CN101920406B - Sn-Ag-Zn-Cr eutectic lead-free solder - Google Patents
Sn-Ag-Zn-Cr eutectic lead-free solder Download PDFInfo
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- CN101920406B CN101920406B CN2010102829054A CN201010282905A CN101920406B CN 101920406 B CN101920406 B CN 101920406B CN 2010102829054 A CN2010102829054 A CN 2010102829054A CN 201010282905 A CN201010282905 A CN 201010282905A CN 101920406 B CN101920406 B CN 101920406B
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- Prior art keywords
- scolder
- solder
- free solder
- present
- eutectic lead
- Prior art date
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 36
- 230000005496 eutectics Effects 0.000 title claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 238000003466 welding Methods 0.000 abstract description 9
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 239000010935 stainless steel Substances 0.000 abstract description 5
- 238000005476 soldering Methods 0.000 abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 17
- 238000003723 Smelting Methods 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910000599 Cr alloy Inorganic materials 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910000765 intermetallic Inorganic materials 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 229910017944 Ag—Cu Inorganic materials 0.000 description 4
- 230000003026 anti-oxygenic effect Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 239000010963 304 stainless steel Substances 0.000 description 3
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004100 electronic packaging Methods 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 206010023126 Jaundice Diseases 0.000 description 2
- 229910020816 Sn Pb Inorganic materials 0.000 description 2
- 229910020836 Sn-Ag Inorganic materials 0.000 description 2
- 229910020922 Sn-Pb Inorganic materials 0.000 description 2
- 229910020988 Sn—Ag Inorganic materials 0.000 description 2
- 229910008783 Sn—Pb Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 229910017692 Ag3Sn Inorganic materials 0.000 description 1
- 229910019192 Sn—Cr Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Electric Connection Of Electric Components To Printed Circuits (AREA)
Abstract
An Sn-Ag-Zn-Cr eutectic lead-free solder in the technical field of welding materials comprises the following components in percentage by mass: 0.005-1% of Cr, 3-5% of Ag, 0.5-5% of Zn, 0.5% of adjusting element and the balance of Sn. The invention can improve the oxidation resistance and corrosion resistance of the material, improve the mechanical properties such as ductility, strength and the like, and obviously weaken the corrosion action on a stainless steel soldering tin groove and the like.
Description
Technical field
What the present invention relates to is a kind of scolder of technical field of welding materials, specifically is a kind of Sn-Ag-Zn-Cr eutectic lead-free solder.
Background technology
Up to the present, the scolder that is used for microelectronics Packaging and assembling in a large number mainly is that traditional Sn-Pb is a scolder.Yet when electronic product, equipment were dropped as general industry discarded object and house refuse, the Pb in natural environment in the scolder became branch to be dissolved out, and invades underground water, thereby the environment and the mankind are caused great harm.Therefore; Comprise in recent years many countries of China numerous and confused formulate or making laws, rules; Limit the use of leaded material; Substituting traditional Sn-Pb with lead-free solder is that solder containing pb has become the irreversible main trend of global field of microelectronic fabrication, actively seeks the vital task that nontoxic new solder also becomes current electron trade.Sn-Ag-Zn is that scolder more and more received researcher's concern over the past two years as more potential solder alloy.
Compare the most frequently used Sn-Ag-Cu ternary scolder at present, the cost and the fusing point of Sn-Ag-Zn ternary scolder are suitable with the Sn-Ag-Cu scolder.Retrieval through to the prior art file is found, in " pb-free solder technology " (Science Press, 2004.7, the 39 pages), mentions the Sn-Ag-Cu series solder, and it is higher that this scolder removes fusing point, and outside price was more expensive, also existing some had problem to be solved.Under or situation that Ag scolder higher lower, be prone to form thick fragility Ag in cooling velocity
3Sn, Cu
6Sn
5Phase causes fragility to increase, and ductility reduces, decrease of fatigue strength.And report that in " The effects of third alloying elements on the bulk Ag3Sn formation in slowly cooled Sn-3.5Ag lead-free solder " (J Mater Sci:Mater Electron (2008) 19:275-280) and some other document the Sn-Ag-Zn scolder can effectively suppress fragility Ag
3Sn, Cu
6Sn
5The growth of phase improves the mechanical property and the ageing stability of material.But according to document " Effect of zinc additions on structure and properties of Sn-Ag eutectic lead-free solder alloy " (J Mater Sci:Mater Electron (2008) 19:81-84) and document " Effect of thermal ageing on (Sn-Ag; Sn-Ag-Zn)/and PtAg, Cu/Al
2O
3Solder joints " (JOURNAL OF MATERIALS SCIENCE:MATERIALS IN ELECTRONICS 9 (1998) 373-381) and some other bibliographical informations, the Sn-Ag-Zn scolder has certain inferior position on antioxygenic property, wetability, solder joint initial strength and the corrosivity to rustless steel container.Because above problem is not resolved, so the relative Sn Ag-Cu of Sn-Ag-Zn scolder scolder does not possess competitive advantage at present.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists; A kind of Sn-Ag-Zn-Cr eutectic lead-free solder is provided; Can improve non-oxidizability, the corrosion resistance of material, simultaneously mechanical performances such as ductility, intensity improve, and the corrosiveness of stainless steel solder bath etc. is obviously weakened.
The present invention realizes that through following technical scheme component of the present invention and mass percent thereof are: Cr is 0.005-1%, and Ag is 3-5%, and Zn is 0.5-5%, adjustment type element 0.5%, and surplus is Sn.
The content of described Cr is preferably 0.01-0.8%, further is preferably 0.02-0.5%.
Described adjustment type element is any one among Ni, Ga, In or the P.
The present invention relates to the preparation method of above-mentioned Sn-Ag-Zn-Cr lead-free solder, comprise direct smelting process and distribution smelting process, wherein:
Described direct smelting process is meant: said component is directly mixed the back melting make lead-free solder;
Described component is a metallic element Powdered, granular or the block shape;
Described distribution smelting process is meant: prepare Sn-Cr alloy, Ag-Cr alloy, Zn-Cr alloy, Sn-Zn-Cr alloy and Sn-Ag-Cr alloy successively, then above-mentioned alloy is mixed the back melting with the adjustment type element and obtain lead-free solder.
Described melting is meant: under the environment of vacuum, fused salt or inert gas shielding or reducing gas protection, carry out melting.
The present invention has improved the antioxygenic property and the resistance to corrosion of Sn-Ag-Zn ternary eutectic scolder through adding Cr; Experiment shows; The affiliation that adds of Cr forms the Cr barrier layer between surperficial Sn, Cu oxide layer and base metal; In high temperature or corrosive environment, this barrier layer can stop Sn, Cu to external diffusion, thereby has improved the antioxygenic property and the decay resistance of scolder; The adding of Cr makes scolder tissue and welding point interface tissue that tangible refinement arranged in addition, has improved the reliability of scolder mechanical property and solder joint; Solidification temperature range at scolder forms the Sn-Zn-Cr intermetallic compound simultaneously, has improved the intensity of scolder through the dispersion-strengtherning of intermetallic compound; The existence of Cr can reduce scolder greatly to containing the dissolution velocity of Cr alloy in addition, avoids or improves the corrosion to stainless steel solder bath material.When Cr content less than 0.005% the time, no dispersion-strengthened action is difficult to form the barrier layer of Cr at the solder surface annex, improves not enough to the chemical property and the mechanical performance of scolder; When content is higher than 1%, be prone to cause the segregation of composition, this segregation makes the Cr barrier layer inhomogeneous, and sunburner is bigger to the negative effect of wetability and mechanical performance etc.If the content of Cr is when the 0.02-0.5% scope in the control scolder; Barrier layer thickness is even, moderate, can produce dispersion-strengthened action, reduces the corrosion to stainless steel etc.; Do not have tangible segregation phenomena again, make the chemical property of scolder and mechanical performance all be in optimum state.Solder alloy obviously weakens stainless corrosiveness.Ga that adds among the present invention and In not only can improve the wettability of scolder, can generate intermetallic compound with Cr simultaneously, can generate CrGa with Cr simultaneously
4, Cr
5Ga
6, CrIn
2Deng intermetallic compound, in alloy, play the effect of dispersion-strengtherning, thereby improve the mechanical strength of scolder.And the adding of Ni not only can suppress Ag
3The growth of Sn intermetallic compound, the plasticity of raising scolder, the while can also be improved the deelectric transferred ability of scolder.The adding of P has improved the antioxygenic property of scolder, thereby has improved the wetability of scolder.Compare common Sn-Ag-Zn scolder, the present invention improves on mechanical performances such as non-oxidizability, corrosion resistance, ductility, fatigue durability, and the corrosiveness of stainless steel solder bath etc. is obviously weakened.
Scolder provided by the invention can be used in a lot of fields, as makes welding rod, welding wire, weld tabs, soldered ball, welding powder, soldering paste etc.These products can be used in each welding link of Electronic Packaging or assembling; Form electrode salient point (Bump), chip attach like serigraphy on the Electronic Packaging chips; BGA, CSP soldered ball; SMT such as Reflow Soldering, wave-soldering assembling, various used for electronic packaging substrates, printed circuit board solder joint form, and various repairing welding, manual welding etc.In a word, scolder provided by the invention, its application is wide.
The specific embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1
Component of the present invention and mass percent thereof are: Cr=0.005%, and Ag=3.5%, Zn=1.5%, surplus is Sn, processes the Sn-3.5Ag-1.5Zn-0.005Cr solder through direct smelting process or substep smelting process.
Various performance measurements show: the fusing point of this scolder, wetability, tensile strength and Sn-3.5Ag-1.5Zn solder are basic identical; At 85 ℃, humidity is that yellowing phenomenon reduces after advancing experiment in 24 hours under 85% the etching condition, and after 250 ℃ of x25 hour high-temperature oxydations are tested; Glossiness is better than the Sn-3.5Ag-1.5Zn scolder.Less to 304 stainless steel corrosions; Ductility improves about 5% than Sn-3.5Ag-1.5Zn scolder; Back fragility increase phenomenon is not obvious slowly cooling off.
Embodiment 2
Component of the present invention and mass percent thereof are: Cr=0.01%, and Ag=3.5%, Zn=1.5%, surplus is Sn, processes the Sn-3.5Ag-1.5Zn-0.01Cr solder through direct smelting process or substep smelting process.
Various performance measurements show: the fusing point of this scolder, wetability, tensile strength and Sn-3.5Ag-1.5Zn solder are basic identical; At 85 ℃, humidity is that yellowing phenomenon further reduces after advancing experiment in 24 hours under 85% the etching condition, and after 250 ℃ of x25 hour high-temperature oxydations are tested; Glossiness also is better than the Sn-3.5Ag-1.5Zn scolder.Less to 304 stainless steel corrosions; Ductility improves about 5-10% than Sn-3.5Ag-1.5Zn scolder; Back fragility increase phenomenon is not obvious slowly cooling off.
Embodiment 3
Component of the present invention and mass percent thereof are: Cr=0.03%, and Ag=3.5%, Zn=1.5%, surplus is Sn, processes the Sn-3.5Ag-1.5Zn-0.03Cr solder through direct smelting process or substep smelting process.
Various performance measurements show: the fusing point of this scolder, wetability, tensile strength and Sn-3.5Ag-1.5Zn solder are basic identical; At 85 ℃, humidity is after advancing experiment in 24 hours under 85% the etching condition, not have the jaundice phenomenon, and after 250 ℃ of x25 hour high-temperature oxydations are tested; Glossiness is much better than the Sn-3.5Ag-1.5Zn scolder.304 stainless steel corrosions there is not clear dissolution; Ductility improves about 15% than Sn-3.5Ag-1.5Zn scolder; Back fragility increase phenomenon is not obvious slowly cooling off.
Embodiment 4
Component of the present invention and mass percent thereof are: Cr=0.03%, and Ag=3.5%, Zn=4%, surplus is Sn, processes the Sn-3.5Ag-4Zn-0.03Cr solder through direct smelting process or substep smelting process.
Various performance measurements show: the tensile strength of this scolder and Sn-3.5Ag-1.5Zn solder are basic identical; Detect through DSC, liquidus temperature reduces about 2 ℃, and melting range enlarges about 1 ℃ simultaneously.Through sprawling experiment, wetability improves about 7% than the Sn-3.5Ag-1.5Zn scolder.At 85 ℃, humidity is after advancing experiment in 24 hours under 85% the etching condition, not have the jaundice phenomenon, and after 250 ℃ of x25 hour high-temperature oxydations are tested; Glossiness is much better than the Sn-3.5Ag-1.5Zn scolder.304 stainless steels there is not clear dissolution; Ductility improves about 20% than Sn-3.5Ag-1.5Zn scolder; Back fragility increase phenomenon is obvious slowly cooling off.
Claims (3)
1. Sn-Ag-Zn-Cr eutectic lead-free solder, it is characterized in that its component and mass percent are: Cr is 0.005-1%, and Ag is 3-5%, and Zn is 0.5-5%, adjustment type element 0.5%, and surplus is Sn; Described adjustment type element is any one among Ni, Ga, In or the P.
2. Sn-Ag-Zn-Cr eutectic lead-free solder according to claim 1 is characterized in that the content of described Cr is 0.01-0.8%.
3. Sn-Ag-Zn-Cr eutectic lead-free solder according to claim 1 is characterized in that the content of described Cr is 0.02-0.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102829054A CN101920406B (en) | 2010-09-16 | 2010-09-16 | Sn-Ag-Zn-Cr eutectic lead-free solder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102829054A CN101920406B (en) | 2010-09-16 | 2010-09-16 | Sn-Ag-Zn-Cr eutectic lead-free solder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101920406A CN101920406A (en) | 2010-12-22 |
| CN101920406B true CN101920406B (en) | 2012-05-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102829054A Expired - Fee Related CN101920406B (en) | 2010-09-16 | 2010-09-16 | Sn-Ag-Zn-Cr eutectic lead-free solder |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102371438A (en) * | 2011-10-17 | 2012-03-14 | 上海交通大学 | Sn-Cu-Bi-Al lead-free solder |
| CN104353840B (en) * | 2014-11-25 | 2017-11-03 | 北京康普锡威科技有限公司 | A kind of LED inexpensive lead-free solder alloy powders and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2599890B2 (en) * | 1993-02-22 | 1997-04-16 | エイ・ティ・アンド・ティ・コーポレーション | Lead-free solder material |
| CN101132881A (en) * | 2004-12-01 | 2008-02-27 | 爱尔发加热有限公司 | Solder alloy |
| CN101214589A (en) * | 2008-01-14 | 2008-07-09 | 哈尔滨工业大学 | Multi-component leadless solder |
| CN101733577A (en) * | 2009-11-26 | 2010-06-16 | 上海大学 | Sn-Ag-Cu-Zn-Cr quinary alloy lead-free solder |
-
2010
- 2010-09-16 CN CN2010102829054A patent/CN101920406B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2599890B2 (en) * | 1993-02-22 | 1997-04-16 | エイ・ティ・アンド・ティ・コーポレーション | Lead-free solder material |
| CN101132881A (en) * | 2004-12-01 | 2008-02-27 | 爱尔发加热有限公司 | Solder alloy |
| CN101214589A (en) * | 2008-01-14 | 2008-07-09 | 哈尔滨工业大学 | Multi-component leadless solder |
| CN101733577A (en) * | 2009-11-26 | 2010-06-16 | 上海大学 | Sn-Ag-Cu-Zn-Cr quinary alloy lead-free solder |
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| Publication number | Publication date |
|---|---|
| CN101920406A (en) | 2010-12-22 |
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