CN101088698A - No-lead soft brazing alloy - Google Patents
No-lead soft brazing alloy Download PDFInfo
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- CN101088698A CN101088698A CN 200610051969 CN200610051969A CN101088698A CN 101088698 A CN101088698 A CN 101088698A CN 200610051969 CN200610051969 CN 200610051969 CN 200610051969 A CN200610051969 A CN 200610051969A CN 101088698 A CN101088698 A CN 101088698A
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Abstract
The no-lead soft brazing alloy has low Cu corrosion, high wettability and excellent mechanical performance. There are four types of no-lead soft brazing alloy, the first one consists of Cu 1.0.4-0.9 wt%, In 0.005-0.095 wt%, P 0.001-0.15 wt%, and Sn for the rest; the second one consists of Cu 2.0.4-0.9 wt%, In 0.005-0.095 wt%, P 0.001-0.15 wt%, Ni 0.01- 0.2 wt%, and Sn for the rest; the third one consists of Cu 3.0.4-0.9 wt%, In 0.005-0.095 wt%, P 0.001- 0.15 wt%, RE 0.002-0.2 wt%, and Sn for the rest; and the fourth one consists of Cu 4.0.4-0.9 wt%, In 0.005-0.095 wt%, P 0.001-0.15 wt%, Ni 0.01-0.2 wt%, RE 0.002-0.2 wt%, and Sn for the rest. The present invention is suitable for no-lead assembling and packaging in electronic industry.
Description
The present invention relates to soft solder, lead-free solder particularly is mainly used in the no-lead assembling and the encapsulation of electron trade.
Background technology
Wave-soldering has remarkable advantages such as the reliable and low cost of high efficiency, high solder joint, is the important process in the electronics assembling, and solder performance then is the important prerequisite that can electronic devices and components realize good wave soldering.Traditional wave-soldering solder is a tin-lead solder, yet in recent years, people more and more pay close attention to plumbous to the pollution of environment with to healthy infringement, many countries have put into effect a series of decrees in succession and rules are prevented and treated the ecological problem that electronic product brings, the plumbous use in electronic product of restriction.Under this main trend of unleaded green manufacturing, electron trade has also begun unleaded wave soldering.
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.As the US5527628 patent of the state university of JS3027441 patent and Iowa of Senju Metal Industry Co., Ltd, disclosing Sn-Ag-Cu separately respectively is lead-free solder; The CN1087994C patent of Panasonic Electric Equipment Industrial Co.,Ltd and the CN1586793A patent application of Beijing University of Technology disclose separately, and the Sn-Zn of exploitation is a lead-free solder; It is lead-free solder that the CN1496780A patent application of Senju Metal Industry Co., Ltd discloses a kind of Sn-Cu; It is lead-free solder etc. that the CN1040302C of Korea S Samsung Electro-Mechanics Co., Ltd, CN1040303C patent and CN1139607A patent application disclose Sn-Bi.
Sn-0.7Cu (Cu account for solder gross mass 0.7%) soft solder is because cost is low, and aspects such as weldability, physics and mechanical property can satisfy the technological requirement of wave-soldering, are the lead-free solders of use amount maximum on the present wave-soldering technology.Yet the Sn-0.7Cu soft solder is serious to the Cu corrosion on the pcb board (printed board) in the wave soldering process, causes the Cu concentration in the tin liquor constantly to increase, and fusing point rises, and easily causes weld defects such as drawing point, Xi Qiao, and welding spot reliability is poor.
Summary of the invention
The present invention to solve lead-free solder in the known technology in the wave soldering process to excessive this problem of copper corrosion, lead-free solder of the present invention is provided for this reason, this soft solder is low to the copper dissolution extent, and has advantages such as good mechanical performance and wetability.
For addressing the above problem, the present invention is divided into following several soft solders.
The one special character is that it is made up of the component of following mass percent in this solder gross mass:
Cu 0.4％-0.9％
In 0.005％-0.095％
P 0.001％-0.15％
The Sn surplus
Its two special character is that it is made up of the component of following mass percent in this solder gross mass:
Cu 0.4％-0.9％
In 0.005％-0.095％
P 0.001％-0.15％
Ni 0.01％-0.2％
The Sn surplus
Its three special character is that it is made up of the component of following mass percent in this solder gross mass:
Cu 0.4％-0.9％
In 0.005％-0.095％
P 0.001％-0.15％
RE 0.002％-0.2％
The Sn surplus
Its four special character is to it is characterized in that it is made up of the component of following mass percent in this solder gross mass:
Cu 0.4％-0.9％
In 0.005％-0.095％
P 0.001％-0.15％
Ni 0.01％-0.2％
RE 0.002％-0.2％
The Sn surplus
Add the Cu element and can significantly reduce the dissolution extent of soft solder to copper, Cu content is not obvious less than its effect in 0.4% o'clock; And Cu content can cause the solder fusing point too high greater than 0.9% o'clock, the wetability variation.Leadless tin-base soft solder Cu content of the present invention is chosen in the 0.4%-0.9% scope.
Add element In and can significantly reduce the dissolution extent of soft solder, and can improve the wetability and the plasticity of soft solder copper.In content was less than 0.005% o'clock, and its effect is not obvious; Yet In content is greater than 0.095% o'clock, and it is little to the variation of copper dissolution extent that it reduces soft solder, and In is noble metal, and too high levels can cause the significantly rising of production cost.Lead-free solder In content of the present invention is chosen in the 0.005%-0.095% scope.
Add the antioxygenic property that element P can improve soft solder, reduce the product quantity of slag of flow of molten solder.P content was less than 0.001% o'clock, and its effect is not obvious; And P content is greater than 0.15% o'clock, and soft solder plasticity is relatively poor.Lead-free solder P content of the present invention is chosen in the 0.001%-0.15% scope.
The plasticity that an amount of Ni element can significantly improve soft solder is added in infinitely solid solution of Ni and Cu.Ni content was less than 0.01% o'clock, and its effect is not obvious; Yet Ni content was greater than 0.2% o'clock, and the intensity of soft solder and wetability can reduce.Lead-free solder Ni content of the present invention is chosen in the 0.01%-0.2% scope.
Add RE element energy refinement soft solder alloy organizing, improve the mechanical property of soft solder.RE content is less than at 0.002% o'clock, and its effect is not obvious; Yet RE content surpasses at 0.2% o'clock, and RE easily gathers partially in crystal boundary, causes alloy mechanical property relatively poor.Lead-free solder RE content of the present invention is chosen in the 0.002%-0.2% scope.
Lead-free solder of the present invention, show through test and calculating following embodiment of the invention soft solder, it is low to the Cu dissolution extent on the pcb board in the wave-soldering process, can significantly suppress the increase of Cu concentration in the tin liquor, and solderability is good, intensity and antioxygenic property height can increase substantially the yield rate of completed knocked down products.
The specific embodiment
Further specify lead-free solder of the present invention below by specific embodiment.
Embodiment 1
The Sn of 48.5Kg and the Cu of 1.5Kg are put into alumina crucible, insert melting in the intermediate frequency furnace, 600 ℃ of smelting temperatures are incubated 2 hours, come out of the stove after fully stirring, and the Sn-Cu intermediate alloy that contains 3%Cu is made in cooling.
The Sn of 49.5Kg and the In of 0.5Kg are put into alumina crucible, insert melting in the intermediate frequency furnace, 400 ℃ of smelting temperatures are incubated 1 hour, come out of the stove after fully stirring, and the Sn-In intermediate alloy that contains 1%In is made in cooling.
The Sn of 49.75Kg is put into the alumina crucible melting, and smelting temperature is 500 ℃; After the tin fusing, the P with 0.25Kg is pressed in the tin liquor with the foraminate graphite bell jar of peripheral band, and constantly stirs; Be incubated 6 hours, come out of the stove after fully stirring, the Sn-P intermediate alloy that contains 0.5%P is made in cooling.
The Sn of 49.5Kg and the Ni of 0.5Kg are put into alumina crucible, insert melting in the vacuum medium frequency induction melting furnace, smelting temperature is 700 ℃, is incubated 1 hour, comes out of the stove after fully stirring, and the Sn-Ni intermediate alloy that contains 1%Ni is made in cooling.
The Sn of 49.5Kg and the RE of 0.5Kg 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-RE intermediate alloy that contains 1%RE is made in cooling.
Get above-mentioned Sn-Cu intermediate alloy 0.750Kg, Sn-In intermediate alloy 0.030Kg, Sn-P intermediate alloy 0.020Kg and pure tin 4.200Kg, insert melting in the stainless-steel pan, smelting temperature is 600 ℃, and temperature retention time is 1 hour, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 2
Get embodiment 1 Sn-Cu intermediate alloy 1.167Kg, Sn-In intermediate alloy 0.050Kg, Sn-P intermediate alloy 1.000Kg and pure tin 2.783Kg, insert melting in the stainless-steel pan, smelting temperature is 600 ℃, and temperature retention time is 1 hour, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 3
Get embodiment 1 Sn-Cu intermediate alloy 1.167Kg, Sn-In intermediate alloy 0.250Kg, Sn-P intermediate alloy 0.500Kg, Sn-Ni intermediate alloy 0.100Kg and pure tin 2.983Kg insert melting in the stainless-steel pan, and smelting temperature is 600 ℃, temperature retention time is 1 hour, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 4
Get embodiment 1 Sn-Cu intermediate alloy 1.000Kg, Sn-In intermediate alloy 0.150Kg, Sn-P intermediate alloy 0.750Kg, Sn-Ni intermediate alloy 0.250Kg, Sn-RE intermediate alloy 0.050Kg and pure tin 2.800Kg, insert melting in the stainless-steel pan, smelting temperature is 600 ℃, and temperature retention time is 1 hour, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 5
Get embodiment 1 Sn-Cu intermediate alloy 1.433Kg, Sn-In intermediate alloy 0.460Kg, Sn-P intermediate alloy 0.080Kg, Sn-Ni intermediate alloy 0.550Kg, Sn-RE intermediate alloy 0.500Kg and pure tin 1.977Kg, insert melting in the stainless-steel pan, smelting temperature is 600 ℃, and temperature retention time is 1 hour, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 6
Get embodiment 1 Sn-Cu intermediate alloy 0.833Kg, Sn-In intermediate alloy 0.3 50Kg, Sn-P intermediate alloy 0.150Kg, Sn-Ni intermediate alloy 0.700Kg, Sn-RE intermediate alloy 0.020Kg and pure tin 2.947Kg, insert melting in the stainless-steel pan, smelting temperature is 600 ℃, and temperature retention time is 1 hour, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 7
Get embodiment 1 Sn-Cu intermediate alloy 1.333Kg, Sn-In intermediate alloy 0.250Kg, Sn-P intermediate alloy 1.300Kg, Sn-Ni intermediate alloy 0.900Kg, Sn-RE intermediate alloy 0.950Kg and pure tin 0.267Kg, insert melting in the stainless-steel pan, smelting temperature is 600 ℃, and temperature retention time is 1 hour, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
The Sn-0.7Cu lead-free solder of selecting use amount maximum on the present wave-soldering for use as a comparison, the composition of embodiment and Comparative Examples is shown in Table 1.
Table 1 brazing filler metal compositions useful and content
| Embodiment and Comparative Examples | Component and content (wt%) | |||||
| Cu | In | P | Ni | RE | Sn | |
| Embodiment 1 | 0.45 | 0.006 | 0.002 | - | - | Surplus |
| Embodiment 2 | 0.7 | 0.01 | 0.1 | - | - | Surplus |
| Embodiment 3 | 0.7 | 0.05 | 0.05 | 0.02 | - | Surplus |
| Embodiment 4 | 0.6 | 0.03 | 0.075 | 0.05 | 0.01 | Surplus |
| Embodiment 5 | 0.86 | 0.092 | 0.008 | 0.11 | 0.1 | Surplus |
| Embodiment 6 | 0.5 | 0.07 | 0.015 | 0.14 | 0.004 | Surplus |
| Embodiment 7 | 0.8 | 0.05 | 0.13 | 0.18 | 0.19 | Surplus |
| Comparative Examples | 0.7 | - | - | - | - | Surplus |
For estimating the dissolution extent of patent of the present invention to Cu on the PCB substrate, carried out the corrosion test experiments, and with remaining the copper rate as estimating the evaluation index of solder to Cu dissolution extent on the substrate: the Cu linear diameter/Cu line green diameter after surplus copper rate (%)=immersed solder, adopt the miking copper wire diameter.The surplus big more solder that shows of copper rate is low more to the dissolution extent of Cu, and promptly anti-corrosion performance is good more.The test technology of surplus copper rate is: be the Cu line of 0.300mm in 400 ℃ of tin liquors that immerse fusions down 4 seconds with diameter, immersion length is 4mm; Comparative Examples is the Sn-0.7Cu lead-free brazing of use amount maximum on the wave-soldering technology, and test result sees Table 2.By table 2 as seen, the surplus copper rate of solder embodiment of the present invention is all than Comparative Examples height, wherein the surplus copper rate of embodiment 5～7 is far above Comparative Examples, this explanation solder of the present invention is very low to the dissolution extent of Cu, use lead-free brazing of the present invention to carry out the wave soldering components and parts and can significantly reduce soldering tin is gone up the Cu plate to PCB dissolution extent, can effectively suppress the increase of Cu concentration in the tin liquor, help improving the yield rate of completed knocked down products.
The erodible test result of table 2
| Embodiment and Comparative Examples | The corrosion test | ||
| Cu line green diameter (mm) | Cu linear diameter (mm) after the immersed solder | Surplus copper rate (%) | |
| Embodiment 1 | 0.300 | 0.244 | 81.3 |
| Embodiment 2 | 0.300 | 0.268 | 89.2 |
| Embodiment 3 | 0.300 | 0.271 | 90.4 |
| Embodiment 4 | 0.300 | 0.264 | 88.1 |
| Embodiment 5 | 0.300 | 0.296 | 98.7 |
| Embodiment 6 | 0.300 | 0.280 | 93.3 |
| Embodiment 7 | 0.300 | 0.292 | 97.5 |
| Comparative Examples | 0.300 | 0.242 | 80.8 |
Adopt differential thermal analyzer to test the fusion temperature of each embodiment and Comparative Examples, test result sees Table 3.By table 3 as seen, lead-free solder fusing point of the present invention lower (＜230 ℃, close with the Comparative Examples fusing point) can carry out soldering under 260 ℃ temperature; And molten temperature region is also less, can guarantee molten solder rapid solidification at short notice, reduces soldered fitting and finishes that cause is vibrated and the possibility that ftractures can satisfy the encapsulation requirement of electronic material at process of setting.
Table 3 fusing point test result
| Embodiment and Comparative Examples | Fusion temperature (℃) | |
| Solidus temperature | Liquidus temperature | |
| Embodiment 1 | 227 | 230 |
| Embodiment 2 | 227 | 227 |
| Embodiment 3 | 227 | 227 |
| Embodiment 4 | 227 | 228 |
| Embodiment 5 | 227 | 229 |
| Embodiment 6 | 227 | 229 |
| Embodiment 7 | 227 | 230 |
| Comparative Examples | 227 | 227 |
Carried out rate of spread test by GB11364-89 " solder spreadability and add seam property test method " national standard, sprawling substrate is the thick red copper sheet of 0.2mm.Each solder rate of spread test technology is all identical, and probe temperature is 260 ℃, and the time is 2s, and adopts identical scaling powder (the diethylamine hydrochloric acid configuration by 25g rosin, 75g isopropyl acetone and 0.39g forms), and test result sees Table 4.By table 4 as seen, the lead-free solder rate of spread of the present invention is all than Comparative Examples height, and this is that antioxygenic property is better because lead-free solder of the present invention has added micro-anti-oxidant element P, thereby help the abundant reaction between solder and copper base, wettability has obtained enhancing.
According to JIS tension test standard, and adopt electronic universal material testing machine test solder mechanical property, test temperature is 25 ℃ of room temperatures, the results are shown in Table 4.By the result as seen, the percentage elongation of lead-free solder of the present invention all is higher than Comparative Examples, and promptly the plasticity ratio Comparative Examples is good, and intensity and Comparative Examples are close.Wherein the intensity of embodiment 2～5, embodiment 7 and plasticity all are higher than Comparative Examples.Thereby lead-free solder of the present invention has excellent mechanical property, can not only satisfy the requirement of strength of soldered fitting, and be easy to be processed to multiple shape to satisfy different welding demands.
Table 4 mechanical property and wetability test result
| Embodiment and Comparative Examples | Hot strength (MPa) | Percentage elongation (%) | The rate of spread (%) |
| Embodiment 1 | 34.4 | 45.6 | 78.06 |
| Embodiment 2 | 43.7 | 30.4 | 78.65 |
| Embodiment 3 | 45.4 | 33.0 | 76.67 |
| Embodiment 4 | 45.5 | 33.1 | 76.04 |
| Embodiment 5 | 39.8 | 49.5 | 78.25 |
| Embodiment 6 | 36.4 | 47.8 | 78.49 |
| Embodiment 7 | 42.0 | 25.9 | 77.07 |
| Comparative Examples | 38.4 | 23.6 | 71.32 |
According to above-mentioned analysis, lead-free solder of the present invention is very little to the Cu dissolution extent on the pcb board in welding process, not only help improving the stability of soldering tin composition in the welding process, and help improving the yield rate of completed knocked down products, it is excessive to the copper dissolution extent to solve present Sn-0.7Cu soft solder, has a strong impact on this problem of welding stability; Lead-free solder of the present invention also has good wetability and higher mechanical property simultaneously.
Claims (4)
1. lead-free solder is characterized in that it is made up of the component of following mass percent in this solder gross mass:
Cu 0.4％-0.9％
In 0.005％-0.095％
P 0.001％-0.15％
The Sn surplus
2. lead-free solder is characterized in that it is made up of the component of following mass percent in this solder gross mass:
Cu 0.4％-0.9％
In 0.005％-0.095％
P 0.001％-0.15％
Ni 0.01％-0.2％
The Sn surplus
3. lead-free solder is characterized in that it is made up of the component of following mass percent in this solder gross mass:
Cu 0.4％-0.9％
In 0.005％-0.095％
P 0.001％-0.15％
RE 0.002％-0.2％
The Sn surplus
4. lead-free solder is characterized in that it is made up of the component of following mass percent in this solder gross mass:
Cu 0.4％-0.9％
In 0.005％-0.095％
P 0.001％-0.15％
Ni 0.01％-0.2％
RE 0.002％-0.2％
The Sn surplus
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| CNB2006100519697A CN100469511C (en) | 2006-06-14 | 2006-06-14 | No-lead soft brazing alloy |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100519697A CN100469511C (en) | 2006-06-14 | 2006-06-14 | No-lead soft brazing alloy |
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| CN101088698A true CN101088698A (en) | 2007-12-19 |
| CN100469511C CN100469511C (en) | 2009-03-18 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010060299A1 (en) * | 2008-11-28 | 2010-06-03 | 广州瀚源电子科技有限公司 | Reducing dross method of lead-free solder |
| CN102642098A (en) * | 2012-04-23 | 2012-08-22 | 浙江省冶金研究院有限公司 | High-temperature antioxidant lead-free welding rod for dip soldering of enameled wire |
| CN101381826B (en) * | 2008-09-26 | 2012-11-07 | 南昌大学 | Sn-Cu base leadless solder alloy and preparation method |
| CN109702374A (en) * | 2019-02-13 | 2019-05-03 | 南昌大学 | A kind of Sn-Cu-Ni-In lead-free solder alloy and preparation method thereof |
| CN115319221A (en) * | 2022-07-26 | 2022-11-11 | 云南电网有限责任公司昆明供电局 | Cable core joint brazing method based on Sn-based material |
-
2006
- 2006-06-14 CN CNB2006100519697A patent/CN100469511C/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381826B (en) * | 2008-09-26 | 2012-11-07 | 南昌大学 | Sn-Cu base leadless solder alloy and preparation method |
| WO2010060299A1 (en) * | 2008-11-28 | 2010-06-03 | 广州瀚源电子科技有限公司 | Reducing dross method of lead-free solder |
| EP2359981A1 (en) * | 2008-11-28 | 2011-08-24 | Guangzhou Solderwell Enterprise Co., Ltd. | Reducing dross method of lead-free solder |
| EP2359981A4 (en) * | 2008-11-28 | 2011-10-05 | Guangzhou Solderwell Entpr Co Ltd | Reducing dross method of lead-free solder |
| CN102642098A (en) * | 2012-04-23 | 2012-08-22 | 浙江省冶金研究院有限公司 | High-temperature antioxidant lead-free welding rod for dip soldering of enameled wire |
| CN109702374A (en) * | 2019-02-13 | 2019-05-03 | 南昌大学 | A kind of Sn-Cu-Ni-In lead-free solder alloy and preparation method thereof |
| CN109702374B (en) * | 2019-02-13 | 2021-02-09 | 南昌大学 | Sn-Cu-Ni-In lead-free solder alloy and preparation method thereof |
| CN115319221A (en) * | 2022-07-26 | 2022-11-11 | 云南电网有限责任公司昆明供电局 | Cable core joint brazing method based on Sn-based material |
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| CN100469511C (en) | 2009-03-18 |
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Assignee: SHENZHEN TONG FANG ELECTRONIC NEW MATERIAL Co.,Ltd. Assignor: ZHEJIANG ASIA GENERAL SOLDERING & BRAZING MATERIAL Co.,Ltd. Contract fulfillment period: 2009.4.3 to 2014.4.5 Contract record no.: 2009440001527 Denomination of invention: Lead-free solder Granted publication date: 20090318 License type: Exclusive license Record date: 20091014 |
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