CN100439027C - Lead-free welding flux alloy suitable for dissimilar metals soldering flux of aluminum and copper - Google Patents
Lead-free welding flux alloy suitable for dissimilar metals soldering flux of aluminum and copper Download PDFInfo
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- CN100439027C CN100439027C CNB2007100263789A CN200710026378A CN100439027C CN 100439027 C CN100439027 C CN 100439027C CN B2007100263789 A CNB2007100263789 A CN B2007100263789A CN 200710026378 A CN200710026378 A CN 200710026378A CN 100439027 C CN100439027 C CN 100439027C
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Abstract
A lead-free solder alloy suitable for copper-aluminum heterogenic metal soft braze welding. The weight percentage of its components is the following: Zn 0.1 ~ 3.0, Cu 0.2 ~ 3.5, Ce 0.001 ~ 0.6, P 0.001 ~ 0.14, Ge or/and Ga 0. 001 ~ 0.13 and the rest is Sn. The solder alloy in the invention has better spreading property on the connection of copper-aluminum heterogenic metal, and the extensibility of alloy is better than Sn-0.7Cu and Sn63Pb37 solder alloy, it applies to soft braze welding of copper-aluminum heterogenic metal.
Description
Technical field
The present invention relates to a kind of leadless welding alloy of heterogenous metal brazing, particularly a kind of leadless welding alloy that is applicable to the solder of copper aluminum dissimilar metal.
Background technology
Along with the continuous development of electronics and information industry, the quantity of electronic product sharply increases.Copper be widely used in printed circuit board, various lead, and demand is increasing, but it is influenced by natural reserves, does not satisfy the demand of social development owing to have favorable conductive, heat conduction and corrosion resistance.Non-renewable resources such as metallic copper consume in a large number, make people recognize consumingly, must be rationally, effectively utilize resource.For the consideration to the utilization of resources and material cost, people need to have proposed scheme close with performance and the aluminium replacement that reserves are abundant relatively in the exploitation of some product (as copper conductor).In implementation process, discovery will realize aluminium substitution copper, and at first the problem that will solve is exactly the connectivity problem of copper aluminium.Because aluminium and brazing connect the welding that belongs to dissimilar metal, there are bigger physics and the difference on the chemical property between the two, so bring very big difficulty to welding.The connection of copper aluminium mainly contains several methods such as melting, Solid-State Welding, soldering.Because copper aluminium fusing point differs bigger, electric arc is difficult to simultaneously heat fused copper and aluminium during melting, and there is intermetallic compound in weld seam, causes welding point fragility big, so suitable low of mechanical strength, and only being fit to some has the occasion of specific (special) requirements; Solid-State Welding comprises friction welding (FW) (low temperature friction welding (FW) and high temperature friction weldering), electric resistance welding, cold welding etc., above-mentioned these methods are all used on producing, but Solid-State Welding can not be used in many occasions, particularly the precision components of some in electron trade owing to be subjected to the restriction of design of part form; Most method is to add transition zone in the aluminium side, becomes the connectivity problem of metal of the same race, and such method one is a complex process; The 2nd, inapplicable in many occasions.The connectivity problem of copper aluminium all is not well solved in the electronic welding field always, especially aspect solder.But because the flexibility of method for welding, adaptability is strong, can select different solders, obtain the soldered fitting of varying strength and different operating temperature, be fit to different occasions, therefore the solderable material of the copper aluminium connection usefulness of compliance with environmental protection requirements is under the new situation satisfied in exploitation, is to realize with the key point of aluminium for copper.
Sn63Pb37 eutectic solder alloy provides being connected of electric, hot conduction and machinery as the main connection material of electronics industry, has satisfied this requirement with its good performance, has obtained extensive use in the hyundai electronics assembly industry.Since plumbous to environment harm and the murder by poisoning of human body more and more is subject to people's attention, electronics, power product is unleaded has been globalization tendency.
At present, can be formed good wetting the combination with copper by the lead-free solder of extensively recommending to use such as Sn-3.0Ag-0.5Cu, Sn-0.7Cu alloy, but and the mutual solubility between the metallic aluminium little, soldering that all can not compatible well Cu-Al dissimilar metal.Because the fragility of intermetallic compound greatly reduces the intensity and the toughness of welding point, and easily causes fire check, makes the reliability of welding point obviously descend.The silver-colored simultaneously rising that has also brought the solder alloy cost, also having limited Sn-Ag-Cu is the use of alloy.
Summary of the invention
The purpose of this invention is to provide a kind of leadless welding alloy that is applicable to the solder of copper aluminum dissimilar metal.
Solder alloy of the present invention, composed of the following components by weight percentage: Zn 0.1～3.0, and Cu 0.2～3.5, and Ce 0.001～0.6, and P 0.001～0.14, and Ge is or/and Ga 0.001～0.13, and surplus is Sn.
From the Zn-Al phasor, can see,, in very large range generate solid solution, therefore can improve bond strength and the wetability thereof of solder on the Al mother metal because Zn, Al mutual solubility are bigger.The result of study of joint interface shows that there are two kinds of structures in solder simultaneously with combining of Al mother metal.Under the effect of brazing flux, solder all has stronger wetting action at Al crystal boundary and grain surface, the crystal boundary that Zn in the solder can be higher along the surface and the edges and corners of crystal grain are to Al crystal grain internal penetration, produce Zn-Al solid solution in the edge of crystal grain, form solder and combine with solid solution between mother metal.Meanwhile, in the bur growth course, Zn and Sn infiltrate Al, form the embedding combination of Al-Sn-Zn needle-like solid solution in solder on some point of Al mother metal, and Here it is, and soldered fitting has the reason of specific intensity.Solder intensity can increase along with the increase of Zn content, and fusion temperature is also on a declining curve.But a large amount of Zn easily forms oxidation and causes alloy to have bigger surface tension at solder surface, has had a strong impact on wetability, so evidence Zn content is 0.1～3.0%, is preferably 0.2～2.8%, further is 0.5～2.4%.
In containing the solder of Zn, add Cu, can make that the Zn atom and the Cu of middle free state have generated the Cu-Zn compound to the rich Zn of alloy mutually, even when fusing, because fusion temperature is lower, can there be the shot-range ordered structure of Cu-Zn in the alloy in a large number, even Medium-range Order Structure, this will inevitably reduce the activity of Zn atom, reduce of the oxidation of Zn atom, thereby effectively reduce the surface tension of liquid solder on the solder surface, make liquid solder can be preferably on the Cu mother metal drawout come and obtain littler angle of wetting.Add in the time of Cu, Zn and can suppress the copper speed of growth of Cu-Zn intermetallic compound at the interface, reduce the corrosion of Zn, improve joint mechanical intensity aluminium.
The adding of Cu can also improve the wetability of solder on copper, improves mechanical performance, can suppress the corrosion of Cu substrate in brazing filler metal alloy.The tensile strength of solder also can obviously be strengthened because of the interpolation of Cu, and the affiliation that adds of Cu reduces the percentage elongation of solder and the contraction percentage of area.If Cu content is too little, performance improvement is not obvious; Too high Cu content then causes fusion temperature to raise, and the wetability variation also can generate fragility Cu-Sn intermetallic compound, even the appearance of Cu-Zn phase, has reduced the bond strength of alloy.So evidence Cu content is 0.2～3.5%, is preferably 0.2～3.3%, further be 0.3～2.9%.
Because comprehensive mechanical performance, processing performance and serviceability that rare earth can improve solder are added in catharsis, metamorphism and the microalloying effect of rare earth element.Common way all is the mishmetal that adds based on Ce, La.Through repetition test research, the result shows that La does not have too big effect to improving alloy property, and Ce is as a kind of surface active element, but crystal grain thinning after the adding, improve the solder corrosion resistance, improve strength of joint, efficiently solve the inefficacy hidden danger that problems such as creep, heat fatigue take place cause soldered fitting.The adding of Rare-Earth Ce has the effect of degasification and modulation alloy refinement.In scolder, dissolve gases such as aerobic, nitrogen usually, because the existence of oxygen, solder alloy is easy to oxidized, and rare earth element ce has certain suction-operated to oxygen, make the oxidability of oxygen descend, can also make the oxide layer surface become fine and close by loose, scolder is difficult for further oxidized, thereby improves the oxidation resistance of scolder.But along with the increase of Ce content, can generate too much oxide at face of weld, hinder scolder sprawling on mother metal, so Ce content is 0.001～0.6%, be preferably 0.005～0.3%, further be 0.009～0.2%.
In scolder, add non-oxidizability and wetability that P can improve alloy.Its non-oxidizability and wetability can be further enhanced by adding Ge, Ga.Can spread to solder surface under the P that exists in the scolder, Ge or the Ga molten state, and form the collection skin layer of one deck structure exquisiteness, densification on the surface.Because the effect of collection skin layer has avoided fusion welding directly to contact with air, prevented that the scolder of fusing is oxidized, wettability is improved.
If the P addition is few, performance there is not improvement basically, content is too much, can form the melting solder alloy with viscosity on its surface, causes weld defect.So P content is 0.001～0.14%, be preferably 0.0015～0.11%, most preferably be 0.002～0.1%.
Similarly, if Ge, Ga too high levels can cause the increase of melting solder surface viscosity, hinder welding operation.So Ge is preferably 0.001～0.10% or/and the content of Ga is 0.001～0.13%, most preferably is 0.0015～0.09%.
The adding of anti-oxidant element P, Ge, Ga has prevented that effectively the easily oxidizable owing to Zn from bringing the easy oxidation of solder, strengthened the practicality of solder.
The specific embodiment
In the preparation process of alloy of the present invention, because the increasing of the fusing point difference of Sn, Zn, Cu, Ce, P, and Ce, Zn and the easy scaling loss of P, in order accurately to control alloying component, guarantee product quality, adopted the form of intermediate alloy to add various alloying elements, the preparation method is as follows:
The Sn-Cu intermediate alloy: 99.95% smart Sn is joined in the graphite crucible, heats up in the fusing back, to the fusion temperature of Cu, adds 99.95% pure Cu.Smart Sn prepares by 90: 10 with the mass percent of pure Cu, stirs, and leaves standstill, and is cast into that to contain that Cu measures be 10% Sn-Cu intermediate alloy ingot.
The Sn-Zn intermediate alloy: 99.95% smart Sn is joined in the graphite crucible, heats up in the fusing back, to the fusion temperature of Zn, adds 99.95% Zn.Smart Sn prepares by 91: 9 with the mass percent of Zn, stirs, and leaves standstill, and is cast into that to contain that Zn measures be 9% Sn-Zn intermediate alloy ingot.
The Sn-Ce intermediate alloy: 99.95% smart Sn is joined in the graphite crucible, heats up in the fusing back, to the fusion temperature of Ce, adds 99.95% Ce.Smart Sn prepares by 91: 3 with the mass percent of Ce, stirs, and leaves standstill, and is cast into that to contain that Ce measures be 3% Sn-Ce intermediate alloy ingot.
Sn-P intermediate alloy: 99.95% smart Sn is joined in the graphite crucible, be warming up to 500 ℃ after the fusing, add the P of AR level.The mass percent of smart Sn and P was prepared by 98: 2, stirred, and left standstill, and was cast into P content and is 2.0% Sn-P intermediate alloy ingot.
Calculate the good Sn-Cu intermediate alloy ingot of weighing, Sn-Zn intermediate alloy ingot, Sn-Ce intermediate alloy ingot, Sn-P intermediate alloy ingot and Ge or/and Ga adopts the crucible induction melting with the alloying component for preparing by alloying component.Be stirred well to fully fusing, leave standstill a period of time, casting, the solder alloy ingot that obtains, the product by further being processed into alloying component of the present invention is as forms such as weldering Sn bar, weldering Sn rod, weldering Sn silk, weldering Sn ball and weldering Sn cream.The specific embodiment is as follows:
Embodiment 1: each component is respectively by weight percentage: Zn 0.7%, and Cu 0.6%, and Ce 0.01%, and P 0.002%, and Ga 0.0015%, and surplus is Sn.
Embodiment 2: each component is respectively by weight percentage: Zn 0.9%, and Cu 0.8%, and Ce 0.05%, and P 0.0265%, and Ga 0.0118%, and Ge 0.0117%, and surplus is Sn.
Embodiment 3: each component is respectively by weight percentage: Zn 1.1%, and Cu 1.2%, and Ce 0.08%, and P 0.051%, and Ga 0.0458%, and surplus is Sn.
Embodiment 4: each component is respectively by weight percentage: Zn 1.5%, and Cu 1.6%, and Ce 0.1%, and P 0.0755%, and Ga 0.0679%, and surplus is Sn.
Embodiment 5: each component is respectively by weight percentage: Zn 1.85%, and Cu 2.1%, and Ce 0.12%, and P 0.1%, and Ga 0.09%, and surplus is Sn.
Solder alloy in the foregoing description has been carried out the measurement of tensile property and spreadability, realized the welding of aluminum steel on copper coin down at 260 ℃, and on cupping machine, carry out tension test, the record breaking load.Spreadability test adopts solder alloy to sprawl on aluminium flake.
Result of the test is as shown in the table:
| The alloy numbering | Tensile property (N) | Spreadability (%) |
| Embodiment 1 | 147.8 | 70.1 |
| Embodiment 2 | 155.1 | 76.4 |
| Embodiment 3 | 171.3 | 75.0 |
| Embodiment 4 | 179.0 | 73.8 |
| Embodiment 5 | 188.4 | 71.9 |
| Sn63Pb37 | 135.6 | 90.3 |
| Sn-0.7Cu | 143.2 | 65.3 |
As can be seen from the above table, solder alloy of the present invention has better spreadability in the connection of copper aluminum dissimilar metal, and the tensile property of alloy is better than Sn63Pb37 and Sn-0.7Cu solder alloy.
The present invention is not limited to above-mentioned case study on implementation, in actual application, the use occasion of the performance requirement that different field that can basis is different, select the alloying component in above-mentioned each case study on implementation, the perhaps heterogeneity proportioning except that above-mentioned case study on implementation, but all be no more than the scope of claims of the present patent application.
Claims (11)
1. leadless welding alloy that is applicable to the solder of copper aluminum dissimilar metal, it is characterized in that composed of the following components by weight percentage: Zn 0.1～3.0, and Cu 0.2～3.5, Ce 0.001～0.6, P0.001～0.14, Ge is or/and Ga 0.001～0.13, and surplus is Sn.
2. the leadless welding alloy that is applicable to the solder of copper aluminum dissimilar metal according to claim 1 is characterized in that Zn content is 0.2～2.8%.
3. the leadless welding alloy that is applicable to the solder of copper aluminum dissimilar metal according to claim 1 and 2 is characterized in that Zn content is 0.5～2.4%.
4. the leadless welding alloy that is applicable to the solder of copper aluminum dissimilar metal according to claim 1 is characterized in that Cu content is 0.2～3.3%.
5. according to claim 1 or the 4 described leadless welding alloys that are applicable to the solder of copper aluminum dissimilar metal, it is characterized in that Cu content is 0.3～2.9%.
6. the leadless welding alloy that is applicable to the solder of copper aluminum dissimilar metal according to claim 1 is characterized in that Ce content is 0.005～0.3%.
7. according to claim 1 or the 6 described leadless welding alloys that are applicable to the solder of copper aluminum dissimilar metal, it is characterized in that Ce content is 0.009～0.2%.
8. the leadless welding alloy that is applicable to the solder of copper aluminum dissimilar metal according to claim 1 is characterized in that P content is 0.0015～0.11%.
9. according to claim 1 or the 8 described leadless welding alloys that are applicable to the solder of copper aluminum dissimilar metal, it is characterized in that P content is 0.002～0.1%.
10. the leadless welding alloy that is applicable to the solder of copper aluminum dissimilar metal according to claim 1 is characterized in that Ge or/and Ga content is 0.001～0.10%.
11., it is characterized in that Ge or/and Ga content is 0.0015～0.09% according to claim 1 or the 10 described leadless welding alloys that are applicable to the solder of copper aluminum dissimilar metal.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100263789A CN100439027C (en) | 2007-01-18 | 2007-01-18 | Lead-free welding flux alloy suitable for dissimilar metals soldering flux of aluminum and copper |
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| CNB2007100263789A CN100439027C (en) | 2007-01-18 | 2007-01-18 | Lead-free welding flux alloy suitable for dissimilar metals soldering flux of aluminum and copper |
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| CN100439027C true CN100439027C (en) | 2008-12-03 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102814595B (en) * | 2012-05-05 | 2015-04-08 | 大连理工大学 | Sn-Zn based near-eutectic lead-free solder alloy for aluminum-bronze soft soldering |
| CN103317253B (en) * | 2013-06-03 | 2015-07-22 | 北京科技大学 | Zn-Al-Cu-based solder for aluminum/copper brazing and preparing method thereof |
| CN105618954A (en) * | 2016-03-15 | 2016-06-01 | 力创(台山)电子科技有限公司 | Welding flux for welding in electro-hydraulic servo valve assembly technology |
| CN106736006A (en) * | 2016-11-30 | 2017-05-31 | 安徽华众焊业有限公司 | Zn Al Cu base solders and preparation method thereof |
| CN108213764A (en) * | 2017-12-13 | 2018-06-29 | 华南理工大学 | A kind of tin base leadless soldering-flux alloy for effectively reducing base material meltage |
| CN107999996B (en) * | 2017-12-13 | 2019-12-10 | 华南理工大学 | tin-base lead-free solder alloy for soft soldering of aluminum and aluminum alloy |
| CN110303269A (en) * | 2019-07-02 | 2019-10-08 | 华侨大学 | For the Sn-Cu-Ti solder of low temperature brazing diamond and application |
| CN113579547B (en) * | 2021-08-12 | 2023-03-10 | 郑州机械研究所有限公司 | Brazing filler metal paste for copper-aluminum dissimilar metal brazing flux-free brazing and brazing method |
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| US20030021718A1 (en) * | 2001-06-28 | 2003-01-30 | Osamu Munekata | Lead-free solder alloy |
| JP2005254298A (en) * | 2004-03-12 | 2005-09-22 | Nippon Steel Corp | Solder alloy for semiconductor packaging and method for manufacturing the same, and solder ball and electronic member |
| EP1647352A1 (en) * | 2004-10-16 | 2006-04-19 | Stannol GmbH | Solder material |
| WO2006059115A1 (en) * | 2004-12-01 | 2006-06-08 | Alpha Fry Limited | Solder alloy |
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- 2007-01-18 CN CNB2007100263789A patent/CN100439027C/en not_active Expired - Fee Related
Patent Citations (6)
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|---|---|---|---|---|
| US20030021718A1 (en) * | 2001-06-28 | 2003-01-30 | Osamu Munekata | Lead-free solder alloy |
| CN1400081A (en) * | 2001-06-28 | 2003-03-05 | 千住金属工业株式会社 | Lead-free welding flux alloy |
| JP2003094195A (en) * | 2001-06-28 | 2003-04-02 | Senju Metal Ind Co Ltd | Lead-free solder alloy |
| JP2005254298A (en) * | 2004-03-12 | 2005-09-22 | Nippon Steel Corp | Solder alloy for semiconductor packaging and method for manufacturing the same, and solder ball and electronic member |
| EP1647352A1 (en) * | 2004-10-16 | 2006-04-19 | Stannol GmbH | Solder material |
| WO2006059115A1 (en) * | 2004-12-01 | 2006-06-08 | Alpha Fry Limited | Solder alloy |
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