of fusings after the upset, in addition magnetic stirs and water-cooled simultaneously.At least five times so repeatedly, obtain the tin silver zinc lead-free solder buttony that diameter is about 3.0-3.5cm; The crucible that tin silver zinc lead-free solder is put under the vacuum protection is heated to 255 ℃; fast it is made by shrend and generate silver-colored zinc thermo elastic martensite in the scolder; make it between 35 ℃ and 115 ℃, have double process shape-memory effect, obtain having the tin silver zinc self adaptive lead-free solder of shape-memory properties.The micro-metallographic of the resulting self adaptive lead-free solder in preparation back as shown in Figure 4.
Embodiment 4:
With purity is that 99.99% tin, silver, zinc, gallium are 92.5: 4: 2 by mass ratio: 1.5 are heated to 1400 ℃ of fusings in the vacuum melting furnace under the argon shield, and in addition magnetic stirs simultaneously, so that alloy composition is even, water-cooled is solidified then.Again will alloy reheat 1400 ℃ of fusings after the upset, in addition magnetic stirs and water-cooled simultaneously.At least five times so repeatedly, obtain the tin silver zinc lead-free solder buttony that diameter is about 3.0-3.5cm; The crucible that tin silver zinc lead-free solder is put under the vacuum protection is heated to 260 ℃; fast it is made by shrend and generate silver-colored zinc thermo elastic martensite in the scolder; make it between 40 ℃ and 120 ℃, have double process shape-memory effect, obtain having the tin silver zinc self adaptive lead-free solder of shape-memory properties.
Embodiment 5:
Be 99.99% tin, silver, zinc by mass ratio with purity be in vacuum melting furnace argon shield under to be heated to 1450 ℃ of fusings at 96.5: 3.0: 0.5, in addition magnetic stirs simultaneously, so that alloy composition is even, water-cooled is solidified then.Again will alloy reheat 1450 ℃ of fusings after the upset, in addition magnetic stirs and water-cooled simultaneously.At least five times so repeatedly, obtain the tin silver zinc lead-free solder buttony that diameter is about 3.0-3.5cm; The crucible that tin silver zinc lead-free solder is put under the vacuum protection is heated to 270 ℃; fast it is made by shrend and generate silver-colored zinc thermo elastic martensite in the scolder; make it between 45 ℃ and 125 ℃, have double process shape-memory effect, obtain having the tin silver zinc self adaptive lead-free solder of shape-memory properties.
Embodiment 6:
With purity is that 99.99% tin, silver, zinc, gallium, indium are 86.5: 4.5: 2.5 by mass ratio: in vacuum melting furnace argon shield under be heated to 1500 ℃ of fusings at 2.5: 4, in addition magnetic stirs simultaneously, so that alloy composition is even, water-cooled is solidified then.Again will alloy reheat 1500 ℃ of fusings after the upset, in addition magnetic stirs and water-cooled simultaneously.At least five times so repeatedly, obtain the tin silver zinc lead-free solder buttony that diameter is about 3.0-3.5cm; The crucible that tin silver zinc lead-free solder is put under the vacuum protection is heated to 280 ℃; fast it is made by shrend and generate silver-colored zinc thermo elastic martensite in the scolder; make it between 50 ℃ and 130 ℃, have double process shape-memory effect, obtain having the tin silver zinc self adaptive lead-free solder of shape-memory properties.
The present invention open and the self adaptive lead-free solder component and the preparation method that propose, those skilled in the art can be by using for reference this paper content, and links such as appropriate change parameter realize.Self adaptive lead-free solder component of the present invention and preparation method are described by preferred embodiment, person skilled obviously can be changed or suitably change and combination content as herein described in not breaking away from content of the present invention, spirit and scope, realizes the technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (1)
1. a self adaptive lead-free solder composition prepares the method for scolder, it is characterized in that: the component that will prepare in proportion is heated to 1200 ℃ of-1500 ℃ of fusings in the vacuum melting furnace under the argon shield, simultaneously in addition magnetic stirs, so that alloying component is even, water-cooled is solidified then; Again will alloy reheat 1200 ℃ of-1500 ℃ of fusings after the upset, in addition magnetic stirs and water-cooled simultaneously; Repeatable operation is up to obtaining the lead-free solder buttony that diameter is 3.0-3.5cm like this; The vessel in heating that scolder is put under the vacuum protection arrives 230-280 ℃, fast it is made by shrend and generate silver-colored zinc thermo elastic martensite in the scolder, make it between 20 ℃-120 ℃, have double process shape-memory effect, obtain having the tin silver zinc self adaptive lead-free solder of shape-memory properties; The component of scolder and percentage by weight are: tin 86.5-96.5, silver-colored 3.0-4.5, zinc 0.5-2.5, gallium 0-2.5, indium 0-4.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006101297839A CN100411804C (en) | 2006-11-30 | 2006-11-30 | Self adaptive lead-free solder component and preparation method thereof |
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| CNB2006101297839A CN100411804C (en) | 2006-11-30 | 2006-11-30 | Self adaptive lead-free solder component and preparation method thereof |
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| CN1962157A CN1962157A (en) | 2007-05-16 |
| CN100411804C true CN100411804C (en) | 2008-08-20 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101318269B (en) * | 2008-07-14 | 2012-12-26 | 天津大学 | Tin-Silver-Zinc system lead-free solder with low silver content |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5762866A (en) * | 1993-02-22 | 1998-06-09 | Lucent Technologies Inc. | Article comprising a Pb-free solder having improved mechanical properties |
| JP2001246493A (en) * | 1999-12-28 | 2001-09-11 | Toshiba Corp | Soldering material, device or apparatus using same and its producing method |
| CN1322606A (en) * | 2000-05-08 | 2001-11-21 | 上海飞轮有色冶炼厂 | Low-tin lead alloy solder and its production process |
| CN1586793A (en) * | 2004-07-16 | 2005-03-02 | 北京工业大学 | SnZn series lead-free welding flux |
| US20050199679A1 (en) * | 2002-07-01 | 2005-09-15 | Yunosuke Nakahara | Sn-ag based lead-free solder |
| CN1672858A (en) * | 2005-05-09 | 2005-09-28 | 天津大学 | Shape memory Co-Zn-Al alloy grains reinforced composite Sn-Ag welding material and its prepn process |
-
2006
- 2006-11-30 CN CNB2006101297839A patent/CN100411804C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5762866A (en) * | 1993-02-22 | 1998-06-09 | Lucent Technologies Inc. | Article comprising a Pb-free solder having improved mechanical properties |
| JP2001246493A (en) * | 1999-12-28 | 2001-09-11 | Toshiba Corp | Soldering material, device or apparatus using same and its producing method |
| CN1322606A (en) * | 2000-05-08 | 2001-11-21 | 上海飞轮有色冶炼厂 | Low-tin lead alloy solder and its production process |
| US20050199679A1 (en) * | 2002-07-01 | 2005-09-15 | Yunosuke Nakahara | Sn-ag based lead-free solder |
| CN1586793A (en) * | 2004-07-16 | 2005-03-02 | 北京工业大学 | SnZn series lead-free welding flux |
| CN1672858A (en) * | 2005-05-09 | 2005-09-28 | 天津大学 | Shape memory Co-Zn-Al alloy grains reinforced composite Sn-Ag welding material and its prepn process |
Non-Patent Citations (2)
| Title |
|---|
| 自适应无铅焊料的开发与研究. 韦晨.材料导报，第20卷第3期. 2006 |
| 自适应无铅焊料的开发与研究. 韦晨.材料导报，第20卷第3期. 2006 * |
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