CN101880792B - Anti-corrosive anti-oxidation Pb-free solder alloy for aluminum soldering - Google Patents
Anti-corrosive anti-oxidation Pb-free solder alloy for aluminum soldering Download PDFInfo
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- CN101880792B CN101880792B CN201010194371XA CN201010194371A CN101880792B CN 101880792 B CN101880792 B CN 101880792B CN 201010194371X A CN201010194371X A CN 201010194371XA CN 201010194371 A CN201010194371 A CN 201010194371A CN 101880792 B CN101880792 B CN 101880792B
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Abstract
The invention relates to a method for producing an anti-corrosive anti-oxidation Pb-free solder alloy for aluminum soldering. The Pb-free solder alloy consists of the following components in percentage by weight: 0.5 to 5.0 percent of Zn, 0.05 to 2.8 percent of Ag, 0.05 to 0.8 percent of Ga, 0.01 to 0.5 percent of Al, 0.002 to 0.020 percent of P, and the balance of Sn. The Pb-free solder alloy produced according to the inventive method has the melting range of between 198 and 225 DEG C, has better corrosion resistance compared with the conventional Sn-Zn solder and Sn-Ag-Cu solder, and has excellent oxidation resistance and wettability; and a solder joint with high strength can be obtained after the aluminum solder is adopted.
Description
Technical field
The present invention relates to a kind of production method that is applied to the leadless welding alloy of aluminum soft soldering.This brazing filler metal alloy is applicable in the industry such as Electronic Packaging aluminium matter structure or element is connected through brazing mode and be fixed on setting structure or the framework that affiliated technical field is the solder of electronic and electrical equipment.
Background technology
Along with electronics and electric equipment products constantly develop to miniaturization, lightweight, low energy consumption direction, require the employed material should be more and more light, requirement simultaneously must have good comprehensive performances.Though copper has good electrical conductivity, thermal conductivity, corrosion resistance and excellent mechanical property; Be widely used in various industrial circles and along with rapid economic development demand increasing; But it is few in natural reserves, and exploitation and processing cost are high.Therefore, for a long time, people hope to adopt performance close and contain abundant light metal instead of copper at some industrial circles always.Aluminium and alloy thereof have that density is little, light weight, heat conduction and electric conductivity good (being only second to Ag, Cu, Au), good corrosion resistance, low cost and other advantages, become the best replacer of copper undoubtedly.In industries such as automobile, naval vessel, Aero-Space, buildings, the application of aluminium and aluminium alloy is very extensively with ripe.Along with the copper price continues to rise, also more and more receive publicity for copper with aluminium in the Electronic Packaging field.The aluminum soft soldering technology has wide application prospect in the Electronic Packaging; But also be faced with many problems; For example: how to remove the aluminium surface compact effectively and stable oxide film during soldering, how to improve scolder and aluminium soldered fitting corrosion resistance and how to solve aluminum soft soldering technology than problems such as complicacies.
The existing scolder that is applied to aluminum soft soldering mainly contains: Sn-Pb, Sn-Ag-Cu, Sn-Zn etc. are scolder.From Sn-Al phasor and Pb-Al phasor, Sn and Al do not dissolve each other basically, in β-Sn solid solution, can dissolve atomic percentage and be about 1% Al, and Pb and Al almost completely can not dissolve each other.Therefore, Sn-Pb scolder wetting fine with aluminium base under the brazing flux effect, but the bond strength of soldered fitting very low (solid solubility of Sn and Pb and Al is extremely low, interface difficulty formation compound).Simultaneously, the electrode potential of Sn-Pb solder alloy and Al substrate differs greatly, and the etching problem that electrochemical action causes is very serious, and for example, soldered fitting promptly destroys after in 3wt% salt solution, soaking a couple of days.In addition, it is worthy of note that along with the enhancing of global environmental consciousness, various countries have made laws or issued that rules forbid containing the use of the solder of toxicant Pb.The Sn-Ag-Cu series lead-free solder is the first-selection of the replacement tradition solder containing pb generally admitted of present global industry, is widely used in the solder of copper.Aluminum soft soldering aspect, Sn-Ag-Cu scolder be owing to contain a certain amount of Ag, adopts that the corrosion resistance of joint will improve much than the solder alloy that does not add Ag behind this scolder brazed aluminum substrate.But it is little that this is the mutual solubility of alloy and aluminium, and the intermetallic compound that Ag and Al form departing from a side of aluminium base, is that the intensity and the toughness of joint is poor slightly behind the scolder brazed aluminum substrate so adopt this, and the reliability of soldered fitting also decreases.Though adopt the soldered fitting behind the Sn-Zn scolder brazed aluminum substrate to have very high intensity; But in the Sn-Zn scolder because the easy oxidation characteristic of Zn; Make this scolder non-oxidizability with and at the non-constant of the wetability of aluminium base, be unfavorable for the production and the application of this scolder.In addition, the soldered fitting of Sn-Zn scolder and aluminium is anticorrosive also relatively poor, in 3.0wt% salt solution, soaks less than promptly rupturing in a week under the general normal temperature.
Summary of the invention
The technical problem that the present invention will solve is to overcome the technical disadvantages when having lead-free brazing solder aluminium now, and a kind of production method with good resistance corrosion and antioxidizing leadless solder alloy is provided.
A kind of aluminum soft soldering of the present invention is with production method anticorrosive and the oxidation resistant lead-free solder alloy; This leadless welding alloy comprises following composition: Zn 0.5～5.0% by weight percentage, and Ag 0.05～2.8%, and Ga 0.05～0.8%; Al 0.01～0.5%; P 0.002～0.02%, and Sn is a surplus, and this production method comprises following process:
The pure Sn ingot that (1) will weigh up is in proportion put into smelting furnace, and smelting furnace is warming up to 330～360 ℃, adds Ag and even the stirring 15～25 minutes then;
(2) rising furnace temperature when the temperature of treating smelting furnace reaches 380～390 ℃, adds behind the Al in proportion and stirred 15～25 minutes;
(3) treat that temperature of smelting furnace is raised to 390～410 ℃, add antioxidant composition Ga and P in proportion and stirred 15～20 minutes;
(4) with smelting furnace temperature drop to 330～360 ℃, add Zn in proportion and stirred 15～25 minutes, drag for slag, this leadless welding alloy of coming out of the stove;
In the process of above-mentioned (1) to (4), all adopt agitator to stir, to guarantee the uniformity of alloying component with 320～360 rev/mins speed.
Further, this alloy is cast into solder bar or solder.
Further, this alloy further is processed into solder or glass putty.
Further, the Al that is added, Ga, P element all adopt Zn-Al, Sn-Ga and Sn-P intermediate alloy.
It is 198～225 ℃ that this aluminum soft soldering uses fusion temperature anticorrosive and the oxidation resistant lead-free solder alloy, and wetability is good and soldered fitting intensity is higher on aluminium base.
The specific embodiment
A kind of aluminum soft soldering of the present invention comprises following composition: Zn 0.5～5.0% by weight percentage with anticorrosive and oxidation resistant lead-free solder alloy, and Ag 0.05～2.8%, and Ga 0.05～0.8%, and Al 0.01～0.5%, and P 0.002～0.02%, and Sn is a surplus.
Because Al and Zn solid solubility degree are big, in very big content range, form solid solution, therefore add the bond strength that Zn can obviously improve solder alloy and Al substrate.But the content of Zn can not be too high in the solder alloy; Cause the non-oxidizability of scolder poor on the one hand during the Zn too high levels (easily oxidizable mainly due to the Zn metal causes); To cause the wetability of scolder poor on the other hand, and cause the interfacial reaction of scolder non-oxidizability difference and scolder and Al substrate acutely to cause mainly due to the Zn of high-load.Experimental result shows, the addition of Zn is 0.5～5.0% better, is preferably 0.8～3.0% (all be weight percentage, down with).
The corrosion resistance difference of aluminum soft soldering joint is to hinder the one of the main reasons of aluminum soft soldering technology extensive use.Research shows that the Ag that adds trace in the solder alloy can improve the corrosion resistance of solder alloy and aluminum substrate soldered fitting significantly.Contain the Ag solder alloy forming the rich Ag layer of the continuous Ag-Al of one deck,, can strengthen the corrosion resistance of soldered fitting greatly because the existence of Ag-Al compound makes the electrode potential of the electrode potential of joint interface layer apparently higher than Al and scolder with the Al basal body interface.In addition, research also shows, in Sn-Zn hypoeutectic solder alloy, adds the obviously tissue of refinement solder alloy of a spot of Ag, shortens the melting range of scolder simultaneously.Experimental result shows that the addition of Ag is 0.05～2.8%, is preferably 1.0～2.5%.
As previously mentioned; The non-oxidizability that contains the Zn solder alloy is relatively poor; In order to improve the antioxygenic property of solder alloy; When aluminum soft soldering of the present invention designed with the lead-free solder composition, the content of Zn was limited in 0.5～5.0% on the one hand, in solder alloy, added surface active element P, Ga and the Al of the trace anti-oxidant as scolder on the other hand.Element P has been widely used in the solder alloy as anti-oxidant, and its oxidation resistant main cause is that element P also preferentially generates dense oxidation film isolation Sn with the oxygen reaction at the liquid solder surface enrichment, Zn contacts with the direct of oxygen; The addition of P is 0.002～0.020%, is preferably 0.008～0.02%.The antioxidation temperature of P generally is lower than 350 ℃, so the non-oxidizability effect that the P element provides when temperature after the solder alloy fusion surpasses 350 ℃ is not obvious.Ga has that fusing point is low, boiling point is high and low density characteristics, and after adding the Ga element of trace in the scolder, Ga covers the fusion welding surface and plays oxygen contacts in isolated solder and the air work in order to reach the purpose of raising scolder non-oxidizability during solder fusing; Even because the boiling point height of Ga makes its antioxidation also very obvious under the condition of high temperature.Aluminum soft soldering of the present invention is with in the lead-free solder, and the addition of Ga is 0.05～0.8%, is preferably 0.10～0.45%.Al has precedence over the Zn phase oxidation when the solder alloy soldering, and forms fine and close oxide-film at solder surface, thereby hinders the non-oxidizability of the further oxidation raising solder alloy of scolder, but the Al too high levels can influence the wetability of scolder; In the lead-free solder of the present invention, the addition of Al is 0.01～0.5%.
Below in conjunction with concrete embodiment the present invention is done further description.
Above embodiment all can carry out according to the following steps:
The pure Sn ingot that (1) will weigh up is in proportion put into smelting furnace furnace heats to 330～360 ℃, adds Ag then and to stir 15～25 minutes;
(2) rising furnace temperature, when the temperature of treating smelting furnace reached 380～390 ℃, the Al of additional proportion also stirred 15～25 minutes;
(3) treat that temperature of smelting furnace is raised to 390～410 ℃, add anti-oxidant medicament Ga and P and stirred 15～20 minutes,
(4) temperature of smelting furnace is dropped to 330～360 ℃, add Zn in proportion and stirred 15～25 minutes, drag for slag, the cast tin bar or be further used for solder or the production of glass putty of coming out of the stove.
In the process of above-mentioned (1) to (5), all adopt agitator to stir, to guarantee the uniformity of alloying component with 320～360 rev/mins speed.
1) method of testing of spreading area:
(1) will be heavily for after the solder alloy to be measured of 0.5g is stained with the scaling powder of an amount of preparation, place on the 1060 aluminium sheet test films after the prior cleaning (dipping in acetone with absorbent cotton carries out decontamination and handle); The length and width height of 1060 aluminium sheet test films is 40mm * 40mm * 0.5mm;
The aluminium sheet test film that (2) will be placed with scolder and scaling powder places temperature to be set on 260 ℃ the hot plate electric furnace and keeps about 30 seconds, guarantees scaling powder and melt solder balls and sprawls;
(3) take off test film from the hot plate electric furnace, clean the spreading area of taking pictures to the reference of sample and same known area and utilize image analysis processing software calculating sample in the back.
2) corrosion resistance test specimen preparation and test method:
The shape of soldered fitting sample is that size is shown in accompanying drawing 1 in this corrosion resistance test.The length of the anticorrosive sample of soldered fitting is of a size of: 2mm * 2mm * 1mm, brazing temperature is 260 ℃.
Soldered fitting corrosion resistance test method is following: the soldered fitting sample is soaked in the salt solution of 3.0wt%; Sealing also places 70 ± 1 ℃ insulating box (replacing in per 24 hours is the salt solution of identical initial concentration once); Corresponding etching time (immersion fate) is estimated the corrosion resistance of soldered fitting when breaking off according to the joint sample; Immersion fate corresponding when also promptly rupturing shows that at most its corrosion resistance is good, otherwise then poor.
Annotate: the scaling powder of sprawling the employing of test and corrosion resistance test mainly is made up of zinc salt, tin salt and organic amine.
Though disclosed the specific embodiment of the present invention above, they are not the limitations of the scope of the invention, know those skilled in the art person the modification and the variation of the above practical implementation is also contained within the scope of the present invention.
Claims (4)
1. an aluminum soft soldering is with production method anticorrosive and the oxidation resistant lead-free solder alloy; This leadless welding alloy is composed of the following components by weight percentage: Zn 0.5～5.0%, Ag 0.05～2.8%, Ga0.05～0.8%, Al 0.01～0.5%, P 0.002～0.020%; Sn is a surplus, and this production method comprises following process:
The pure Sn ingot that (1) will weigh up is in proportion put into smelting furnace, and smelting furnace is warming up to 330～360 ℃, adds Ag and even the stirring 15～25 minutes then;
(2) rising furnace temperature when the temperature of treating smelting furnace reaches 380～390 ℃, adds behind the Al in proportion and stirred 15～25 minutes;
(3) treat that temperature of smelting furnace is raised to 390～410 ℃, add antioxidant composition Ga and P in proportion and stirred 15～20 minutes;
(4) with smelting furnace temperature drop to 330～360 ℃, add Zn in proportion and stirred 15～25 minutes, drag for slag, this leadless welding alloy of coming out of the stove;
In the process of above-mentioned (1) to (4), all adopt agitator to stir, to guarantee the uniformity of alloying component with 320～360 rev/mins speed.
2. aluminum soft soldering as claimed in claim 1 is with production method anticorrosive and the oxidation resistant lead-free solder alloy:
This alloy is cast into solder.
3. according to claim 1 or claim 2 aluminum soft soldering is with production method anticorrosive and the oxidation resistant lead-free solder alloy:
This alloy further is processed into solder or glass putty.
4. a kind of aluminum soft soldering according to claim 1 is with production method anticorrosive and the oxidation resistant lead-free solder alloy, and it is characterized in that: the Al that is added, Ga, P element all adopt Zn-Al, Sn-Ga and Sn-P intermediate alloy.
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| CN201010194371XA CN101880792B (en) | 2010-06-07 | 2010-06-07 | Anti-corrosive anti-oxidation Pb-free solder alloy for aluminum soldering |
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| CN201010194371XA CN101880792B (en) | 2010-06-07 | 2010-06-07 | Anti-corrosive anti-oxidation Pb-free solder alloy for aluminum soldering |
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| CN101880792B true CN101880792B (en) | 2012-08-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102699562B (en) * | 2012-06-11 | 2015-02-25 | 太原理工大学 | Aluminum low-temperature soft solder and manufacturing method thereof |
| CN102922162B (en) * | 2012-11-01 | 2014-11-26 | 青岛英太克锡业科技有限公司 | Aluminum welding tin paste and preparation method thereof |
| CN106098808B (en) * | 2016-08-10 | 2017-11-28 | 中国科学院电工研究所 | A kind of crystal silicon solar battery base metal front electrode and preparation method thereof |
| CN108060328A (en) * | 2017-12-14 | 2018-05-22 | 蔡郅林 | One kind has writing function alloy and preparation method |
| CN108620765A (en) * | 2018-05-09 | 2018-10-09 | 长沙小如信息科技有限公司 | A kind of automobile metal plate work welding material and welding procedure |
| CN109128570A (en) * | 2018-11-06 | 2019-01-04 | 长沙浩然医疗科技有限公司 | A kind of oxidation-resistant alloy solder and preparation method thereof |
| CN112322929A (en) * | 2020-10-28 | 2021-02-05 | 云南锡业集团（控股）有限责任公司研发中心 | Intermediate alloy for improving oxidation resistance of solder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1443626A (en) * | 2003-04-16 | 2003-09-24 | 浙江大学 | Leadless welding flux with optimum informance and price ratio |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1443626A (en) * | 2003-04-16 | 2003-09-24 | 浙江大学 | Leadless welding flux with optimum informance and price ratio |
| 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 |
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