CN101880792A - 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
- Publication number
- CN101880792A CN101880792A CN 201010194371 CN201010194371A CN101880792A CN 101880792 A CN101880792 A CN 101880792A CN 201010194371 CN201010194371 CN 201010194371 CN 201010194371 A CN201010194371 A CN 201010194371A CN 101880792 A CN101880792 A CN 101880792A
- Authority
- CN
- China
- Prior art keywords
- alloy
- free solder
- solder
- anticorrosive
- solder alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to an anti-corrosive anti-oxidation Pb-free solder alloy for aluminum soldering and a production method thereof. 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 has the melting range of between 198 and 22 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 leadless welding alloy that is applied to aluminum soft soldering.This solder alloy is applicable in the industry such as Electronic Packaging and aluminium matter structure or element to be connected by brazing mode and is fixed on setting structure or the framework that affiliated technical field is the soldering of electronic and electrical equipment.
Background technology
Along with electronics and electric equipment products constantly develop to miniaturization, lightweight, less 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, solidity to corrosion 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 standing stock, exploitation and tooling cost height.Therefore, for a long time, people wish 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 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, aerospace, 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 brazed joint erosion resistance and how to solve aluminum soft soldering technology than problems such as complexity.
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 substantially, can dissolve atomic percent and be about 1% Al in β-Sn sosoloid, 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 bonding strength of brazed joint very low (solid solubility of Sn and Pb and Al is extremely low, the difficult compound that forms in interface).Simultaneously, the electropotential of Sn-Pb welding flux alloy and Al substrate differs greatly, and the etching problem that electrochemical action causes is very serious, and for example, brazed joint promptly destroys soak a couple of days in 3wt% salt solution after.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 soldering of copper.Aluminum soft soldering aspect, Sn-Ag-Cu scolder be owing to contain a certain amount of Ag, adopts that the erosion resistance of joint will improve much than the welding flux 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 brazed joint also decreases.Though adopt the brazed joint 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 oxidation-resistance with and at the non-constant of the wettability of aluminium base, be unfavorable for the production and the application of this scolder.In addition, the brazed joint of Sn-Zn scolder and aluminium is anticorrosive also relatively poor, soaks less than promptly rupturing in a week in 3.0wt% salt solution under the general normal temperature.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the technical disadvantages when having lead-free brazing soldering aluminium now, and a kind of have good resistance corrosion and antioxidizing leadless welding flux alloy are provided.
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, Ag0.05～2.8%, and Ga 0.05～0.8%, and Al 0.01～0.5%, and P 0.002～0.02%, and Sn is a surplus.
Further, the described lead-free solder alloy that is used for aluminum soft soldering is cast into solder piece or solder bar.
Further, the described lead-free solder alloy that is used for aluminum soft soldering is processed into solder wire, solder paillon foil or solder powder.
Further, Al, the Ga in this alloying constituent, P element all adopt Zn-Al, Sn-Ga and Sn-P master alloy.
A kind of as the described aluminum soft soldering of above technical scheme comprises following process with production method anticorrosive and the oxidation resistant lead-free solder alloy:
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 for the treatment of 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 homogeneity of alloying constituent 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 master alloy.
This aluminum soft soldering is 198～225 ℃ with the temperature of fusion of anticorrosive and oxidation resistant lead-free solder alloy, and wettability is good and brazed joint intensity is higher on aluminium base.
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, form sosoloid in very big content range, therefore add the bonding strength that Zn can obviously improve welding flux alloy and Al substrate.But the content of Zn can not be too high in the welding flux alloy, cause the oxidation-resistance 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 wettability of scolder poor on the other hand, and cause the surface reaction of scolder oxidation-resistance difference and scolder and Al substrate acutely to cause mainly due to high-load Zn.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 erosion resistance difference of aluminum soft soldering joint is to hinder the one of the main reasons of aluminum soft soldering technology widespread use.Studies show that the Ag that adds trace in the welding flux alloy can improve the erosion resistance of welding flux alloy and aluminum substrate brazed joint significantly.Contain the Ag welding flux alloy forming the rich Ag layer of one deck successive Ag-Al,, can strengthen the erosion resistance of brazed joint greatly because the existence of Ag-Al compound makes the electropotential of the electropotential of joint interface layer apparently higher than Al and scolder with the Al basal body interface.In addition, research also shows, adds the obviously tissue of refinement welding flux alloy of a spot of Ag in Sn-Zn hypoeutectic welding flux alloy, 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 oxidation-resistance that contains the Zn welding flux alloy is relatively poor, in order to improve the antioxidant property of welding flux alloy, when aluminum soft soldering of the present invention designs with the lead-free solder composition, the content of Zn is limited in 0.5～5.0% on the one hand, adds micro-surface active element P, Ga and the Al antioxidant as scolder on the other hand in welding flux alloy.Element P has been widely used in the welding flux alloy as antioxidant, and its oxidation resistant major cause is that element P also preferentially contacts with the direct of oxygen with the isolation of oxygen reaction generation dense oxidation film Sn, Zn at the liquid solder surface enrichment; The addition of P is 0.002～0.020%, is preferably 0.008～0.02%.The antioxygenation temperature of P generally is lower than 350 ℃, so the oxidation-resistance effect that the P element provides when temperature after the welding flux 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 work that isolated solder contacts with oxygen in the air in order to reach the purpose of raising scolder oxidation-resistance during solder fusing; Even because the boiling point height of Ga makes its antioxygenation 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 welding flux alloy soldering, and forms fine and close oxide film at solder surface, thereby hinders the oxidation-resistance of the further oxidation raising welding flux alloy of scolder, but the Al too high levels can influence the wettability of scolder; In the lead-free solder of the present invention, the addition of Al is 0.01～0.5%.
The invention will be further described below in conjunction with specific embodiment.
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 for the treatment of 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 homogeneity of alloying constituent with 320～360 rev/mins speed.
1) testing method of spreading area:
(1) will be heavily for after the welding flux alloy to be measured of 0.5g is stained with the soldering flux 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;
(2) the aluminium sheet test film that will be placed with scolder and soldering flux places temperature to be set on 260 ℃ the hot plate electric furnace and keeps about 30 seconds, guarantees soldering flux 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:
In this corrosion resistance test the shape of brazed joint sample be size as shown in Figure 1.The length of the anticorrosive sample of brazed joint is of a size of: 2mm * 2mm * 1mm, brazing temperature is 260 ℃.
Brazed joint corrosion resistance test method is as follows: the brazed joint sample is soaked in the salt solution of 3.0wt%, sealing also places 70 ± 1 ℃ thermostat container (replacing in per 24 hours is the salt solution of identical starting point concentration once), the etching time of correspondence (immersion fate) is estimated the erosion resistance of brazed joint when disconnecting according to the joint sample, the immersion fate of correspondence shows that at most its erosion resistance is good when also promptly rupturing, otherwise then poor.Annotate: the soldering flux 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 above concrete modifications and variations of implementing is also contained within the scope of the present invention.
Claims (8)
1. an aluminum soft soldering is with anticorrosive and oxidation resistant lead-free solder alloy, and it is characterized in that: it comprises following composition by weight percentage:
Zn 0.5～5.0％；
Ag 0.05～2.8％；
Ga 0.05～0.8％；
Al 0.01～0.5％；
P 0.002～0.02％；
The Sn surplus.
2. a kind of aluminum soft soldering as claimed in claim 1 is with anticorrosive and oxidation resistant lead-free solder alloy, and it is characterized in that: the described lead-free solder alloy that is used for aluminum soft soldering is cast into solder piece or solder bar.
3. a kind of aluminum soft soldering as claimed in claim 1 or 2 is with anticorrosive and oxidation resistant lead-free solder alloy, and it is characterized in that: described lead-free solder alloy is processed into solder wire, solder paillon foil or solder powder.
4. a kind of aluminum soft soldering as claimed in claim 1 is with anticorrosive and oxidation resistant lead-free solder alloy, and it is characterized in that: Al, Ga, P element all adopt Zn-Al, Sn-Ga and Sn-P master alloy.
5. an aluminum soft soldering as claimed in claim 1 comprises following process with production method anticorrosive and the oxidation resistant lead-free solder alloy:
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 for the treatment of 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 homogeneity of alloying constituent with 320～360 rev/mins speed.
6. aluminum soft soldering as claimed in claim 5 is with production method anticorrosive and the oxidation resistant lead-free solder alloy:
This alloy is cast into solder bar or solder.
As claim 5 or 6 described aluminum soft solderings with production method anticorrosive and the oxidation resistant lead-free solder alloy:
This alloy further is processed into solder or glass putty.
8. a kind of aluminum soft soldering according to claim 5 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 master alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010194371XA CN101880792B (en) | 2010-06-07 | 2010-06-07 | Anti-corrosive anti-oxidation Pb-free solder alloy for aluminum soldering |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010194371XA CN101880792B (en) | 2010-06-07 | 2010-06-07 | Anti-corrosive anti-oxidation Pb-free solder alloy for aluminum soldering |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101880792A true CN101880792A (en) | 2010-11-10 |
| CN101880792B CN101880792B (en) | 2012-08-22 |
Family
ID=43052932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010194371XA Active CN101880792B (en) | 2010-06-07 | 2010-06-07 | Anti-corrosive anti-oxidation Pb-free solder alloy for aluminum soldering |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101880792B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102699562A (en) * | 2012-06-11 | 2012-10-03 | 太原理工大学 | Aluminum low-temperature soft solder and manufacturing method thereof |
| CN102922162A (en) * | 2012-11-01 | 2013-02-13 | 青岛英太克锡业科技有限公司 | Aluminum welding tin paste and preparation method thereof |
| CN106098808A (en) * | 2016-08-10 | 2016-11-09 | 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 |
-
2010
- 2010-06-07 CN CN201010194371XA patent/CN101880792B/en active Active
Patent 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 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102699562A (en) * | 2012-06-11 | 2012-10-03 | 太原理工大学 | Aluminum low-temperature soft solder and manufacturing method thereof |
| CN102699562B (en) * | 2012-06-11 | 2015-02-25 | 太原理工大学 | Aluminum low-temperature soft solder and manufacturing method thereof |
| CN102922162A (en) * | 2012-11-01 | 2013-02-13 | 青岛英太克锡业科技有限公司 | Aluminum welding tin paste and preparation method thereof |
| CN106098808A (en) * | 2016-08-10 | 2016-11-09 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101880792B (en) | 2012-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101880792B (en) | Anti-corrosive anti-oxidation Pb-free solder alloy for aluminum soldering | |
| EP3062956B1 (en) | Lead-free, silver-free solder alloys | |
| CN108971793B (en) | Low-temperature lead-free solder | |
| CN101348875A (en) | Tin, bismuth and copper type low temperature lead-free solder alloy | |
| CN101417375A (en) | Leadless welding alloy for welding electronic elements | |
| CN1861311A (en) | Lead-free anti-oxidation rare-earth-contg. type SnZn alloy welding flux, and its prepn. method | |
| CN101381826A (en) | Sn-Cu base leadless solder alloy and preparation method | |
| JP2017501879A (en) | Zinc-based lead-free solder composition | |
| Torres et al. | Effect of antimony additions on corrosion and mechanical properties of Sn-Bi eutectic lead-free solder alloy | |
| JP6247819B2 (en) | Aluminum solder and solder joints | |
| CN102152022A (en) | Corrosion-resistant Sn-Zn-based lead-free solder with high oxidation resistance | |
| CN101486133A (en) | Lead-free solder for aluminum soft soldering | |
| CN101988165A (en) | High-temperature oxidation resistant lead-free tin-coated alloy | |
| Takemoto et al. | Role of electrode potential difference between lead-free solder and copper base metal in wetting | |
| CN106825983B (en) | SnAgSbNi series lead-free soldering tin alloy and preparation method and application thereof | |
| CN101234456B (en) | Tin silver gold leadless welding material and preparation thereof | |
| JP4076182B2 (en) | Lead-free solder alloy | |
| JP2016019992A (en) | Aluminium soldering and solder joint | |
| JP2016172286A (en) | Solder for aluminum, and solder joint | |
| CN102337422B (en) | A kind of high temperature bends down the unleaded application warding off tin alloy of corrode | |
| JP2006320913A (en) | High temperature solder alloy | |
| CN101804527A (en) | Sn-Zn based unleaded brazing material with low Zn | |
| CN101920406B (en) | Sn-Ag-Zn-Cr eutectic lead-free solder | |
| TW200817126A (en) | Electronic connecting materials for the Sn-Zn-Ag system lead-free solder alloys | |
| CN103753047B (en) | Lead-free solder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |