CN1718354A - Sn-Ag-Cu-Cr alloy leadless parent metal - Google Patents
Sn-Ag-Cu-Cr alloy leadless parent metal Download PDFInfo
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- CN1718354A CN1718354A CN 200510028445 CN200510028445A CN1718354A CN 1718354 A CN1718354 A CN 1718354A CN 200510028445 CN200510028445 CN 200510028445 CN 200510028445 A CN200510028445 A CN 200510028445A CN 1718354 A CN1718354 A CN 1718354A
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- scolder
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Abstract
A non-lead Sn-Ag-Cu-Cr alloy solder contains Cr (0.005-1 mass %), Ag (0-5), Cu (0-2) and Sn (rest). It has high antioxidizing, anticorrosion and antifatigue performance and high ductility.
Description
Technical field
That the present invention relates to is a kind of preparation method of welding technology field, specifically, is a kind of Sn-Ag-Cu-Cr alloy 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 immerses underground water, thereby the environment and the mankind are caused greatly 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 has also become current electron trade.Up to now, the lead-free solder kind of having developed is a lot, but all exists such and such problem, has the also few of actual application value.Wherein, near eutectic composition is Sn-3.5Ag-0.75Cu Sn-Ag-Cu ternary alloy three-partalloy, 217 ℃ of fusing points, compare with other lead-free solder, wetability is good, the mechanical strength height, have higher endurance and thermal shock, practical value is bigger, is that current generally acknowledged tool substitutes the lead-free solder of Sn-Pb conventional solder, and might becomes the lead-free brazing of standard from now on.
Find by prior art documents, clear the 39th page of villous themeda natural pond gram in " pb-free solder technology " (Science Press, 2004.7), mentioning Sn-Ag-Cu is scolder, and it is higher that this scolder removes fusing point, and beyond price was more expensive, also existing some had problem to be solved.Under or condition that Ag content higher lower, easily form thick fragility Ag in cooling velocity
3Sn, Cu
6Sn
5Phase causes fragility to increase, and ductility reduces, decrease of fatigue strength.Have, Sn-Ag-Cu such as BGA soldered ball are alloy product again, placing or easily oxidation jaundice of surface in corrosive environment, cause welding performance to descend.Also have, serious to equipment corrosions such as stainless steel solder baths when being used for wave-soldering, have to change into expensive titanium or titanium alloy material.Above problem will have a strong impact on the application that this is a scolder as not solving.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, a kind of Sn-Ag-Cu-Cr alloy lead-free solder is provided, mechanical performances such as its non-oxidizability, corrosion resistance, ductility, fatigue durability are improved, and the corrosiveness to stainless steel solder bath etc. obviously weakens simultaneously.
The present invention is achieved by the following technical solutions, and component of the present invention and mass percent thereof are: Cr is 0.005-1%, and Ag is 0-5%, and Cu is 0-2%, and surplus is Sn.
The mass percent of Cr is further defined to 0.01-0.8%.
The mass percent of Cr is further defined to 0.02-0.5% again.
The content of described Ag or Cu only can one is zero, i.e. the present invention also is applicable to Sn-Ag-Cr and Sn-Cu-Cr solder.
Cr is stainless important composition element, has good anti-corrosion and non-oxidizability, and parsing shows, behind the introducing alloying elements cr, has formed the barrier layer of Cr between surperficial Sn or Cu oxide layer and the base metal in the Sn-Ag-Cu scolder.In high temperature or corrosive environment, this barrier layer can stop Sn, Cu to external diffusion, and then has improved the non-oxidizability and the corrosion resistance of scolder.In addition, there are report Cr and Sn element can form Sn
3Cr
2Intermetallic compound, this can play dispersion-strengtherning, crystal grain thinning and prevention Ag in scolder
3Sn, Cu
6Sn
5The effect of growing up mutually, thereby can prevent the deterioration of scolder increases the mechanical performances such as tensile strength, ductility of scolder.Have again, lead-free solder such as Sn-Ag-Cu, Sn-Cu corrosion stainless steel weld groove mainly is that Sn is to stainless corrosion, the existence of Cr element in the scolder can reduce scolder greatly to containing the dissolution velocity of Cr alloy, avoids or improves corrosion to stainless steel solder bath material.When the content of Cr in the Sn-Ag-Cu-Cr solder less than 0.005% the time, no dispersion-strengthened action is difficult to form the barrier layer of Cr at the near surface of scolder, and is obvious inadequately to the improvement of the chemical property of scolder and mechanical performance; When content is higher than 1%, easily cause component segregation, this segregation makes the Cr barrier layer inhomogeneous, and sunburner is bigger to the negative effect of wetability and mechanical performance etc.When if the content of Cr is in the 0.02-0.5% scope in the control scolder, stop the Cr barrier layer of Zn oxidation even, thickness is moderate, can produce dispersion-strengthened action, reduction is to the corrosion of stainless steel etc., do not have tangible segregation phenomena again, make the chemical property of scolder and mechanical performance all be in optimum state.
Sn-Ag-Cu-Cr alloy novel lead-free solder provided by the invention can prepare with a lot of methods, it is the direct smelting process of available four kinds of direct mixed smeltings of metal, the also available Sn-Cr that produces earlier, Ag-Cr, binary or ternary intermediate alloys such as Cu-Cr, Sn-Cu-Cr, Sn-Ag-Cr, Sn-Ag-Cu prepare the substep method of smelting of the final scolder of Sn-Ag-Cu-Cr again.In the preparation, the maximum temperature of melting will can be as the criterion with all metal or alloy in off-bottom, otherwise can cause that the chemical composition of scolder or metallographic structure are inhomogeneous, influences the performance of scolder.Because the alloy easy oxidization burning loss of Cr in the preparation, thus be preferably in vacuum during melting inertia is arranged or protective conditions such as reducibility gas, fused salt under melting.Used raw material can be powdered pure metal, granular simple metal during melting, also can be block simple metal.When adopting the powdery metal melting, speed of melting is very fast, but scaling loss easily, and during the melting of reguline metal, smelting temperature is higher, and the time is longer, but is difficult for scaling loss, cuts both ways.
Characteristics of the present invention are by add the Cr element in the Sn-Ag-Cu alloy, make scolder keep the original good wettability of Sn-Ag-Cu alloy, in the time of advantages such as high mechanical properties, the non-oxidizability and the corrosion resistance of scolder are enhanced about more than once, the ductility of scolder improves 5-30%, corrosivity to brazing point and stainless steel solder bath reduces more than 50%, and has overcome the relatively poor shortcoming of creep-resistant property in use, and the reliability of scolder is further enhanced.
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 in Electronic Packaging or the assembling, form electrode salient point (Bump), chip attach as serigraphy on the Electronic Packaging chips, BGA, CSP soldered ball, SMT such as Reflow Soldering, wave-soldering assembling, the formation of various used for electronic packaging substrates, printed circuit board solder joint, and various repairing welding, manual welding or the like.In a word, scolder provided by the invention, its application is wide.
The specific embodiment
Embodiment 1
Component of the present invention and mass percent thereof are: Cr=0.005%, and Ag=3.5%, Cu=0.75%, surplus is Sn, makes the Sn-3.5Ag-0.75Cu-0.005Cr solder by direct smelting process or substep smelting process.
Various performance measurements show: the fusing point of this scolder, wetability, tensile strength and Sn-3.5Ag-0.75Cu solder are basic identical; At 85 ℃, humidity be under 85% the etching condition after experiment in 24 hours, the jaundice oxidative phenomena reduces, and after resistance to high temperature oxidation experiment in 250 ℃ * 25 hours, glossiness is better than the Sn-3.5Ag-0.75Cu scolder; Less to 304 stainless steel corrosions; Ductility improves about 5% than Sn-3.5Ag-0.75Cu 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%, Cu=0.75%, surplus is Sn, makes the Sn-3.5Ag-0.75Cu-0.01Cr solder by direct smelting process or substep smelting process.
Various performance measurements show: the fusing point of this scolder, wetability, tensile strength and Sn-3.5Ag-0.75Cu solder are basic identical; At 85 ℃, humidity be under 85% the etching condition after experiment in 24 hours, the jaundice oxidative phenomena further reduces, and after resistance to high temperature oxidation experiment in 250 ℃ * 25 hours, glossiness also is better than the Sn-3.5Ag-0.75Cu scolder, and is less to 304 stainless steel corrosions; Ductility improves 5-10% than Sn-3.5Ag-0.75Cu scolder; Slowly cooling off the no fragility increase in back phenomenon.
Embodiment 3
Component of the present invention and mass percent thereof are: Cr=0.02%, and Ag=3.5%, Cu=0.75%, surplus is Sn, makes the Sn-3.5Ag-0.75Cu-0.02Cr solder by direct smelting process or substep smelting process.
Various performance measurements show: the fusing point of this scolder, wetability, tensile strength and Sn-3.5Ag-0.75Cu scolder are basic identical; At 85 ℃, humidity be under 85% the etching condition after experiment in 24 hours, do not have obviously jaundice oxidative phenomena, and after resistance to high temperature oxidation experiment in 250 ℃ * 25 hours, glossiness is much better than the Sn-3.5Ag-0.75Cu scolder; 304 stainless steels there is not clear dissolution; Ductility improves 10-15% than Sn-3.5Ag-0.75Cu scolder; Slowly cooling off the no fragility increase in back phenomenon.
Embodiment 4
Component of the present invention and mass percent thereof are: Cr=0.25%, and Ag=3.5%, Cu=0.75%, surplus is Sn, makes the Sn-3.5Ag-0.75Cu-0.25Cr solder by direct smelting process or substep smelting process.
Various performance measurements show: the fusing point of this scolder, wetability, tensile strength and Sn-3.5Ag-0.75Cu solder are basic identical; At 85 ℃, humidity be under 85% the etching condition after experiment in 24 hours, do not have the jaundice oxidative phenomena, and after resistance to high temperature oxidation experiment in 250 ℃ * 25 hours, glossiness is better than the Sn-3.5Ag-0.75Cu scolder far away; 304 stainless steels there is not clear dissolution; Ductility improves 20-25% than Sn-3.5Ag-0.75Cu scolder; Slowly cooling off the no fragility increase in back phenomenon.
Embodiment 5
Component of the present invention and mass percent thereof are: Cr=0.5%, and Ag=3.5%, Cu=0.75%, surplus is Sn, makes the Sn-3.5Ag-0.75Cu-0.5Cr solder by direct smelting process or substep smelting process.
Various performance measurements show: the fusing point of this scolder, wetability and Sn-3.5Ag-0.75Cu solder are basic identical; At 85 ℃, humidity be under 85% the etching condition after experiment in 24 hours, do not have the jaundice oxidative phenomena, and after resistance to high temperature oxidation experiment in 250 ℃ * 25 hours, glossiness is better than the Sn-3.5Ag-0.75Cu scolder far away; 304 stainless steels there is not clear dissolution; Tensile strength slightly improves, and ductility improves 20-30% than Sn-3.5Ag-0.75Cu scolder; Slowly cooling off the no fragility increase in back phenomenon.
Embodiment 6
Component of the present invention and mass percent thereof are: Cr=0.8%, and Ag=3.5%, Cu=0.75%, surplus is Sn, makes the Sn-3.5Ag-0.75Cu-0.8Cr solder by direct smelting process or substep smelting process.
Various performance measurements show: the fusing point of this scolder, wetability and Sn-3.5Ag-0.75Cu solder are basic identical; At 85 ℃, humidity be under 85% the etching condition after experiment in 24 hours, do not have the jaundice oxidative phenomena, and after resistance to high temperature oxidation experiment in 250 ℃ * 25 hours, glossiness is better than the Sn-3.5Ag-0.75Cu scolder far away; 304 stainless steels there is not clear dissolution; Tensile strength improves, and ductility improves 10-15% than Sn-3.5Ag-0.75Cu scolder; Slowly cooling off the no fragility increase in back phenomenon.
Embodiment 7
Component of the present invention and mass percent thereof are: Cr=1%, and Ag=3.5%, Cu=0.75%, surplus is Sn, makes the Sn-3.5Ag-0.75Cu-1Cr solder by direct smelting process or substep smelting process.
Various performance measurements show: the fusing point of this scolder, wetability and Sn-3.5Ag-0.75Cu solder are basic identical; At 85 ℃, humidity be under 85% the etching condition after experiment in 24 hours, do not have the jaundice oxidative phenomena, and after resistance to high temperature oxidation experiment in 250 ℃ * 25 hours, glossiness is better than the Sn-3.5Ag-0.75Cu scolder far away; 304 stainless steels there is not clear dissolution; Tensile strength improves, and ductility slightly improves than Sn-3.5Ag-0.75Cu scolder; Slowly cooling off the no fragility increase in back phenomenon.
Embodiment 8
Component of the present invention and mass percent thereof are: Cr=0.25%, and Ag=5%, Cu=2%, surplus is Sn, makes the Sn-5Ag-2Cu-0.25Cr solder by direct smelting process or substep smelting process.
Various performance measurements show: the fusing point of this scolder, wetability, tensile strength and Sn-5Ag-2Cu solder are basic identical; At 85 ℃, humidity be under 85% the etching condition after experiment in 24 hours, do not have the jaundice oxidative phenomena, and after resistance to high temperature oxidation experiment in 250 ℃ * 25 hours, glossiness is better than the Sn-5Ag-2Cu scolder far away; 304 stainless steels there is not clear dissolution; Ductility improves 20-30% than Sn-5Ag-2Cu scolder; Slowly cooling off the no fragility increase in back phenomenon.
Embodiment 9
Component of the present invention and mass percent thereof are: Cr=0.25%, and Ag=0%, Cu=0.75%, surplus is Sn, makes the Sn-5Ag-2Cu-0.25Cr solder by direct smelting process or substep smelting process.
Various performance measurements show: the fusing point of this scolder, wetability, tensile strength and Sn-5Ag-2Cu solder are basic identical; At 85 ℃, humidity be under 85% the etching condition after experiment in 24 hours, do not have the jaundice oxidative phenomena, and after resistance to high temperature oxidation experiment in 250 ℃ * 25 hours, glossiness is better than the Sn-5Ag-2Cu scolder far away; 304 stainless steels there is not clear dissolution; Ductility improves 20-30% than Sn-0.75Cu scolder; Slowly cooling off the no fragility increase in back phenomenon.
Embodiment 10
Component of the present invention and mass percent thereof are: Cr=0.25%, and Ag=3.5%, Cu=0%, surplus is Sn, makes the Sn-3.5Ag-0.25Cr solder by direct smelting process or substep smelting process.
Various performance measurements show: the fusing point of this scolder, wetability, tensile strength and Sn-3.5Ag solder are basic identical; At 85 ℃, humidity be under 85% the etching condition after experiment in 24 hours, do not have the jaundice oxidative phenomena; And after resistance to high temperature oxidation experiment in 250 ℃ * 25 hours, glossiness is better than the Sn-3.5Ag scolder far away; 304 stainless steels there is not clear dissolution; Ductility improves 20-25% than Sn-3.5Ag scolder; Slowly cooling off the no fragility increase in back phenomenon.
Claims (4)
1. a Sn-Ag-Cu-Cr alloy lead-free solder is characterized in that, component and mass percent thereof are: Cr is 0.005-1%, and Ag is 0-5%, and Cu is 0-2%, and surplus is Sn.
2. Sn-Ag-Cu-Cr alloy lead-free solder according to claim 1 is characterized in that, Cr is 0.01-0.8%.
3. Sn-Ag-Cu-Cr alloy lead-free solder according to claim 2 is characterized in that, Cr is 0.02-0.5%.
4. Sn-Ag-Cu-Cr alloy lead-free solder according to claim 1 is characterized in that, the content of described Ag or Cu only can one be zero.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510028445 CN1718354A (en) | 2005-08-04 | 2005-08-04 | Sn-Ag-Cu-Cr alloy leadless parent metal |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510028445 CN1718354A (en) | 2005-08-04 | 2005-08-04 | Sn-Ag-Cu-Cr alloy leadless parent metal |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423938B (en) * | 2007-10-30 | 2011-02-16 | 株式会社电装 | Metallic material for brazing, brazing method, and heat exchanger |
| CN104384747A (en) * | 2014-10-08 | 2015-03-04 | 深圳市唯特偶新材料股份有限公司 | Cold-storage-free soldering tin paste and preparing method of cold-storage-free soldering tin paste |
| CN106132612A (en) * | 2014-10-17 | 2016-11-16 | 富士电机株式会社 | Leadless soft soldering method and solder article |
| CN108356441A (en) * | 2018-05-16 | 2018-08-03 | 深圳市亿铖达工业有限公司 | A kind of Sn base solders and preparation method thereof can be used for automotive electronics encapsulation |
-
2005
- 2005-08-04 CN CN 200510028445 patent/CN1718354A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423938B (en) * | 2007-10-30 | 2011-02-16 | 株式会社电装 | Metallic material for brazing, brazing method, and heat exchanger |
| CN104384747A (en) * | 2014-10-08 | 2015-03-04 | 深圳市唯特偶新材料股份有限公司 | Cold-storage-free soldering tin paste and preparing method of cold-storage-free soldering tin paste |
| CN106132612A (en) * | 2014-10-17 | 2016-11-16 | 富士电机株式会社 | Leadless soft soldering method and solder article |
| CN108356441A (en) * | 2018-05-16 | 2018-08-03 | 深圳市亿铖达工业有限公司 | A kind of Sn base solders and preparation method thereof can be used for automotive electronics encapsulation |
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