CN102990250A - Sn-Cu-Ni-Ce-Cr lead-free solder and preparation method thereof - Google Patents
Sn-Cu-Ni-Ce-Cr lead-free solder and preparation method thereof Download PDFInfo
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- CN102990250A CN102990250A CN201210542227XA CN201210542227A CN102990250A CN 102990250 A CN102990250 A CN 102990250A CN 201210542227X A CN201210542227X A CN 201210542227XA CN 201210542227 A CN201210542227 A CN 201210542227A CN 102990250 A CN102990250 A CN 102990250A
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- tin
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Abstract
The invention discloses a Sn-Cu-Ni-Ce-Cr lead-free solder which comprises the following components by weight percent: 0.5-5.0% of Cu, 0.06-1.0% of Cr, 0.01-1.0% of Ce, 0.01-0.15% of Ni and the balance of Sn. Further, the content of the Cr is 0.2-0.7% through optimization. The lead-free solder has the characteristics that the solder splash yield is high relative to a Sn-Cu-Ni-Ce solder, and the solder splash yield is increased by utilizing the properties of the Cr and adjusting the Cr content, so that the lead-free solder with good mechanical properties, good wettability and strong antioxidant ability are obtained, and can be widely applied to the technical field of electronic materials.
Description
Technical field
The present invention relates to a kind of tin cuprum series leadless solder, particularly a kind of Sn-Cu-Ni-Ce-Cr lead-free solder.
Background technology
In the unleaded process of scolder, it is that bianry alloy and SnAgCu are the systems such as ternary alloy three-partalloy that lead-free solder mainly contains SnAg system, SnCu system, SnZn system, SnBi, compares with traditional SnPb scolder all to have inherent defect.SnAg(SnAgCu) be that scolder is being better than the SnPb scolder aspect fatigue durability and the tensile strength, creep properties and ductility are all good, but its fusing point is higher, and argentiferous is more, high expensive, and antioxidant anticorrosive poor performance.SnCu be scolder relatively other lead-free solder costs are minimum, but alloy melting point, soldering reliability, technique yield and anti-oxidant aspect Shortcomings.SnBi is that the scolder fusing point is low, and tensile strength and croop property are superior, and wetability is good, but high expensive, thermal stability are not enough.SnZn is that the scolder cost is low, and fusing point and SnPb scolder are the most approaching, but easily oxidation, slag tap many, the difficult preparation of solder flux.
For many defectives of above-mentioned lead-free solder, add other metallic elements or introduce second and equate that method can strengthen and improve solder performance to a certain extent.Wherein, in 200510011703.5 1 kinds of SnCuNiCe solders of Chinese patent, by in the SnCu alloy, adding the addition of C e and Ni, it is high to have overcome preferably fusing point, the shortcomings such as wetability is poor, reduced preferably production cost, but the poor shortcoming of oxidation resistance is still obvious in process of production, slag yield can output 45-55 kilogram scruff up to raw material per ton.
Summary of the invention
The objective of the invention is for the poor shortcoming of SnCuNiCe solder non-oxidizability, propose a kind ofly to have kept that the original fusing point of SnCuNiCe solder is low, wetability good, low cost and other advantages, can improve again anti-oxidant and lead-free solder electrical property, reduce well the slag yield of scolding tin.
The objective of the invention is to reach by following technical proposals:
A kind of Sn-Cu-Ni-Ce-Cr lead-free solder is characterized in that it has adopted the raw material of following weight percentage to make:
Cu 0.5-5.0%, Cr 0.06-1.0%, Ce 0.01-1.0%, Ni 0.01-0.15%, all the other are Sn.
Described a kind of Sn-Cu-Ni-Ce-Cr lead-free solder, the percentage by weight that it is characterized in that Cr is 0.2-0.7%.
The present invention has added the Cr element on the basis of original SnCuNiCe solder, and Cr has good non-oxidizability and resistance to corrosion in alloy.Under the impact of rare earth element ce, the Cr element of molten condition forms fine and close Cr because capillary effect is gathered in alloy surface with oxygen element
2O
3Oxide-film, Effective Raise high-temperature oxidation resistance.Oxide-film can be seen the gloss of solder as thin as a wafer clearly.Cr plays the surface tension of reduction liquid metal and the effect of liquid-solid interface energy as a kind of surface active element when welding, improved wettability.The simultaneously combination of Cr, two kinds of elements of Ni can improve the electrode potential of alloy itself, reduces the possibility of chemical attack and electrochemical corrosion.
When the content of Cr is less than 0.06wt% in the SnCuNiCeCr solder, because the Gibbs free energy of Sn is low, the diffusion velocity of Ni is also large than Cr, form the oxide of layering at alloy surface, the thin inequality of oxide-film, effectively in the blocks air oxygen enter and with the contacting of Sn element, oxidation resistance does not obviously change, the scruff that generates in the smelting furnace process is many.When Cr content was higher than 1.0wt%, the oxide-film uneven distribution of alloy surface had reduced wetability and ductility.And the content of control Cr is between 0.06-1.0wt% the time, and alloy surface generation selective oxidation forms the Cr of single densification
2O
3Oxide layer stops the further oxidation of Sn and Ni, has improved antioxygenic property, mechanical performance, the electrical property of scolder.The content of Cr is 0.2-0.7wt% in the control scolder, the alloy content better performances that obtains, and it is stable that antioxygenic properties etc. keep, and wettability improves.
Sn-Cu-Ni-Ce-Cr solder provided by the invention can be prepared from by following method:
(1) after melting in stanniferous 99.95% the refined tin adding graphite crucible, is warming up to 1050 ~ 1150
oC, the smart copper of adding cupric 99.95%, the weight ratio of its copper consumption and tin is 10:90, stirring with wooden stirring rod is smelted into the liquid tin copper alloy, leaves standstill the tin copper intermediate alloy ingot of casting cupric 10% after 30 minutes;
(2) after melting in stanniferous 99.95% the refined tin adding graphite crucible, be warming up to 900 ~ 950
oC adds potassium chloride and covers liquid level, adds the metallic cerium that contains cerium 99.99% again, the weight ratio of its cerium consumption and tin is 10:90, again metallic cerium is pressed in the liquid tin, become the liquid tin cerium alloy with wooden stirring rod stir-melting after, leave standstill and cast the tin cerium intermediate alloy ingot that contains cerium 10% after 30 minutes;
(3) after melting in stanniferous 99.95% the refined tin adding graphite crucible, be warming up to 1550 ~ 1650
oC adds nickeliferous 99.95% metallic nickel again, and the weight ratio of its nickel consumption and tin is 10:90, and stirring with wooden stirring rod is smelted into the liquid tin nickel alloy, leaves standstill to cast nickeliferous 10% tin nickel intermediate alloy ingot after 30 minutes;
(4) after melting in stanniferous 99.95% the refined tin adding graphite crucible, be warming up to 1950 ~ 2050
oC adds the crome metal that contains chromium 99.95% again, and the weight ratio of its chromium consumption and tin is 10:90, and stirring with wooden stirring rod is smelted into the liquid tin evanohm, leaves standstill to cast the tin chromium intermediate alloy ingot that contains chromium 10% after 30 minutes;
(5) get the tin copper intermediate alloy ingot 5-50 weight portion of (1) item, (2) the tin cerium intermediate alloy ingot 0.1-10 weight portion of item, (3) a tin nickel intermediate alloy ingot 0.1-1.5 weight portion and (4) Xiang Xige intermediate alloy ingot 0.6-10 weight portion and the not enough tin amount 28.5-94.2 weight portion of adding surplus tin, add in the stainless-steel pan and carry out melting, pour into the lead-free solder rod, obtaining containing copper, cerium, nickel, chromium, surplus is the lead-free solder of tin.Through follow-up tie rod drawing process, can be made into unleaded tin bar, unleaded tin silk.
Can find out that from the test result of Fig. 1 Sn-Cu-Ni-Ce-Cr solder alloy of the present invention has good antioxygenic property, electrical property, uniform structure, wetability is good, and cost is low, and whole technical process slag yield is low.
Description of drawings
Fig. 1 is raw material mechanical property, solder joint stretching, shear stress, wettability, the rate of spread, scruff rate, metallographic testing result.
The specific embodiment
Get the gun-metal ingot 50kg described in the preparation method provided by the invention, tin evanohm ingot 10kg, tin-cerium alloy ingot 10kg, carry out melting in the not enough tin amount 28.5kg adding stainless-steel pan of tin-nickel alloy ingot 1.5kg and not good surplus tin, be cast into lead-free solder, obtain by tin 92.85%, copper 5%, chromium 1%, cerium 1%, of the present invention product of nickel 0.15% for originally making.
Get the gun-metal ingot 40kg described in the preparation method provided by the invention, tin evanohm ingot 8kg, tin-cerium alloy ingot 0.8kg, tin-nickel alloy ingot 0.8kg adds stainless-steel pan with the not enough tin amount 50.4kg that adds surplus tin and carries out melting, be cast into lead-free solder, obtain the product of the present invention of being made for raw material by tin 95.04%, copper 4%, chromium 0.8%, cerium 0.08%, nickel 0.08%.
Get the gun-metal ingot 30kg described in the preparation method provided by the invention, tin evanohm ingot 5kg, tin-cerium alloy ingot 8kg, tin-nickel alloy ingot 1.2kg and the not enough tin amount 55.8kg that adds surplus tin add in the stainless-steel pan and carry out melting, be cast into lead-free solder, obtain the product of the present invention of being made for raw material by tin 95.58%, copper 3%, chromium 0.5%, cerium 0.8%, nickel 0.12%.
Get the gun-metal ingot 10kg described in the preparation method provided by the invention, tin evanohm ingot 7kg, tin-cerium alloy ingot 5kg, tin-nickel alloy ingot 1.0kg and the not enough tin amount 77kg that adds surplus tin add in the stainless-steel pan and carry out melting, be cast into lead-free solder, obtain the product of the present invention of being made for raw material by tin 97.7%, copper 1%, chromium 0.7%, cerium 0.5%, nickel 0.1%.
Get the gun-metal ingot 15kg described in the preparation method provided by the invention, tin evanohm ingot 0.8kg, tin-cerium alloy ingot 2kg, tin-nickel alloy ingot 0.3kg and the not enough tin amount 81.9kg that adds surplus tin add in the stainless-steel pan and carry out melting, be cast into lead-free solder, obtain the product of the present invention of being made for raw material by tin 98.19%, copper 1.5%, chromium 0.08%, cerium 0.2%, nickel 0.03%.
Get the gun-metal ingot 8kg described in the preparation method provided by the invention, tin evanohm ingot 2kg, tin-cerium alloy ingot 0.5kg, tin-nickel alloy ingot 0.5kg and the not enough tin amount 89kg that adds surplus tin add in the stainless-steel pan and carry out melting, be cast into lead-free solder, obtain the product of the present invention of being made for raw material by tin 98.9%, copper 0.8%, chromium 0.2%, cerium 0.05%, nickel 0.05%.
Embodiment 7
Get the gun-metal ingot 5kg described in the preparation method provided by the invention, tin evanohm ingot 0.6kg, tin-cerium alloy ingot 0.1kg, tin-nickel alloy ingot 0.1kg and the not enough tin amount 94.2kg that adds surplus tin add in the stainless-steel pan and carry out melting, be cast into lead-free solder, obtain the product of the present invention of being made for raw material by tin 99.42%, copper 0.5%, chromium 0.06%, cerium 0.01%, nickel 0.01%.
Comparative Examples
Get the gun-metal ingot 7kg described in the preparation method provided by the invention, tin-cerium alloy ingot 0.1kg, tin-nickel alloy ingot 1kg and the not enough tin amount 91.9kg that adds surplus tin add in the stainless-steel pan and carry out melting, be cast into lead-free solder, obtain the tin copper nickel cerium lead-free solder of being made for raw material by tin 99.19%, copper 0.7%, cerium 0.01%, nickel 0. 1%.
After testing, fusing point is at 225-226
oAbout C, raw material mechanical property, solder joint stretching, shear stress, maximum wetting power, the tin silk rate of spread are not added the scruff content that high-temperature anti-oxidant produces, and structure is as shown in table 1.As can be seen from Figure 1, compare with tin copper nickel cerium alloy scolder, raw material mechanical property, hot strength, shear strength are all more stable, and wetability has preferably lifting, and the scruff productive rate obviously descends.
Claims (2)
1. Sn-Cu-Ni-Ce-Cr lead-free solder is characterized in that it has adopted the raw material of subordinate's percentage by weight to make:
Cu 0.5-5.0%, Cr 0.06-1.0%, Ce 0.01-1.0%, Ni 0.01-0.15%, all the other are Sn.
2. a kind of Sn-Cu-Ni-Ce-Cr lead-free solder according to claim 1, the percentage by weight that it is characterized in that Cr is 0.2-0.7%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210542227XA CN102990250A (en) | 2012-12-14 | 2012-12-14 | Sn-Cu-Ni-Ce-Cr lead-free solder and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210542227XA CN102990250A (en) | 2012-12-14 | 2012-12-14 | Sn-Cu-Ni-Ce-Cr lead-free solder and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53120658A (en) * | 1977-03-30 | 1978-10-21 | Seiko Epson Corp | Improved brazing filler metal |
| CN1895838A (en) * | 2005-07-12 | 2007-01-17 | 北京有色金属研究总院 | Sn-Ag-Cu-Cr-X lead-free soldering material and its preparation |
| CN1895837A (en) * | 2005-07-12 | 2007-01-17 | 北京有色金属研究总院 | Sn-Cu-Cr lead-free soldering material and its preparation |
| CN101850480A (en) * | 2009-03-31 | 2010-10-06 | 宁波银羊焊锡材料有限公司 | Lead-free solder |
-
2012
- 2012-12-14 CN CN201210542227XA patent/CN102990250A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53120658A (en) * | 1977-03-30 | 1978-10-21 | Seiko Epson Corp | Improved brazing filler metal |
| CN1895838A (en) * | 2005-07-12 | 2007-01-17 | 北京有色金属研究总院 | Sn-Ag-Cu-Cr-X lead-free soldering material and its preparation |
| CN1895837A (en) * | 2005-07-12 | 2007-01-17 | 北京有色金属研究总院 | Sn-Cu-Cr lead-free soldering material and its preparation |
| CN101850480A (en) * | 2009-03-31 | 2010-10-06 | 宁波银羊焊锡材料有限公司 | Lead-free solder |
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Application publication date: 20130327 |