CN1239290C - Leadless soft brazing alloy for wave crest soldering - Google Patents
Leadless soft brazing alloy for wave crest soldering Download PDFInfo
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- CN1239290C CN1239290C CN 03111446 CN03111446A CN1239290C CN 1239290 C CN1239290 C CN 1239290C CN 03111446 CN03111446 CN 03111446 CN 03111446 A CN03111446 A CN 03111446A CN 1239290 C CN1239290 C CN 1239290C
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Abstract
The present invention relates to a leadless soft soldering alloy, particularly to a leadless soft soldering alloy for wave crest soldering. The present invention contains 0.1 to 2.0% (weight percentage) of Cu, 0.001 to 1% (weight percentage) of P, and Sn with the rest weight percentage; 0.001 to 1% (weight percentage) of Ni is added in the leadless soft soldering alloy metioned above; 0.001 to 1% (weight percentage) of mischmetal RE of La and Ce is added in the leadless soft soldering alloy metioned above. The present invention solves the problems of large quantities of metal oxide generated on the surface of a soldering pot and high possibility of soldered spot bridge linkage occurring when the existing Sn-Cn leadless soft soldering alloy is used. The soldering alloy of the present invention can be formed into soldering tin bars, soldering tin rods, soldering tin wires, soldering tin balls, soldering paste, etc. by the traditional technology processing, so the present invention can supply soldering alloys needed by PCB assembly, SMT microelectronic surface encapsulation and adhesive package, etc.
Description
Technical field: the present invention relates to a kind of no-lead soft soldering, particularly a kind of wave-soldering no-lead soft soldering.
Background technology: at present, the typical solders that is used for electronics industry Electronic Packaging and assembling is the Sn-Pb alloy.Though the Sn-Pb alloy has characteristics such as excellent wetability and weldability, electric conductivity, mechanical property, cost are lower, Pb and contain the poisonous and harmful substance that the Pb thing is the healthy and contaminated environment of harm humans.Along with being gradually improved and strictness of legislations of environmental protection, ban use of plumbous cry surging day by day, Japan, European Union and the U.S. have all worked out the unleaded process of scolder of oneself in succession, and wherein Japanese enterprises has been brought into use no-lead soft soldering in its product.In February, 2003, official's instruction of European Parliament and the official approval WEEE of EU Committee (Waste Electrical and Electronic Equipment) and RoHS (Restriction ofHazardous Subsfances) comes into force, mandatory requirement was from July 1st, 2006, and the electronic product of selling on the European market is necessary for unleaded electronic product.Therefore, in electronics industry, need a kind of unleaded solder alloy to replace traditional Sn-Pb solder alloy.With in the no-lead soft soldering, the Sn0.7Cu eutectic alloy is because low price, raw material supply abundance, solder alloy element easily reclaim, favorable mechanical performance and series of advantages such as machinability and more traditional SnPb scolder welding spot reliability height can be as main no-lead soft soldering when wave-soldering (227 ℃ of higher melt of scolder then relative less with the components and parts influence to equipment) at current wave-soldering.Yet,, in the scolder fusion process, easily produce the microstructure segregation phenomenon for the Sn-Cu brazing filler metal.The Sn0.7Cu no-lead soft soldering exists the comparison distinct issues to comprise 2 points when carrying out wave-soldering in addition, any is the bridging of solder joint, the on the other hand dissolving of the Cu in the printed substrate in fusion welding, this has not only changed the composition of fusion welding, and the Cu that forms with Sn
6Sn
5Intermetallic compound is mutually because Cu
6Sn
5Phase density is low than Sn0.7Cu, can be deposited in the fusion welding pot bottom and make that removal is difficult unusually, and this has just shortened the service life of scolder.Therefore Japanese Nihon is at United States Patent (USP) 6,180, the leadless solder be made up of Sn-(0.3～0.7) Cu-(0.04～0.1) Ni is proposed on the basis of SnCu eutectic composition in 055, element Ni can suppress the dissolving of Cu in fusion welding, reduces the dissolution velocity of Cu in molten solder and the possibility of bridging generation.On the other hand and since Sn-Cu be the content of Sn in the leadless solder up to more than the 99wt%, in use compare the generation that can increase metal oxide greatly with traditional Sn-37Pb scolder.
Summary of the invention: for solving existing Sn-Cu is the unleaded cored solder high problem of possibility that scolder pot surface metal oxide generation is too high in use, the solder joint bridging takes place, and the invention provides a kind of wave-soldering leadless solder.Wave-soldering of the present invention is made up of following component in percentage by weight with leadless solder: Cu 0.1～2.0%, P 0.001～1%, Sn surplus.In this cored solder alloy, also has unavoidable impurities.In the above-mentioned leadless solder, further add the Ni of weight 0.001～1%.In the above-mentioned leadless solder, further add the La and the Ce mishmetal Re of weight 0.001～1%.Leadless solder involved in the present invention does not use the lead of hypertoxicity in as the tin of the basic composition of scolder and lead, have the solderability better than existing scolder.Describe effect and the optimum content thereof that respectively adds element among the present invention below in detail.Add Cu and can form binary eutectic to reduce the fusing point of scolder with Sn in 0.7% weight, 227 ℃ the time.As previously mentioned, compare with traditional SnPb scolder, the Sn-Cu eutectic has series of advantages, comprises the density (7.4g/mm of scolder
3) than SnPb (8.4g/mm
3) low, high heat conductance, low-resistivity, mechanical performance and welding spot reliability etc.Preferably 0.5～1.0% of copper content, more preferably 0.3～0.7%.Owing to the present invention with the Cu element not leaded a large amount of tin (reaching more than 99%) that contains in generation, therefore when reality is used, can increase the generation of scolder pot fusion welding surface metal oxide.Therefore, be added with the oxidation that 0.001～1% element P can stop solder alloy effectively, because the kelvin effect of element P, the upper surface of molten braze alloy forms one deck very thin films in the scolder pot, by the oxidation reaction that takes place at solder surface:
；
Can hinder solder alloy directly and being in contact with one another of surrounding air.On the other hand, the existence of element Cu has also promoted the kelvin effect of P in the scolder, thereby prevents the further oxidation of solder surface.If the addition of element P is less than 0.001%, this anti-oxidation effect is just not obvious, adds the solderability of the element P meeting deterioration solder alloy more than 1%.When adding P, P content preferably 0.005～0.5% in alloy, and more preferably 0.005～0.1%.Can further add micro-Ni among the present invention on the basis of SnCu solder interpolation element P, Ni mainly plays a part two aspects.Can suppress the dissolving of Cu in solder in printed circuit Cu substrate and the components and parts pin on the one hand, reduce Cu in the fusion welding
6Sn
5Growing amount, prolonged service life of scolder; On the other hand since Ni to Cu
6Sn
5The dissolving of compound in mutually can change the intermetallic compound form, promptly changed into spherically by needle-like, and the mobile influence of the relative molten solder of spheroidizing compound is much smaller, thereby reduces the formation of bridging.If Ni content is less than 0.001%, its effect is just not obvious, adds 1% above Ni and can make the solder performance variation, and fusing point raises.When adding Ni, in alloy preferably 0.01～0.5% of Ni content.Also add proper amount of rare-earth element Re among the present invention improving the tissue of solder,, the tissue of solder is played a part metamorphic homogenization, thereby improve the mechanical property of brazing filler metal alloy because the Re element can promote the forming core of solder in process of setting.The adding of Re can also significantly improve solder creep resistant fatigue behaviour.If Re content is less than 0.001%, its effect is just not obvious, adds 1% above Re and can make the solder performance variation, and fusing point raises.When adding Re, in alloy preferably 0.05～0.5% of Re content.According to the effect of above each composition, scolder of the present invention does not contain Pb, compare with existing Sn-Cu solder alloy, and still be all to have shown superior characteristic aspect the creep resistant fatigue properties of scolder in solidified structure, the mechanical property of scolder.No-lead soft soldering of the present invention with above-mentioned composition can be smelted by conventional method, and promptly Sn, Cu are with the raw metal supply, and Ni, P and Re then require to add by the form with intermediate alloy, heating and stirring in crucible, and casting can obtain solder alloy.Solder alloy of the present invention can be processed to form the form of soldering tin bar, scolding tin rod, solder stick, solder ball and soldering paste etc. by traditional handicraft, thereby can satisfy needed solder alloys such as PCB assembling, SMT microelectronics surface encapsulation and surface mount.The object of the present invention is to provide a kind of leadless solder, at SnCu is on the basis of no-lead soft soldering, addition element P, the kelvin effect that the P element is presented in the scolder pot of fusion, can reduce the generation of scolder pot surface metal oxide, the fraction defective when reducing the welding of PCB circuit board; On the basis of adding P, further add element Ni and La, Ce mishmetal Re, Ni can reduce the possibility that the solder joint bridging takes place, and the dissolving of inhibition Cu in solder, adding Re can make the thick rich Sn in the alloy graining tissue be inhibited mutually, promptly by metamorphism to the solder solidification and crystallization process by using, realize the homogenising of solidified structure, thereby improve the mechanical property and the creep resistant fatigue properties of brazing filler metal alloy.
The specific embodiment
The specific embodiment one: the wave-soldering of present embodiment is made up of following component in percentage by weight with leadless solder: Cu 0.1～2.0%, P 0.001～1%, Sn surplus.
The specific embodiment two: what present embodiment and the specific embodiment one were different is that above-mentioned leadless solder is made up of following component in percentage by weight: Cu 0.1～2.0%, P 0.001～1%, Ni 0.001～1%, Sn surplus.
The specific embodiment three: what present embodiment and the specific embodiment one, two were different is that above-mentioned leadless solder is made up of following component in percentage by weight: Cu 0.1～2.0%, P 0.001～1%, Ni 0.001～1%, La and Ce mishmetal Re 0.001～1%, Sn surplus.
The specific embodiment four: what present embodiment and the specific embodiment one were different is that copper content is 0.5～1.0%.
The specific embodiment five: what present embodiment and the specific embodiment one were different is that P content is 0.005～0.5%.
The specific embodiment six: what present embodiment and the specific embodiment two were different is that Ni content is 0.01～0.5%.
The specific embodiment seven: what present embodiment and the specific embodiment three were different is that Re content is 0.05～0.5%.
The specific embodiment eight: the leadless solder of present embodiment is made up of following component in percentage by weight: Cu 0.7%, P 0.01～1%, Sn surplus.
The specific embodiment nine: the leadless solder of present embodiment is made up of following component in percentage by weight: Cu 0.7%, P 0.05%, Sn surplus.
The specific embodiment ten: the leadless solder of present embodiment is made up of following component in percentage by weight: Cu 0.7%, P 0.01%, Ni 0.05%, Sn surplus.
The specific embodiment 11: the leadless solder of present embodiment is made up of following component in percentage by weight: Cu 0.7%, P 0.01%, Re 0.05%, Sn surplus.
The leadless solder of above-mentioned embodiment and traditional leadless solder (its composition is Cu0.7%, Sn surplus) have been carried out the antioxygenic property test, be about to scolder and be incubated the burn out rate of observing scolder in 50 hours under 280 ℃ of temperature, concrete result of the test sees Table 1.Therefrom in traditional SnCu (comparative example), add the antioxygenic property that element P (embodiment 8 and embodiment 9) can obviously strengthen scolder as can be seen, especially at P content under 0.01% condition; The oxidation resistance of scolder reduces when P content is higher on the contrary, but still will be higher than the conventional case of not adding element P.
Table 1 embodiment of the invention and traditional SnCu no-lead soft soldering antioxygenic property are relatively
| Alloying component (weight %) | Former weight (g) | Residuals weight (g) | Burn out rate (%) | Temperature retention time (h) | Holding temperature (℃) | |||||
| Sn | Cu | P | Ni | Re | ||||||
| Embodiment 8 | 99.29 | 0.7 | 0.01 | 50 | 49.53 | 0.928 | 50 | 280 | ||
| Embodiment 9 | 99.25 | 0.7 | 0.05 | 50 | 49.18 | 1.627 | 50 | 280 | ||
| Embodiment 10 | 99.24 | 0.7 | 0.01 | 0.05 | 50 | 49.30 | 1.396 | 50 | 280 | |
| Embodiment 11 | 99.24 | 0.7 | 0.01 | 0.05 | 50 | 49.24 | 1.520 | 50 | 280 | |
| Traditional approach | 99.3 | 0.7 | 50 | 47.02 | 5.952 | 50 | 280 | |||
Claims (10)
1, wave-soldering leadless solder is characterized in that it is made up of following component in percentage by weight: Cu 0.1～2.0%, P 0.001～1%, Sn surplus.
2, wave-soldering leadless solder according to claim 1 is characterized in that copper content is 0.5～1.0%.
3, wave-soldering leadless solder according to claim 1 is characterized in that P content is 0.005～0.5%.
4, wave-soldering leadless solder is characterized in that it is made up of following component in percentage by weight: Cu 0.1～2.0%, P 0.001～1%, Ni 0.001～1%, Sn surplus.
5, wave-soldering leadless solder according to claim 4 is characterized in that Ni content is 0.01～0.5%.
6, wave-soldering leadless solder is characterized in that it is made up of following component in percentage by weight: Cu 0.1～2.0%, P 0.001～1%, Ni 0.001～1%, La and Ce mishmetal Re 0.001～1%, Sn surplus.
7, wave-soldering leadless solder according to claim 6 is characterized in that Ni content is 0.01～0.5%.
8, wave-soldering leadless solder according to claim 6 is characterized in that Re content is 0.05～0.5%.
9, wave-soldering leadless solder is characterized in that it is made up of following component in percentage by weight: Cu 0.1～2.0%, P 0.001～1%, La and Ce mishmetal Re 0.001～1%, Sn surplus.
10, wave-soldering leadless solder according to claim 9 is characterized in that Re content is 0.05～0.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03111446 CN1239290C (en) | 2003-04-11 | 2003-04-11 | Leadless soft brazing alloy for wave crest soldering |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03111446 CN1239290C (en) | 2003-04-11 | 2003-04-11 | Leadless soft brazing alloy for wave crest soldering |
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| CN1442272A CN1442272A (en) | 2003-09-17 |
| CN1239290C true CN1239290C (en) | 2006-02-01 |
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| CN 03111446 Expired - Lifetime CN1239290C (en) | 2003-04-11 | 2003-04-11 | Leadless soft brazing alloy for wave crest soldering |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4844393B2 (en) * | 2004-06-01 | 2011-12-28 | 千住金属工業株式会社 | Die bonding method and electronic parts |
| CN1269613C (en) * | 2004-08-24 | 2006-08-16 | 陈明汉 | Improved Sn-0.7 wt% Cu lead-free welding flux |
| JP5018978B1 (en) * | 2010-11-19 | 2012-09-05 | 株式会社村田製作所 | Conductive material, connection method using the same, and connection structure |
| CN102476251A (en) * | 2010-11-25 | 2012-05-30 | 中国科学院金属研究所 | Sn-Cu lead-free welding flux capable of resisting atmospheric corrosion |
| CN102642099A (en) * | 2012-05-05 | 2012-08-22 | 大连理工大学 | Sn-Zn-based lead-free solder alloy for aluminum bronze soldering and method for preparing same |
| CN105397328A (en) * | 2015-12-15 | 2016-03-16 | 瑞声光电科技(常州)有限公司 | Sn-Cu lead-free brazing filler metal and manufacturing method thereof |
| CN107699736B (en) * | 2017-10-24 | 2019-09-06 | 河南科技大学 | One Albatra metal hot dip tin alloy and preparation method thereof |
| CN107502782B (en) * | 2017-10-24 | 2019-06-21 | 河南科技大学 | Copper alloy hot dip rare earth tin-based alloy and preparation method thereof |
| CN113416866A (en) * | 2021-06-29 | 2021-09-21 | 南京青锐风新材料科技有限公司 | Lead-free solder oxidation resistant alloy and production and preparation process thereof |
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Denomination of invention: Lead free solder alloys for wave soldering Effective date of registration: 20210409 Granted publication date: 20060201 Pledgee: Shenzhen small and medium sized small loan Co.,Ltd. Pledgor: YIK SHING TAT INDUSTRIAL Co.,Ltd. Registration number: Y2021980002513 |
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Granted publication date: 20060201 |