CN102039496A - Oxidation-resistant low-silver lead-free brazing filler metal and production method thereof - Google Patents
Oxidation-resistant low-silver lead-free brazing filler metal and production method thereof Download PDFInfo
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- CN102039496A CN102039496A CN2009102086542A CN200910208654A CN102039496A CN 102039496 A CN102039496 A CN 102039496A CN 2009102086542 A CN2009102086542 A CN 2009102086542A CN 200910208654 A CN200910208654 A CN 200910208654A CN 102039496 A CN102039496 A CN 102039496A
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- filler metal
- brazing filler
- solder
- metal alloy
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Abstract
The invention relates to lead-free brazing filler metal alloy for micro-connection of electronic products. The brazing filler metal alloy is characterized by comprising the following components in percentage by weight: 0.3-1.0% of Ag, 0.3-1.2% of Cu, 0.01-0.45% of Al or Mg, 0.01-0.3% of Ga, 0.008-0.03% of P, 0.005-0.03% of Ni and balance of Sn. The Ag content of the lead-free brazing filler metal provided by the invention is low, and the melting temperature is moderate (215-230 DEG C); and moreover, the lead-free brazing filler metal has excellent wettability, oxidation resistance and mechanical properties and can meet the requirements of the micro-interconnection encapsulation technology for the performance of the brazing filler metal.
Description
Technical field
The present invention relates to the brazing filler metal alloy that the little connection of electronic product is used in the field of electronic materials.
Background technology
Along with scientific and technological circle and the public improve constantly the cognition of damaging effect plumbous in the used tin of electronics industry-lead (Sn-Pb) solder, countries in the world have been limited by making laws and even have been forbidden the application of deleterious material such as solder containing lead in industry such as microelectronics.At present, the unleaded of electronic product is rooted in the hearts of the people.Sn-Cu brazing filler metal, Sn-Ag-Cu brazing filler metal and Sn-Bi brazing filler metal etc. replace the Sn-Pb solder gradually and are widely used in the Electronic Packaging industry.Wherein the Sn-Ag-Cu series leadless solder is generally believed first selection that replaces traditional solder containing lead with its excellent wetability, mechanical property etc. by industry.In the Sn-Ag-Cu brazing filler metal, it is extensive that the nearly eutectic Sn-3.0Ag-0.5Cu of ternary lead-free brazing is used outermost, but owing to its Ag that contains high level makes its cost higher.On the other hand, current, consumer electronics product is just becoming a fastest-rising part in the electronics industry, is the increased popularity of the hand-hold electronic equipments and the mobile electronic device of representative with mobile phone, digital camera, video camera, notebook computer, MP3 player etc. particularly.These are handed and compare with most of conditional electronic device with portable type electronic product, and its update is faster, the service life cycle is shorter, and therefore the inefficacy that is caused by temperature cycles has not been the integrity problem of its major concern; But they are easier to be subjected to jolting unexpectedly, to shake, to collide and to fall, and then brings in the electronic package interconnections solder joint another new inefficacy mechanism that is caused by mechanical shock, promptly by falling/impact the integrity problem that causes.The content that reduces Ag in the solder can reduce the modulus of brazing filler metal alloy, improves its anti-drop/impact property; Add Ni and then can improve structure and the pattern of Compound I MC between the interface metal of solder and substrate (as Cu or Ni etc.), also can effectively improve the anti-drop/impact capacity of brazing filler metal alloy.Therefore, the Sn-Ag-Cu solder develops to low silver-colored direction gradually at present.Chinese patent application numbers 200810053841.3 disclose a kind of low-silver solder added easy oxidation element Zn and Bi and cause this solder non-oxidizability and wetability poor.The content (2.0-2.9wt%) of Chinese patent application number 200310115384.3 disclosed a kind of low silver leadless solder Ag is still higher, and the cost of brazing filler metal alloy reduces not obvious.
Summary of the invention
The invention reside in the shortcoming that overcomes prior art, the low silver leadless solder of a kind of low cost, non-oxidizability, good mechanical properties is provided.
Oxidation resistant low-silver lead-free brazing filler metal alloy of the present invention, its prescription consists of by weight percentage:
Ag 0.3-1.0％
Cu 0.3-1.2％
P 0.008-0.030％
Ga 0.01-0.3％
Al (or Mg) 0.01-0.45%
Ni 0.005-0.03％
The Sn surplus
The production method of low silver oxidation resistance of the present invention and anti-drop/strong lead-free solder alloy of impact capacity is as follows:
The pure Sn ingot that (1) will weigh up is in proportion put into smelting furnace and is heated to 340-360 ℃, adds Ag and Cu then and stirs 15-25 minute with 350-400 rev/min mixing speed;
When (2) temperature for the treatment of smelting furnace reached 380-390 ℃, the Al (or Mg) that adds specified amount also stirred 15-25 minute;
(3) add Ni and stirring 15-20 minute;
(4) treat that temperature of smelting furnace is raised to 390-410 ℃, add anti-oxidant medicament Ga and P and stirred 15-20 minute,
(5) will melt temperature drop to 340-360 ℃, and drag for the cast tin bar of coming out of the stove behind the slag and make finished product or be further used for solder production and make the production that powder is used for soldering paste.
The inventor discovers the brazing filler metal for Sn-Ag-Cu, and when the content of Ag during at 0.5-1.0wt%, the wetability of solder approaches the Sn-3.0Ag-0.5Cu brazing filler metal alloy of extensive use.Accompanying drawing 1 be Sn-0.5Ag-0.5Cu solder, Sn-1.0Ag-0.5Cu solder and Sn-3.0Ag-0.5Cu wetability relatively, wherein Fig. 1 (a) be three solders at 280 ℃ with 5%ZnCl
2Saturated rosin solution is done under the brazing flux angle of wetting data with copper base; Fig. 2 (b) is the surface tension of three kinds of solders under 280 ℃ of molten conditions (the solder surface tension wetability of the bright solder of novel more is good more).
Table 1 is that the melting region of part low silver leadless solder and Sn-3.0Ag-0.5Cu solder compares.Table 2 is that the tensile property of part low silver leadless solder and Sn-3.0Ag-0.5Cu body solder compares.As seen, the wetability of low-silver solder is poor unlike the Sn-3.0Ag-0.5Cu solder, and its molten temperature region is 215-230 ℃, and the solder melting range is narrower, and fusion temperature is not high yet.But low-silver solder is with respect to the Sn-3.0Ag-0.5Cu solder, and mechanical property will differ from far away.The present invention adds the Al or the Mg of trace, studies show that the intensity of solder increases by a relatively large margin, and mechanical property is significantly improved.The addition of Al (or Mg) is generally 0.01-0.45wt%, is preferably 0.02-0.3wt%.
The fusion temperature of table 1 part low-silver solder and Sn-3.0Ag-0.5Cu solder relatively
The mechanical property of table 2 part low-silver solder and Sn-3.0Ag-0.5Cu solder relatively
(strain rate: 2 * 10
-3S
-1)
Brazing filler metal alloy is in production and commercial Application, and the antioxygenic property of solder is most important.Solder non-oxidizability difference causes performance wetability variation in the solder application, produces a large amount of scruffs simultaneously and causes huge waste.Add micro-P and the Ga antioxidant as solder in the oxidation resistant low-silver lead-free solder of the present invention, the antioxygen of solder is significantly improved.P is widely used in the brazing filler metal alloy as antioxidant, and oxidation resistant main cause is the oxyphie kelvin effect of element P.The addition of P is 0.008-0.030wt%, is preferably 0.01-0.03wt%.The antioxidation effective temperature of P generally is lower than 350 ℃, so the non-oxidizability effect that the P element provides when the brazing filler metal alloy temperature surpasses 350 ℃ is not obvious.Ga has the characteristics of fusing point low (29.78 ℃), boiling point height (2403 ℃) and density low (5.91g/mL).Add the Ga element of trace in the solder, Ga covers the molten solder surface and plays the effect that prevents the solder oxidation during solder fusing.Because it promptly is also very obvious under the condition of high temperature that the boiling point height of Ga makes its antioxidation.The Ga addition is 0.01-0.3wt%, is preferably 0.04-0.02wt%.
Add in the oxidation resistant low-silver lead-free solder of the present invention and reduce the corrosion of brazing filler metal alloy when micro-Ni element can reduce the brazing filler metal alloy brazed copper copper base.Its cardinal principle is to add the Ni solder easily to form Ni
3Sn
2Intermetallic compound has suppressed Cu
6Sn
5Thereby grow up and reduce the corrosion of solder copper base, Ni can also effectively improve structure and the pattern of Compound I MC between the interface metal of solder and substrate (as Cu or Ni etc.) simultaneously, also can effectively improve the anti-drop/impact capacity of brazing filler metal alloy.The addition of Ni is generally 0.005-0.03wt%, is preferably 0.008-0.03wt%.
Description of drawings
Fig. 1 is the wettability comparison of three kinds of solders of Sn-Ag-Cu, and wherein figure (a) is the angle of wetting comparison of low-silver solder and Sn-3.0Ag-0.5Cu solder and copper base; Figure (b) is that low-silver solder and the surface tension of Sn-3.0Ag-0.5Cu solder under 280 ℃ of environment temperatures compare.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment, need to prove that embodiment does not constitute the restriction to the claimed scope of the present invention.
Annotate: hot strength is to be 2 * 10 in strain rate
-3S
-1Institute's measured value.
Above embodiment all can produce by the following method:
The pure Sn ingot that (1) will weigh up is in proportion put into smelting furnace and is heated to 340 ℃, adds Ag and Cu then and stirs 20 clocks with 360 rev/mins mixing speed;
When (2) temperature for the treatment of smelting furnace reached 380 ℃, the Al (or Mg) that adds specified amount also stirred 15 minutes;
(3) add Ni and stirring 20 minutes;
(4) treat that temperature of smelting furnace is raised to 400 ℃, add anti-oxidant medicament Ga and P and stirred 20 minutes;
(5) will melt temperature drop to 350 ℃, dragging for comes out of the stove behind the slag pours into tin bar and makes finished product or be further used for solder production and make the production that powder is used for soldering paste.
Claims (4)
1. oxidation resistant low-silver lead-free brazing filler metal alloy, it is characterized in that: containing percentage by weight is 0.3-1.0%Ag, 0.3-1.2%Cu, 0.01-0.45%Al or Mg, 0.01-0.3%Ga, 0.008-0.03%P, 0.005-0.03Ni, Sn surplus.
2. oxidation resistant low-silver lead-free brazing filler metal alloy is characterized in that its composition is preferably that to contain percentage by weight be 0.5-0.8%Ag, 0.4-0.8%Cu, 0.02-0.3%Al or Mg, 0.04-0.2%Ga, 0.01-0.03%P, 0.008-0.03%Ni, Sn surplus.
3. the described oxidation resistant low-silver lead-free brazing filler metal alloy of claim 1 is characterized in that:
The pure Sn ingot that (1) will weigh up is in proportion put into smelting furnace and is heated to 340-360 ℃, adds Ag and Cu then and stirs 15-25 minute with 350-400 rev/min mixing speed;
When (2) temperature for the treatment of smelting furnace reached 380-390 ℃, the Al of additional proportion (or Mg) also stirred 15-25 minute;
(3) add Ni and stirring 15-20 minute;
(4) treat that temperature of smelting furnace is raised to 390-410 ℃, add anti-oxidant medicament Ga and P and stirred 15-20 minute,
(5) will melt temperature drop to 340-360 ℃, and drag for the cast tin bar of coming out of the stove behind the slag and make finished product or be further used for solder production and make the production that powder is used for soldering paste.
4. the described oxidation resistant low-silver lead-free brazing filler metal alloy of claim 1 is characterized in that Al, the Mg, the P element that are added all adopt Sn-Al, Sn-Mg and Sn-P intermediate alloy.
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| CN2009102086542A CN102039496A (en) | 2009-10-23 | 2009-10-23 | Oxidation-resistant low-silver lead-free brazing filler metal and production method thereof |
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| CN2009102086542A CN102039496A (en) | 2009-10-23 | 2009-10-23 | Oxidation-resistant low-silver lead-free brazing filler metal and production method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103934590A (en) * | 2014-04-13 | 2014-07-23 | 北京工业大学 | ZnAlMgIn high temperature lead-free solder |
| CN108941969A (en) * | 2018-07-20 | 2018-12-07 | 广东中实金属有限公司 | A kind of lead-free solder and preparation method thereof suitable for varistor |
| CN110936061A (en) * | 2019-12-20 | 2020-03-31 | 重庆科技学院 | Low-silver SAC composite solder with high tensile strength |
| JP2022515254A (en) * | 2018-12-27 | 2022-02-17 | アルファ・アセンブリー・ソリューションズ・インコーポレイテッド | Lead-free solder composition |
| CN115156755A (en) * | 2022-08-12 | 2022-10-11 | 云南锡业集团（控股）有限责任公司研发中心 | Sn-Ag-Cu lead-free solder containing Bi, ni and Ga and preparation method thereof |
-
2009
- 2009-10-23 CN CN2009102086542A patent/CN102039496A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103934590A (en) * | 2014-04-13 | 2014-07-23 | 北京工业大学 | ZnAlMgIn high temperature lead-free solder |
| CN103934590B (en) * | 2014-04-13 | 2016-08-17 | 北京工业大学 | A kind of ZnAlMgIn high-temp leadless solder |
| CN108941969A (en) * | 2018-07-20 | 2018-12-07 | 广东中实金属有限公司 | A kind of lead-free solder and preparation method thereof suitable for varistor |
| JP2022515254A (en) * | 2018-12-27 | 2022-02-17 | アルファ・アセンブリー・ソリューションズ・インコーポレイテッド | Lead-free solder composition |
| CN110936061A (en) * | 2019-12-20 | 2020-03-31 | 重庆科技学院 | Low-silver SAC composite solder with high tensile strength |
| CN115156755A (en) * | 2022-08-12 | 2022-10-11 | 云南锡业集团（控股）有限责任公司研发中心 | Sn-Ag-Cu lead-free solder containing Bi, ni and Ga and preparation method thereof |
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Application publication date: 20110504 |