CN102717200A - Lead-free soft braze welding material and preparation method of lead-free soft braze welding material - Google Patents
Lead-free soft braze welding material and preparation method of lead-free soft braze welding material Download PDFInfo
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- CN102717200A CN102717200A CN201210211982XA CN201210211982A CN102717200A CN 102717200 A CN102717200 A CN 102717200A CN 201210211982X A CN201210211982X A CN 201210211982XA CN 201210211982 A CN201210211982 A CN 201210211982A CN 102717200 A CN102717200 A CN 102717200A
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Abstract
The invention relates to a lead-free soft braze welding material and a preparation method of the lead-free soft braze welding material. The lead-free soft braze welding material adopts Sn (stannum) as substrates and also comprises the following ingredients in percentage by weight: 0.1 percent to 2.5 percent of Cu (copper), 4.1 percent to 6.0 percent of Sb (stibonium), 0.005 percent to 3.0 percent of Ni (nickel), 0.01 percent to 3.0 percent of active carbon and/or 0.01 percent to 3.0 percent of ZnCl2 (zinc chloride), and in addition, a certain amount of NaOH (sodium hydroxide) and NH4Cl (ammonia chloride) can be selectively added, wherein gas including trace O2 (oxygen gas), SO2 (sulfur dioxide), CO2 (carbon dioxide) and the like inside metal can be removed through the addition of active carbon and ZnCl2, so the surface of the metal is protected, the product oxidation is reduced, and the slag yield is reduced. The welding material provided by the invention has the advantages that on the basis of ensuring good welding performance of welding material alloy, the production cost of enterprises is greatly reduced, good economic benefits are realized, in addition, a manufacture method of the welding material alloy is simple, and the industrial implementation is easy.
Description
Technical field
The present invention relates to scolder and manufacturing technology field thereof, be specifically related to a kind of no-lead soft soldering and preparation method thereof.
Background technology
In the industry, soldering is meant the scolder that employing is lower than mother metal fusion temperature, and operating temperature adopts a kind of solder technology that is lower than the mother metal solid phase and is higher than the scolder liquidus curve.Be divided into two kinds of solder and solder brazing according to the height soldering of scolder liquidus temperature.Solder is a kind of low temperature bond technology, compares with solder brazing to have following characteristics: common thermals source such as (1) available flatiron, blowtorch weld processing ease; (2) heating-up temperature is low, and the structure property of base metals changes little, and the copper al member is welded by any way, and its contingent expansion, Strength Changes and distortion are all less; (3) productivity ratio is high, and tens to several thousand weld seams of a performance welding easily are automated production.
Solder commonly used is a leypewter in the electron trade at present, because leypewter has good wetability and electric conductivity, welding performance is fine and cost is low, therefore is used widely.But lead and compound environmental pollution thereof are very big, can harm humans and organism health.Therefore, in electronics industry, be sought after a kind of no-lead soft soldering and replace traditional tin-lead solder.Lead-free solder not only will have good welding performance, and some also requires the solder joint of the scolder light of will making mute, to reduce light to stimulating eyes; Some requires scolder can satisfy the requirement of wiring board secondary welding.Secondary welding is meant and adopts the higher alloy of fusing point that some assemblies are welded on the printed substrate earlier, to have more low-melting scolder other assembly is welded on the identical faces or another side of printed substrate then, and do not cause first kind of assembly to come off.This just requires scolder fusing point of welding for the first time height of will trying one's best.
The Chinese patent notification number is that the patent of invention of CN1242869C discloses a kind of lead-free solder, and it is by weight percentage: silver-colored Ag:1.8%-2.2%, antimony Sb:0.5%-1.0%, copper Cu:1.0%-3.0%, indium In:0.6%-3.0% and surplus are formed for tin Sn.Notification number is the lead-free solder of CN1252842A, and it is by weight percentage: silver-colored Ag:1.0%-3.0%, antimony Sb:0-4.0%, copper Cu:0-2.0%, bismuth Bi:15%-30% and surplus are formed for tin Sn; Notification number is the lead-free solder of CN1475327, and it is by weight percentage: silver-colored Ag:0.01%-0.5%, antimony Sb:0.01-0.5%, copper Cu:2.0-5.0%, indium In:0.002%-0.2%, nickel: 0.01%-0.5%, gallium Ga:0.002%-0.1%, phosphorus P:0.002%-0.1%, rhenium Re:0.01%-2.0% and surplus are that tin is formed.The fusing point of these lead-free solders is all relatively low, and the silver that wherein contains, these two kinds of rare metals of indium, and these two kinds of Kingsoft mineral resources are few, and price is high relatively, and bi content is high, and welding back solder joint is prone to peel off.
Summary of the invention
The problem that the present invention need solve provides that a kind of manufacturing approach is simple, cost is low, performance is good, produces the few no-lead soft soldering of slag.
In order to address the above problem; The technical scheme that the present invention adopted is: a kind of no-lead soft soldering; With tin Sn is substrate, also contains following composition by weight percentage: the active carbon of copper Cu 0.1%-2.5%, antimony Sb 4.1%-6.0%, nickel 0.005%-3.0%, 0.01%-3.0% and/or the zinc chloride ZnCl of 0.01%-3.0%
2
Preferably, the also alternative NaOH NaOH of 0.005%-2.0% or the ammonium chloride NH of 0.005%-2.0% of adding in the said scolder
4Among the Cl one or both.
The manufacturing approach of no-lead soft soldering of the present invention, its step is following:
(1) tin is added in the graphite crucible melt, heating up in molten back, adds copper, treat the copper fusing after, stirring is smelted into liquid gun-metal, leaves standstill to pour mold after a period of time into and be cast into the gun-metal ingot and take out;
(2) tin is added in the graphite crucible melt, heating up in molten back, adds antimony, treat the antimony fusing after, stir, leave standstill and pour mold after a period of time into and be cast into the tin pewter ingot and take out again;
(3) tin is added in the graphite crucible melt, heating up in molten back, adds nickel, treat the antimony fusing after, stir, leave standstill and pour mold after a period of time into and be cast into the tin-nickel alloy ingot and take out again;
(4) with the tin of three kinds of alloy pig, active carbon, zinc chloride, NaOH and/or ammonium chloride making in the above-mentioned steps and surplus, count by weight percentage copper Cu 0.1%-2.5%, antimony Sb 4.1%-6.0%, nickel 0.005%-3.0%, active carbon 0.01%-3.0% and/or zinc chloride ZnCl
2The ratio of 0.01%-3.0% adds in the stainless-steel pan carries out melting, processes solder stick, soldering tin bar, glass putty, tin cream.
Compared with prior art, beneficial effect of the present invention is: not leaded this harmful material in the described soft soldering alloy, satisfy the unleaded welding requirements of electronic product; Adopt fusing point and the low relatively metal of price to improve high-temperature behavior, the antioxygenic property of solder alloy in the alloy, and make scolder be suitable for the secondary welding of wiring board, have good economic benefit; The adding of active carbon, zinc chloride, NaOH, ammonium chloride can be removed the micro-oxygen O of metal inside
2, sulfur dioxide SO
2, carbon dioxide CO
2Deng gas, thereby the protective money metal surface reduces the oxidation of product, reduces slag rate; In addition, the manufacturing approach of said solder alloy is simple, is easy in industry, realize.
The specific embodiment
The disclosed no-lead soft soldering of the present invention is substrate with tin Sn, and other includes following composition by weight percentage: copper Cu 0.1%-2.5%, antimony Sb 4.1%-6.0%, nickel 0.005%-3.0%, active carbon 0.01%-3.0% and/or zinc chloride ZnCl
20.01%-3.0%.
Preferably, the also alternative adding in back is the NaOH NaOH of 0.005%-2.0% or the ammonium chloride NH of 0.005%-2.0% by weight percentage in said scolder
4Among the Cl one or both.
In the leadless welding alloy that with tin Sn is primary raw material, add copper Cu, can increase the mechanical strength of scolder.But the content of Cu can not be too high, because the Cu fusing point is higher, if the high fusion temperature that can significantly increase scolder of Cu content, the wetability of minimizing scolder.Therefore not influence solder wettability basically with the mechanical strength that increases scolder be prerequisite in the present invention, and the Cu weight percent content is decided to be 0.1%-2.5%.
Antimony Sb can improve the high-temperature behavior of scolder among the present invention, and the interpolation of antimony simultaneously also makes the solder joint after the welding present mute light.In the prior art, add argent usually reaching the effect that makes the mute light of solder joint, but silver-colored price is higher.Antimony is compared with silver, has low, the low price of fusing point, is convenient to the advantage of processing and manufacturing.The interpolation of Ni helps the refinement solder alloy, the generation of solder joint bridging phenomenon when reducing welding.
Among the present invention, add active carbon and/or zinc chloride, can remove the oxygen O of metal inside trace
2, sulfur dioxide SO
2, carbon dioxide CO
2Deng gas, thereby the protective money metal surface reduces the oxidation of product, reduces slag rate.
Influential when but active carbon and zinc chloride composition are too much in the solder alloy to the electric conductivity of alloy, also possibly cause failure welding, hinder welding quality.Therefore the addition of these two kinds of materials is due to the active carbon of 0.01%-3.0% and the zinc chloride ZnCl of 0.01%-3.0%
2
The manufacturing approach of no-lead soft soldering of the present invention, its concrete steps are following:
(1) tin is added in the graphite crucible melting, heats up in molten back, adds copper when generally being warming up to 1000-1200 ℃, the copper of adding, and the copper amount generally accounts for the 5%-15% of gun-metal gross weight, so that melting; After treating copper fusing, stirring with stirring rod is smelted into liquid gun-metal, leaves standstill to pour mold after a period of time into and be cast into the gun-metal ingot and take out;
(2) tin is added in the graphite crucible melt; Heat up in molten back; Add antimony when generally being warming up to 600-1000 ℃, the antimony amount of adding generally accounts for the 40%-60% of tin pewter gross weight, treat the antimony fusing after; Stir with stirring rod, leave standstill and pour mold after a period of time into and be cast into the tin pewter ingot and take out again;
(3) tin is added in the graphite crucible melt; Heat up in molten back; Add nickel when generally being warming up to 1500-1800 ℃, the nickel amount of adding generally accounts for the 2%-5% of tin-nickel alloy gross weight, treat the antimony fusing after; Stir with stirring rod, leave standstill and pour mold after a period of time into and be cast into the tin-nickel alloy ingot and take out again;
(4) with the tin of three kinds of alloy pigs that make in the above-mentioned steps, active carbon, zinc chloride, NaOH (can select), ammonium chloride (can select) and surplus, press copper Cu 0.1%-2.5%, antimony Sb 4.1%-6.0%, nickel 0.005%-3.0% and active carbon 0.01%-3.0%, zinc chloride ZnCl
20.01%-3.0%, NaOH NaOH 0.005%-2.0% (can select), ammonium chloride NH
4Cl 0.005%-2.0% (can select), surplus are that the prescription of tin Sn carries out melting than adding in the stainless-steel pan, process solder stick, soldering tin bar, glass putty, tin cream.
In above-mentioned first three step, after alloy melting becomes liquid state, generally leave standstill casting after 30-40 minute.
What must state is that used raw material is the refining raw material of industry in this method.
All adopt the good and resistant to elevated temperatures graphite crucible of thermal conductivity in the said solder alloy ingot fusion process, the graphite crucible stable chemical performance can guarantee by the purity of melting material simultaneously.
No-lead soft soldering of the present invention can be made into various forms, includes but not limited to above-mentioned cited solder stick, soldering tin bar, glass putty, tin cream.
Embodiment 1:
The 90kg refined tin added in the graphite crucible melt, be warming up to 1100 ℃ after molten, add the smart copper of 10kg, stirring with wooden stirring rod is smelted into the liquid tin copper alloy, leaves standstill to pour mold after 30 minutes into and be cast into the taking-up of gun-metal ingot;
In graphite crucible, drop into the 50kg refined tin again and melt, be warming up to 600 ℃-1000 ℃ after molten, add the 50kg star antimony, treat the antimony fusing and stir, leave standstill and pour mold after 30 minutes into and be cast into the tin pewter ingot and take out;
In graphite crucible, drop into the 57kg refined tin again and melt, be warming up to about 1600 ℃ after molten, drop into the 3kg pure nickel, treat the nickel fusing and stir, leave standstill and pour mold after 30 minutes into and be cast into the tin-nickel alloy ingot and take out;
With above-mentioned three kinds of alloy pigs, active carbon and tin that are mixed with by weight percentage, antimony: copper 4.1%: nickel 0.6%: active carbon 0.05%: 0.15% with surplus be tin, add in the stainless-steel pan and carry out melting, be mixed with leadless welding alloy.
Embodiment 2:
Getting three kinds of alloy pigs, active carbon and tin that embodiment 1 prepared is mixed with by weight percentage: antimony: copper 4.8%: nickel 0.1%: active carbon 3.0%: 0.5% with surplus be the lead-free solder of tin.
Embodiment 3:
Getting three kinds of alloy pigs, active carbon and tin that embodiment 1 prepared is mixed with by weight percentage: antimony: copper 6.0%: nickel 2.5%: active carbon 1.5%: 0.3% with surplus be the lead-free solder of tin.
Embodiment 4:
Getting three kinds of alloy pigs, active carbon, zinc chloride and tin that embodiment 1 prepared is mixed with by weight percentage: antimony: copper 4.5%: nickel 0.8%: active carbon 0.5%: zinc chloride 0.2%: 1.5% with surplus be the lead-free solder of tin.
Embodiment 5:
Getting three kinds of alloy pigs, active carbon, zinc chloride and tin that embodiment 1 prepared is mixed with by weight percentage: antimony: copper 4.1%: nickel 0.1%: active carbon 3.0%: zinc chloride 0.5%: 0.08% with surplus be the lead-free solder of tin.
Embodiment 6:
Getting three kinds of alloy pigs, active carbon, zinc chloride and tin that embodiment 1 prepared is mixed with by weight percentage: antimony: copper 6.0%: nickel 2.5%: active carbon 0.05%: zinc chloride 0.05%: 1.6% with surplus be the lead-free solder of tin.
Embodiment 7:
Getting three kinds of alloy pigs, zinc chloride and tin that embodiment 1 prepared is mixed with by weight percentage: antimony: copper 5.5%: nickel 1.0%: zinc chloride 0.005%: 0.05% with surplus be the lead-free solder of tin.
Embodiment 8:
Getting three kinds of alloy pigs, zinc chloride and tin that embodiment 1 prepared is mixed with by weight percentage: antimony: copper 4.1%: nickel 2.5%: zinc chloride 1.5%: 1.5% with surplus be the lead-free solder of tin.
Embodiment 9:
Getting three kinds of alloy pigs, zinc chloride and tin that embodiment 1 prepared is mixed with by weight percentage: antimony: copper 6.0%: nickel 0.1%: zinc chloride 3.0%: 0.8% with surplus be the lead-free solder of tin.
Embodiment 10:
Three kinds of alloy pigs and the tin of getting that embodiment 1 prepared are mixed with by weight percentage: antimony: copper 6.0%: nickel 0.1%: 1.0% and surplus be the lead-free solder of tin.
Embodiment 11:
Three kinds of alloy pigs and the tin of getting that embodiment 1 prepared are mixed with by weight percentage: antimony: copper 4.5%: nickel 1.0%: 0.01% with surplus be the lead-free solder of tin.
Embodiment 12:
Three kinds of alloy pigs and the tin of getting that embodiment 1 prepared are mixed with by weight percentage: antimony: copper 4.1%: nickel 2.5%: 1.5% and surplus be the lead-free solder of tin.
From the leadless welding alloy of above-mentioned 12 embodiment gained, get 6 kinds and carry out performance test, the result is following:
It is thus clear that the no-lead soft soldering function admirable that prescription according to the invention and method make is used said active carbon and/or zinc chloride ZnCl simultaneously
2Effectively the protective money metal surface reduces the oxidation of product, reduces slag rate.
Claims (8)
1. a no-lead soft soldering is substrate with tin Sn, by weight percentage, also contains copper Cu 0.1%-2.5%, antimony Sb 4.1%-6.0%, nickel 0.005%-3.0%; It is characterized in that: also contain by weight percentage zinc chloride ZnCl for the active carbon of 0.01%-3.0% and/or 0.01%-3.0%
2
2. no-lead soft soldering according to claim 1 is characterized in that: also comprise the NaOH NaOH of 0.005%-2.0% and/or the ammonium chloride NH of 0.005%-2.0%
4Cl.
3. the manufacturing approach of a no-lead soft soldering, step is:
Tin added in the graphite crucible melt, heating up in molten back, adds copper, treat the copper fusing after, stirring is smelted into liquid gun-metal, leaves standstill to pour mold after a period of time into and be cast into the gun-metal ingot and take out;
Tin added in the graphite crucible melt, heating up in molten back, adds antimony, treat the antimony fusing after, stir, leave standstill and pour mold after a period of time into and be cast into the tin pewter ingot and take out again;
Tin added in the graphite crucible melt, heating up in molten back, adds nickel, treat the nickel fusing after, stir, leave standstill and pour mold after a period of time into and be cast into the tin-nickel alloy ingot and take out again;
Tin with three kinds of alloy pig, active carbon and/or zinc chloride, NaOH and/or ammonium chloride making in the above-mentioned steps and surplus; In carrying out melting in the ratio adding stainless-steel pan of counting by weight percentage copper Cu 0.1%-2.5%, antimony Sb 4.1%-6.0%, nickel 0.005%-3.0%, active carbon and/or zinc chloride 0.01%-3.0%, process solder stick, soldering tin bar, glass putty, tin cream.
4. the manufacturing approach of no-lead soft soldering according to claim 3 is characterized in that: add copper when tin is warming up to 1000-1200 ℃ after molten in the said step (1), the copper amount of adding accounts for the 5%-15% of gun-metal gross weight.
5. the manufacturing approach of no-lead soft soldering according to claim 3 is characterized in that: add antimony when tin is warming up to 600-1000 ℃ after molten in the said step (2), the antimony amount of adding accounts for the 40%-60% of tin pewter gross weight.
6. the manufacturing approach of no-lead soft soldering according to claim 3 is characterized in that: add nickel when tin is warming up to 1500-1800 ℃ after molten in the said step (3), the nickel amount of adding accounts for the 3%-5% of tin-nickel alloy gross weight.
7. the manufacturing approach of no-lead soft soldering according to claim 3 is characterized in that: all left standstill 30-40 minute after alloy melting becomes liquid state in the said step (1) (2) (3).
8. the manufacturing approach of no-lead soft soldering according to claim 3 is characterized in that: also add the NaOH NaOH of 0.005%-2.0% and/or the ammonium chloride NH of 0.005%-2.0% in the step (4)
4Cl.
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| CN201210211982XA CN102717200A (en) | 2012-06-26 | 2012-06-26 | Lead-free soft braze welding material and preparation method of lead-free soft braze welding material |
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|---|---|---|---|
| CN201210211982XA CN102717200A (en) | 2012-06-26 | 2012-06-26 | Lead-free soft braze welding material and preparation method of lead-free soft braze welding material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103331531A (en) * | 2013-06-20 | 2013-10-02 | 中国人民解放军装甲兵工程学院 | Brazing rod for repairing damages to thin aluminum alloy plate and using method of brazing rod |
| CN103394826A (en) * | 2013-08-22 | 2013-11-20 | 四川朗峰电子材料有限公司 | Technological method for reducing defect of extrusion rod |
| CN108953716A (en) * | 2018-07-06 | 2018-12-07 | 上海市特种设备监督检验技术研究院 | A kind of preparation method of easy fusing alloy plug |
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Application publication date: 20121010 |