CN101357423B - Lead-free welding material - Google Patents
Lead-free welding material Download PDFInfo
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- CN101357423B CN101357423B CN2008101314034A CN200810131403A CN101357423B CN 101357423 B CN101357423 B CN 101357423B CN 2008101314034 A CN2008101314034 A CN 2008101314034A CN 200810131403 A CN200810131403 A CN 200810131403A CN 101357423 B CN101357423 B CN 101357423B
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- intermediate alloy
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Abstract
The invention discloses a lead-free tin solder with high wettability to a fuse nickel-plated copper cap, high strength and plasticity which comprises 3.0-5.0 percent of Cu, 0.05 --1.5 percent of Sb, 0.05-1.8 percent of Bi, 0.1-0.15 percent of Ag, 0.002-0.25 percent of RE, and the balance Sn by weight. The lead-free tin solder is applicable to the lead-free encapsulation in the electronic industry.
Description
The present invention relates to solder alloy, leadless welding alloy particularly is mainly used in the no-lead assembling and the encapsulation of electron trade.
Background technology
Fuse is intended for overload and the electrical equipment used of short-circuit protection, and the safe handling of protection equipment and electrical equipment is widely used in fields such as electric installation, power supply industry, device fabrication and industrial control system.The nickel-clad copper cap is the important composition part of fuse, and the quality of its package quality is determining the quality of fuse.Traditional fuse nickel-clad copper cap encapsulation is a tin-lead solder with scolder, yet in recent years, people more and more pay close attention to plumbous to the pollution of environment with to healthy infringement, countries in the world put into effect a series of decrees in succession and rules prevent the ecological problem that electronic product brings, the plumbous use in electronic product of restriction.Under this main trend of unleaded green manufacturing, fuse nickel-clad copper cap has also begun unleaded encapsulation.
The lead-free solder of having developed at present mainly contains Sn-Ag, Sn-Cu, and Sn-Zn and Sn-Ag-Cu etc., and by adding the series of products that elements such as Ag, Cu, P, Ni, In, Bi obtain different performance.US5527628 patent as the state university of JS3027441 patent and Iowa of Senju Metal Industry Co., Ltd discloses Sn-Ag-Cu series leadless scolder separately respectively; The CN1087994C patent of Panasonic Electric Equipment Industrial Co.,Ltd and the CN1586793A patent application of Beijing University of Technology disclose the tin zinc series leadless scolder of exploitation separately; The CN1496780A patent application of Senju Metal Industry Co., Ltd discloses a kind of tin copper series leadless scolder; The CN1040302C of Korea S Samsung Electro-Mechanics Co., Ltd, CN1040303C patent and CN1139607A patent application disclose tin bismuth series leadless scolder etc.
Though the kind of lead-free solder is more, the lead-free solder that is suitable for and is applied to the encapsulation of nickel-clad copper cap at present is the Sn-0.7Cu scolder.Though in existing lead-free solder, the Sn-0.7Cu scolder is higher relatively to the packaging technology applicability of nickel-clad copper cap, cost is also lower, and its weldability to the nickel-clad copper cap is still relatively poor; Sn-0.7Cu solder fusing temperature lower (227 ℃), to spatter the tin phenomenon serious for tube wall in the encapsulation process; Sn-0.7Cu scolder freezing range is narrow, and the dimensional stability in the copper cap encapsulation process is relatively poor, and above-mentioned these reasons cause the yield rate of nickel-clad copper cap encapsulating products lower.
Summary of the invention
The problem that welding performance was poor, yield rate is low when the present invention will solve fuse nickel-clad copper cap Lead-free in Electronic Packaging in the known technology, lead-free welding material of the present invention is provided for this reason, this scolder has good wettability to the nickel-clad copper cap, and Weldability is strong, can significantly improve the finished product rate.
For addressing the above problem the present invention
Special character is that it is made up of the component of following percetage by weight in this scolder gross weight:
Cu 3.0-5.0％
Sb 0.05-1.5％
Bi 0.05-0.07％
Ag 0.1-0.15％
RE 0.002-0.25％
The Sn surplus
Lead-free welding material alloy composition composition of the present invention and weight percentage thereof are determined according to following reason:
Adding alloying element cu can improve the mechanical property of scolder and strengthen molten temperature region.Yet Cu content is less than at 0.9% o'clock, and its effect is not obvious; And Cu content surpasses at 5.0% o'clock, and the plasticity school is poor, is difficult to carry out machinings such as wire drawing.Lead-free welding material Cu content of the present invention is chosen in the 0.9-5.0% scope, preferably in the 2.0-4.0% scope.
Add alloying element Ag and can reduce the scolder fusing point, improve the wettability of scolder, and improve the intensity of scolder by compound between the tin silver metal that generates the disperse distribution.When Ag content was less than 0.1%, its effect was not obvious; Yet Ag content was greater than 4.0% o'clock, and solder alloy plasticity is relatively poor, and Ag content too much can cause the rapid rising of production cost.Lead-free welding material Ag content of the present invention is chosen in the 0.1-4.0% scope.
Add alloying element Sb and can improve the wettability of scolder, and can further improve scolder intensity the nickel-clad copper cap.Sb content is less than at 0.05% o'clock, and these effects are not obvious; Yet Sb content surpasses at 3.0% o'clock, and its improvement degree to the scolder wettability tends towards stability, and solder hardens, and the plasticity school is poor, is difficult to carry out machinings such as wire drawing.Lead-free welding material Sb content of the present invention is chosen in the 0.05-3.0% scope.
Add bismuth additions and can reduce the solder fusing temperature, improve wettability.Bi content is less than at 0.05% o'clock, and its effect is not obvious.Yet Bi content surpasses at 3.5% o'clock, and alloy plasticity is relatively poor, is difficult to carry out machinings such as wire drawing.Lead-free welding material Bi content of the present invention is chosen in the 0.05-3.5% scope.
Add the tissue of RE element energy refinement solder alloy, improve the mechanical property of scolder.RE content is less than at 0.002% o'clock, and its effect is not obvious; Yet RE content surpasses at 0.5% o'clock, and RE easily gathers partially in crystal boundary, causes alloy mechanical property relatively poor.Lead-free welding material RE content of the present invention is chosen in the 0.002-0.5% scope.
Infinitely solid solution of Ni and Cu, adding the Ni element can refinement solder alloy tissue, can improve the plasticity of scolder again.Ni content is less than at 0.01% o'clock, and its effect is not obvious; The affiliation that adds of Ni content causes the rising of scolder fusing point, considers the upper limit of nickel-clad copper cap package temperature, and Ni content is restricted to 0.8%.Lead-free welding material Ni content of the present invention is chosen in the 0.01-0.8% scope.
Lead-free solder of the present invention shows that through test and calculating to following embodiment of the invention scolder it is good to fuse nickel-clad copper cap solderability, finished product rate height.
The specific embodiment
Further specify lead-free welding material of the present invention below by specific embodiment.
Embodiment 1
The Sn of 40.0Kg and the Cu of 10.0Kg are put into alumina crucible, insert melting in the intermediate frequency furnace, 800 ℃ of smelting temperatures are incubated 2 hours, come out of the stove after fully stirring, and the Sn-Cu intermediate alloy that contains Cu20% is made in cooling.The Sn of 45.0Kg and the Sb of 5.0Kg are put into alumina crucible, insert melting in the intermediate frequency furnace, 400 ℃ of smelting temperatures are incubated 2 hours, come out of the stove after fully stirring, and the Sn-Sb intermediate alloy that contains Sb10% is made in cooling.The Sn of 30.0Kg and the Bi of 20.0Kg are put into alumina crucible, insert melting in the intermediate frequency furnace, 400 ℃ of smelting temperatures are incubated 2 hours, come out of the stove after fully stirring, and the Sn-Bi intermediate alloy that contains Bi40% is made in cooling.The Sn of 40.0Kg and the Ag of 10.0Kg are put into alumina crucible, insert melting in the intermediate frequency furnace, smelting temperature is 800 ℃, and temperature retention time is 2 hours, comes out of the stove after fully stirring, and the Sn-Ag intermediate alloy that contains Ag20% is made in cooling.The Sn of 48.0Kg and the RE of 2.0Kg are put into alumina crucible, insert melting in the vacuum medium frequency induction melting furnace, smelting temperature is 1000 ℃, is incubated 2 hours, comes out of the stove after fully stirring, and the Sn-RE intermediate alloy that contains RE4% is made in cooling.The Sn of 48.0Kg and the Ni of 2Kg are put into alumina crucible, insert melting in the vacuum medium frequency induction melting furnace, smelting temperature is 800 ℃, is incubated 2 hours, comes out of the stove after fully stirring, and the Sn-Ni intermediate alloy that contains Ni4% is made in cooling.
Get above-mentioned Sn-Cu intermediate alloy 0.250Kg, Sn-Sb intermediate alloy 0.035Kg, Sn-Bi intermediate alloy 8.8g and pure tin 4.706Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 2
Get Sn-Cu intermediate alloy 0.750Kg among the embodiment 1, Sn-Sb intermediate alloy 0.750Kg, Sn-Bi intermediate alloy 0.225Kg and pure tin 3.275Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 3
Get Sn-Cu intermediate alloy 1.200Kg among the embodiment 1, Sn-Sb intermediate alloy 1.400Kg, Sn-Bi intermediate alloy 0.413Kg and pure tin 1.987Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 4
Get Sn-Cu intermediate alloy 0.250Kg among the embodiment 1, Sn-Sb intermediate alloy 0.035Kg, Sn-Bi intermediate alloy 8.8g, Sn-Ag intermediate alloy 0.038Kg and pure tin 4.669Kg insert melting in the stainless-steel pan, and smelting temperature is 550 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 5
Get Sn-Cu intermediate alloy 0.750Kg among the embodiment 1, Sn-Sb intermediate alloy 0.750Kg, Sn-Bi intermediate alloy 0.225Kg, Sn-Ag intermediate alloy 0.500Kg and pure tin 2.775Kg insert melting in the stainless-steel pan, and smelting temperature is 550 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 6
Get Sn-Cu intermediate alloy 1.200Kg among the embodiment 1, Sn-Sb intermediate alloy 1.400Kg, Sn-Bi intermediate alloy 0.413Kg, Sn-Ag intermediate alloy 0.950Kg and pure tin 1.037Kg insert melting in the stainless-steel pan, and smelting temperature is 550 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 7
Get Sn-Cu intermediate alloy 0.250Kg among the embodiment 1, Sn-Sb intermediate alloy 0.035Kg, Sn-Bi intermediate alloy 8.8g, Sn-RE intermediate alloy 6.3g and pure tin 4.700Kg insert melting in the stainless-steel pan, and smelting temperature is 550 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 8
Get Sn-Cu intermediate alloy 0.750Kg among the embodiment 1, Sn-Sb intermediate alloy 0.750Kg, Sn-Bi intermediate alloy 0.225Kg, Sn-RE intermediate alloy 0.313Kg and pure tin 2.963Kg insert melting in the stainless-steel pan, and smelting temperature is 550 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 9
Get Sn-Cu intermediate alloy 1.200Kg among the embodiment 1, Sn-Sb intermediate alloy 1.400Kg, Sn-Bi intermediate alloy 0.413Kg, Sn-RE intermediate alloy 0.587Kg and pure tin 1.400Kg insert melting in the stainless-steel pan, and smelting temperature is 550 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 10
Get Sn-Cu intermediate alloy 0.250Kg among the embodiment 1, Sn-Sb intermediate alloy 0.035Kg, Sn-Ag intermediate alloy 0.038Kg, Sn-RE intermediate alloy 6.3g and pure tin 4.671Kg insert melting in the stainless-steel pan, and smelting temperature is 550 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 11
Get Sn-Cu intermediate alloy 0.750Kg among the embodiment 1, Sn-Sb intermediate alloy 0.750Kg, Sn-Ag intermediate alloy 0.500Kg, Sn-RE intermediate alloy 0.313Kg and pure tin 2.688Kg insert melting in the stainless-steel pan, and smelting temperature is 550 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 12
Get Sn-Cu intermediate alloy 1.200Kg among the embodiment 1, Sn-Sb intermediate alloy 1.400Kg, Sn-Ag intermediate alloy 0.950Kg, Sn-RE intermediate alloy 0.587Kg and pure tin 0.863Kg insert melting in the stainless-steel pan, and smelting temperature is 550 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 13
Get Sn-Cu intermediate alloy 0.250Kg among the embodiment 1, Sn-Sb intermediate alloy 0.035Kg, Sn-Bi intermediate alloy 8.8g, Sn-Ag intermediate alloy 0.038Kg, Sn-RE intermediate alloy 6.3g and pure tin 4.662Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 14
Get Sn-Cu intermediate alloy 0.750Kg among the embodiment 1, Sn-Sb intermediate alloy 0.750Kg, Sn-Bi intermediate alloy 0.225Kg, Sn-Ag intermediate alloy 0.500Kg, Sn-RE intermediate alloy 0.313Kg and pure tin 2.462Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 15
Get Sn-Cu intermediate alloy 1.200Kg among the embodiment 1, Sn-Sb intermediate alloy 1.400Kg, Sn-Bi intermediate alloy 0.413Kg, Sn-Ag intermediate alloy 0.950Kg, Sn-RE intermediate alloy 0.587Kg and pure tin 0.450Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 16
Get Sn-Cu intermediate alloy 0.500Kg among the embodiment 1, Sn-Sb intermediate alloy 0.350Kg, Sn-Bi intermediate alloy 0.125Kg, Sn-Ag intermediate alloy 0.250Kg, Sn-Ni intermediate alloy 0.038Kg and pure tin 3.737Kg, insert melting in the stainless-steel pan, smelting temperature is 650 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 17
Get Sn-Cu intermediate alloy 1.000Kg among the embodiment 1, Sn-Sb intermediate alloy 0.500Kg, Sn-Bi intermediate alloy 0.063Kg, Sn-Ag intermediate alloy 0.500Kg, Sn-RE intermediate alloy 0.063Kg, Sn-Ni intermediate alloy 0.500Kg and pure tin 2.375Kg insert melting in the stainless-steel pan, and smelting temperature is 650 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 18
Get Sn-Cu intermediate alloy 0.750Kg among the embodiment 1, Sn-Sb intermediate alloy 1.000Kg, Sn-Bi intermediate alloy 0.188Kg, Sn-Ag intermediate alloy 0.675Kg, Sn-RE intermediate alloy 0.188Kg, Sn-Ni intermediate alloy 0.875Kg and pure tin 1.325Kg insert melting in the stainless-steel pan, and smelting temperature is 650 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 19
Get Sn-Cu intermediate alloy 0.250Kg among the embodiment 1, Sn-Sb intermediate alloy 0.035Kg, Sn-Ag intermediate alloy 0.038Kg, Sn-Ni intermediate alloy 0.125Kg and pure tin 4.553Kg insert melting in the stainless-steel pan, and smelting temperature is 650 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 20
Get Sn-Cu intermediate alloy 0.750Kg among the embodiment 1, Sn-Sb intermediate alloy 0.750Kg, Sn-Ag intermediate alloy 0.500Kg, Sn-Ni intermediate alloy 0.500Kg and pure tin 2.500Kg insert melting in the stainless-steel pan, and smelting temperature is 650 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Embodiment 21
Get Sn-Cu intermediate alloy 1.200Kg among the embodiment 1, Sn-Sb intermediate alloy 1.400Kg, Sn-Ag intermediate alloy 0.950Kg, Sn-Ni intermediate alloy 0.750Kg and pure tin 0.700Kg insert melting in the stainless-steel pan, and smelting temperature is 650 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free welding material bar.
Select for use present nickel-clad copper cap encapsulation to go up and use more Sn-0.7Cu lead-free solder as a comparison, the composition of embodiment and Comparative Examples is seen shown in the following table 1.
Carried out rate of spread test by GB11364-89 " solder spreadability and add seam property test method " national standard, sprawling substrate is the thick nickel plating copper coin of 0.2mm.Each scolder rate of spread test technology is all identical, and probe temperature is 320 ℃, and the time is 15s, and adopts identical scaling powder, and test result is seen following table 2.By table 2 as seen, the rate of spread of lead-free solder of the present invention has higher wettability and weldability much larger than Comparative Examples to the nickel-clad copper cap.
Adopt differential thermal analyzer to test the fusion temperature of each embodiment and Comparative Examples, test result sees Table 2.By table 2 as seen, lead-free welding material fusion temperature of the present invention is than the Comparative Examples height, and molten temperature region is big than Comparative Examples, can guarantee that lead-free welding material is in the semi-molten state in nickel-clad copper cap encapsulation process, reduce and spatter tin and dimensional instability phenomenon, improve the finished product rate.
According to JIS test standard test scolder mechanical property, test temperature is 25 ℃, and test result sees Table 2.By table 2 as seen, the intensity of lead-free solder of the present invention is higher, and percentage elongation is all greater than 20%.Thereby lead-free welding material of the present invention both satisfied the requirement of strength of welding procedure to scolder, had good plasticity again, was easy to be processed to thread to satisfy the package requirements of fuse with the nickel-clad copper cap.
Table 1 solder compositions and content
Table 2 solder performance test result
The remarkable advantage of lead-free welding material of the present invention is: fuse nickel-clad copper cap is had good welding performance, help improving the yield rate of nickel-clad copper cap encapsulating products.
Claims (1)
1. lead-free welding material is characterized in that it is made up of the component of following percetage by weight in this scolder gross weight:
Cu 3.0-5.0％；
Sb 0.05-1.5％；
Bi 0.05-0.07％；
Ag 0.1-0.15％；
RE 0.002-0.25％；
Surplus is Sn.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101314034A CN101357423B (en) | 2005-12-16 | 2005-12-16 | Lead-free welding material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101314034A CN101357423B (en) | 2005-12-16 | 2005-12-16 | Lead-free welding material |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100620363A Division CN100453244C (en) | 2005-12-16 | 2005-12-16 | Lead les tin solder |
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| Publication Number | Publication Date |
|---|---|
| CN101357423A CN101357423A (en) | 2009-02-04 |
| CN101357423B true CN101357423B (en) | 2011-03-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2008101314034A Expired - Fee Related CN101357423B (en) | 2005-12-16 | 2005-12-16 | Lead-free welding material |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1195592A (en) * | 1997-02-15 | 1998-10-14 | 三星电子株式会社 | Leadless alloy for soldering flux |
| US6176947B1 (en) * | 1998-12-31 | 2001-01-23 | H-Technologies Group, Incorporated | Lead-free solders |
| CN1314229A (en) * | 1999-10-12 | 2001-09-26 | 高科技集团公司 | Lead-free welding material |
| CN1346728A (en) * | 2001-09-19 | 2002-05-01 | 大连理工大学 | Lead-free alloy solder containing rare-earth and more alloy components |
| CN1445048A (en) * | 2002-03-20 | 2003-10-01 | 田村化研株式会社 | Solder without lead and paste solder composite |
| CN1475327A (en) * | 2003-06-28 | 2004-02-18 | 亚通电子有限公司 | Antioxidation leadless welding material |
-
2005
- 2005-12-16 CN CN2008101314034A patent/CN101357423B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1195592A (en) * | 1997-02-15 | 1998-10-14 | 三星电子株式会社 | Leadless alloy for soldering flux |
| US6176947B1 (en) * | 1998-12-31 | 2001-01-23 | H-Technologies Group, Incorporated | Lead-free solders |
| CN1314229A (en) * | 1999-10-12 | 2001-09-26 | 高科技集团公司 | Lead-free welding material |
| CN1346728A (en) * | 2001-09-19 | 2002-05-01 | 大连理工大学 | Lead-free alloy solder containing rare-earth and more alloy components |
| CN1445048A (en) * | 2002-03-20 | 2003-10-01 | 田村化研株式会社 | Solder without lead and paste solder composite |
| CN1475327A (en) * | 2003-06-28 | 2004-02-18 | 亚通电子有限公司 | Antioxidation leadless welding material |
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| CN101357423A (en) | 2009-02-04 |
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