CN103317254A - Soldering flux and solder wire for aluminum and aluminum alloy soldering - Google Patents
Soldering flux and solder wire for aluminum and aluminum alloy soldering Download PDFInfo
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- CN103317254A CN103317254A CN 201310247992 CN201310247992A CN103317254A CN 103317254 A CN103317254 A CN 103317254A CN 201310247992 CN201310247992 CN 201310247992 CN 201310247992 A CN201310247992 A CN 201310247992A CN 103317254 A CN103317254 A CN 103317254A
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Abstract
The invention relates to a soldering flux and a solder wire for aluminum and aluminum alloy soldering. The solder wire is composed of a solder alloy on the outer layer and the soldering flux as an inner core, the soldering flux comprises, by weight, 15-30% of tin, 1-3% of silver, and the balance lead, and the soldering flux comprises, by weight, 5-15% of heavy metal fluoride and 85-95% of hydrofluoric silicate of polyhydroxy amine. According to the soldering flux and the solder wire for aluminum and aluminum alloy soldering, tin, lead and silver alloys are used as soldering aluminum, silver and aluminum in a soldering material are reacted during soldering, and a layer of an silver and aluminum solid solution is formed at the position of the boundary of the soldering material and aluminum, so that electrode and potential differences between aluminum and the soldering material are relieved, and corrosion resistance of a soldered joint is greatly improved.
Description
Technical field
The present invention relates to a kind of anticorrosive good aluminum soft soldering solder stick and preparation method thereof, the solder of affiliated technical field electronics, electrical equipment, heat exchanger product etc. also can be used for the soldering of Solder for Al-Cu Joint Welding joint.
Background technology
Soldering is the common technique that in the electronic technology joint of lead or element is welded together, usually be divided into solder brazing and solder two classes: with 450 ℃ brazing temperatures as boundary, the technology that is higher than this temperature is called solder brazing, be lower than this temperature and then be called solder, wherein, solder brazing has big limitation because technological temperature is higher in the connection technology of products such as electronics, electrical equipment; The brazing temperature of solder is lower, and brazing process is little to the heat affecting of product.Iron soldering in the solder, because characteristics such as its flexible operations, convenience, the most frequently used operating procedure that arrives especially, and this operating procedure all need be used usually and has the medicine core solder stick that helps the weldering function.According to the needs of soldering processes, the composition of scaling powder medicine core amount and alloy can carry out actual regulation and control.
The conduction of aluminium and thermal conductivity slightly are inferior to copper, but its proportion only reaches 1/3 of copper for a short time, and the cost performance of aluminium is occupied bigger advantage with respect to copper.As conductive material, the base material of increasing brass ware is replaced by aluminium and aluminium alloy, but aluminium and aluminum alloy surface cover the oxide-film of one deck densification, very stable and difficult removal, this makes and is connected to become a big obstacle on the soldering processes between aluminium and aluminium alloy and other metal device efficiently, reliably.
Requirement as aluminium welding tin wire medicine core scaling powder is: be solid-state at normal temperatures, be convenient to scaling powder and can stablize and be kept in the soldering tin core; The deoxidation film ability of scaling powder is strong, active high during soldering; Postwelding residue corrosivity is little.
By retrieval, find several pieces of patent documentations relevant with the present patent application content, wherein, publication number provides a kind of aluminium welding tin wire for electronic equipment aluminium such as electrical equipment, electric light source, communication, instrument and aluminium alloy for the Chinese patent of CN1398695: inner core is scaling powder, and skin is solder.Outer field solder is made up of 25～35% tin and 65～75% lead by weight percentage; The solder flux of inner core is by weight percentage by 5～20% fluosilicic acid heavy metallic salts, 5～20% fluoboric acid heavy metallic salts, and 60～80% polyethylene polyamines, 5～10% vaseline are formed; The solder flux of outer field solder and inner core solder by weight percentage is 97.5～98.2%, and solder flux is 1.8～2.5%.
Publication number is characterized in that for the Chinese patent of CN101244493 provides a kind of preparation method who comprises aluminum alloy leadless welding wire and the scaling powder thereof of scaling powder wherein lead-free solder is made of tin, silver, copper, aluminium, kirsite; Lead-free soldering flux is made up of following materials by weight: organic carboxyl acid and derivatives active agent 10～20%, high boiling solvent 10～15%, fluorocarbon surfactant: 0.1～2%, corrosion inhibiter: 0.1～0.4%, water-soluble resin: 40～50%, all the other are solvent: isopropyl alcohol, ethanol, or deionized water.
More than the scaling powder of two kinds of patents be inhomogeneous pasty state or liquid state, be unfavorable for can and keep the stable of solder stick inner core; Contain the vaseline or the water-soluble resin filler that in a large number braze ability there are negative effect in these two kinds of scaling powders respectively, the activity in the time of soldering can being reduced inevitably.
Publication number provides a kind of scaling powder for aluminium soldering tin wire core and preparation method thereof for the Chinese patent of CN101412168.This scaling powder is used for the solder stick inner core of aluminium and aluminum alloy soft soldering, by weight percentage, its prescription consists of: modified rosin 14～28%, ammonium fluoroborate 12～24%, organic amine 38～56%, zinc source 4～10%, tin salt 0.5～8%, fluorine surfactant 0.1～2%.The zinc source is zinc salt, zinc powder or activated zinc oxide; Tin salt is the inferior tin of inorganic tin salt or organic acid; Fluorine surfactant is 1～2 kind among FC4430, FC4432, F5010, FSN-100, F501, F502 and the FS-300.
In this scaling powder with rosin as carrier, the braze ability of aluminium and aluminium alloy is played negative effect.Especially described many additives can not be dissolved in the rosin, are a kind of paste of mixing, are unfavorable for improving the braze ability of scaling powder.
Publication number is that CN102922164A discloses a kind of Sn-Zn scolder for the solder solder stick, according to the weight percent meter, comprises Sn:86-92%, Zn:6-12%, In; 0.2-2%, P:0.08-0.8%, this invention includes only scolder.
This patent only belongs to a kind of brazing alloy, does not contain scaling powder, is difficult to independent use.Different fully with the present invention, can not obtain effect of the present invention.
Through contrast, above-mentioned patent documentation is different with the present patent application content, it mainly shows: contain the carrier that in a large number the soldering activity is played negative effect in the disclosed scaling powder of above-mentioned patent documentation, as rosin, vaseline or water-soluble resin, must reduce the activity of scaling powder; Corrosion resistance with above-mentioned brazing filler metal alloy brazed aluminum and aluminum alloy joint is poor.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of scaling powder to reach the solder stick that is used for aluminium and aluminum alloy soft soldering, scaling powder adopts and has extremely strong removal oxide-film ability and the combination of the most highly active perfluoro-compound among the present invention, improve the overall activity of scaling powder, guaranteed the reliability of soldered fitting.The present invention has used the brazing filler metal alloy of argentiferous, has improved the corrosion resistance of soldered fitting effectively.
The present invention solves its technical problem and takes following technical scheme to realize:
A kind of scaling powder for aluminium and aluminum alloy soft soldering, raw material components and the percentage by weight of forming described scaling powder are:
Heavy metal fluoride activating agent 5～15%
The hydrofluoride 85～95% of polyhydroxy amine.
And the preparation method of the hydrofluoride of described polyhydroxy amine is as follows
⑴ place polyhydroxy amine in the evaporation boiler of corrosion resistant coating, is dissolved in water, and the weight ratio of polyhydroxy amine and water is 1:1;
⑵ dropwise add the hydrofluoric acid that concentration is 10-15wt% in evaporation boiler, be adjusted to 6～8 until the pH value;
⑶ will stop heating behind material heating evaporation to 140～150 in the evaporation boiler ℃; ,
⑷ be cooled to 100～110 ℃ with material in the pot, pours polyacrylic container into and continue to be cooled to room temperature, gets white waxy solid, is the hydrofluoride of described polyhydroxy amine;
⑸ drop into reactor with the hydrofluoride of polyhydroxy amine, is heated to 110～130 ℃, after the hydrofluoride for the treatment of polyhydroxy amine melts fully, add described heavy metal fluoride activating agent, treat that the heavy metal fluoride activating agent dissolves fully after, stir, cooled and solidified namely gets scaling powder then.
And, optional 1～3 kind the composition from monoethanolamine, diethanol amine, triethanolamine, AEEA, dihydroxy ethyl ethylenediamine, tetrahydroxyethy-lethylenediamine, triisopropanolamine or trishydroxymethylaminomethane of described polyhydroxy amine.
And described heavy metal fluoride activating agent is selected from zinc fluoride, stannous fluoride, fluoridizes bismuth and any at least two kinds combination of copper fluoride.
A kind of solder stick for aluminium and aluminum alloy soft soldering is made up of brazing filler metal alloy and scaling powder,
Percentage by weight between described brazing filler metal alloy composition and the composition is: tin 15～30%, silver 1～3%, surplus lead;
Described helping welded to being used for the scaling powder of aluminium and aluminum alloy soft soldering.
And the weight ratio of described brazing filler metal alloy and scaling powder is 40～100:1.
And the preparation method of solder stick who is used for aluminium and aluminum alloy soft soldering is as follows:
⑴ prepare brazing filler metal alloy: tin, lead, silver are weighed in proportion, and melting forms uniform brazing filler metal alloy, is cast into ingot casting under 320～380 ℃ of conditions, obtains brazing filler metal alloy;
⑵ synthesize solder stick: utilize extruder that scaling powder is pressed into brazing filler metal alloy as inner core, will be pressed into brazing filler metal alloy cooling back rolling, the wire drawing of scaling powder, make the solder stick of required diameter.
Advantage of the present invention and good effect are:
1, solid-state scaling powder provided by the present invention has been abandoned active relatively poor borofluoride, and adopted active higher perfluoro-compound as activating agent, simultaneously in order to dissolve this perfluoro-compound, the hydrofluoride that has been used highly active polyhydroxy amine is matrix, this matrix has not only played the effect of carrier, and makes the charges that do not contain non-activity in the scaling powder fully.
2, scaling powder of the present invention adopts and has extremely strong removal oxide-film ability and the combination of the most highly active perfluoro-compound, improved the overall activity of scaling powder, in brazing process, owing to have high fluorine ion relative amount in the scaling powder, can remove the oxide-film on aluminium surface rapidly, and heavy metal fluoride is reduced by aluminium base in brazing process, separate out the heavy metal that is in a liquid state and with the mother metal alloying, farthest reduce the interfacial tension between melt solder and the aluminium base, guaranteed the activity of scaling powder maximum.
3, scaling powder provided by the present invention at room temperature is solid-state, is fit to be poured in the solder stick as the medicine core, and the scaling powder that melts in soldering heating process sprawls, covers and protected joint and melt solder to avoid oxidized rapidly.
4, the present invention adopts tin, lead, silver alloy as solder.During soldering, the silver in the solder and aluminium generation solid solution at the at the interface formation one deck silver-aluminium solid solution of solder with aluminium, have slowed down the difference in Electrode Potential between aluminium and the solder, have improved the corrosion resistance of soldered fitting greatly.
The specific embodiment
The invention will be further described below by specific embodiment, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
Need to prove, stannous fluoride involved in the present invention, the heavy metal fluoride activating agent collocation of fluoridizing multiple combinations such as bismuth, copper fluoride and zinc fluoride are not limited to selection and the ratio that following 3 embodiment provide, zinc fluoride, stannous fluoride, fluoridize single in bismuth and the copper fluoride or arbitrarily two or more combinations all can be used as the heavy metal fluoride activating agent, and each component is chosen ratio and is not limit.
The hydrofluoride of related polyhydroxy amine makes by polyhydroxy amine and hydrofluoric acid reaction among the present invention, optional 1～3 kind the composition from monoethanolamine, diethanol amine, triethanolamine, AEEA, dihydroxy ethyl ethylenediamine, tetrahydroxyethy-lethylenediamine, triisopropanolamine or trishydroxymethylaminomethane of described polyhydroxy amine, each included component of above-mentioned composition can be mixed according to arbitrary proportion.
Embodiment 1:
A kind of solder stick for aluminium and aluminum alloy soft soldering is made up of outer brazing filler metal alloy and inner core scaling powder two parts, wherein:
Raw material components and the weight of outer brazing filler metal alloy are respectively: tin 15Kg, silver-colored 1Kg, plumbous 84Kg;
Raw material components and the weight of inner core scaling powder are respectively: zinc fluoride 1.8Kg, the hydrofluoride 85Kg of stannous fluoride 13.2Kg, polyhydroxy amine.
The preparation method of the described inner core scaling powder of present embodiment is as follows:
In the present embodiment, polyhydroxy amine is made up of triethanolamine, tetrahydroxyethy-lethylenediamine and trishydroxymethylaminomethane, and the preparation method is as follows:
⑴ mix above-mentioned triethanolamine, tetrahydroxyethy-lethylenediamine and trishydroxymethylaminomethane and place in the evaporation boiler of corrosion-resistant finishes by equal proportion (weight ratio), be dissolved in water, and the weight ratio of polyhydroxy amine mixture and water is 1:1;
⑵ dropwise add concentration in the evaporation boiler is 10～15% hydrofluoric acid, prevents from splashing, and is adjusted to 6～8 until pH,
⑶ stop heating after material to temperature reaches 140～150 ℃ in the heating evaporation pot;
⑷ pour polypropylene containers into after material is cooled to 100～110 ℃ in the pot to be evaporated and be cooled to room temperature, get white waxy solid, be the hydrofluoride of described mixing polyhydroxy amine;
⑸ prepare scaling powder: take by weighing the hydrofluoride that mixes polyhydroxy amine and drop into reactor by specified wt (85Kg), be heated to 110～130 ℃, add zinc fluoride (1.8Kg) and stannous fluoride (13.2Kg) until completely melted; After treating that zinc fluoride and stannous fluoride dissolve fully, stir 10min, cooled and solidified obtains scaling powder;
The step of preparation solder stick is as follows:
⑴ with brazing filler metal alloy: tin, lead, silver are weighed in proportion, and melting forms uniform brazing filler metal alloy, are cast into ingot casting under 320～380 ℃ of conditions, obtain outer brazing filler metal alloy, and is standby;
⑵ draw medicine core solder stick: utilize extruder that solder flux is pressed into outer brazing filler metal alloy as inner core, cool off back rolling, wire drawing, make the solder stick of required diameter, the weight ratio that feeds intake of outer brazing filler metal alloy and inner core scaling powder is 100:1～3.
Embodiment 2:
A kind of solder stick for aluminium and aluminum alloy soft soldering, identical with embodiment 1, formed by scaling powder two parts of outer field brazing filler metal alloy and inner core equally, wherein:
Raw material components and the weight of outer brazing filler metal alloy are respectively: tin 30Kg, silver-colored 3Kg, plumbous 67Kg;
Raw material components and the weight of inner core scaling powder are respectively: the hydrofluoride 95Kg of zinc fluoride 0.6Kg, stannous fluoride 3.9Kg, copper fluoride 0.5Kg, tetrahydroxyethy-lethylenediamine.
The preparation method is as follows for present embodiment inner core scaling powder:
Polyhydroxy amine in the present embodiment constitutes by tetrahydroxyethy-lethylenediamine is single.
⑴ place tetrahydroxyethy-lethylenediamine in the evaporation boiler of corrosion-resistant finishes, is dissolved in water, and the weight ratio of tetrahydroxyethy-lethylenediamine and water is 1:1;
⑵ dropwise add concentration in the evaporation boiler is 10～15% hydrofluoric acid, regulates pH value to 6～8;
[3] the heating evaporation material reaches 140～150 ℃ until temperature;
[4] pour polypropylene containers into after material in the evaporation boiler is cooled to 100～110 ℃ and be cooled to room temperature, get the white solid material, be the hydrofluoride of described tetrahydroxyethy-lethylenediamine;
⑸ prepare scaling powder: take by weighing the hydrofluoride of above-mentioned tetrahydroxyethy-lethylenediamine and drop into reactor by specified wt (95Kg), be heated to 110～130 ℃, treat that it melts the back fully and adds zinc fluoride 0.6Kg, stannous fluoride 3.9Kg and copper fluoride 0.5Kg; After treating that zinc fluoride, stannous fluoride and copper fluoride dissolve fully, stir 10min, cooled and solidified obtains the inner core scaling powder;
The preparation process of above-mentioned solder stick for aluminium and aluminum alloy soft soldering is:
⑴ prepare brazing filler metal alloy: tin, lead, silver are weighed in proportion, and melting forms uniform brazing filler metal alloy, is cast into ingot casting under 320～380 ℃ of conditions;
⑵ draw solder stick: utilize extruder that scaling powder is pressed into brazing filler metal alloy as inner core, cool off back rolling, wire drawing, make the solder stick of required diameter, the weight ratio that feeds intake of brazing filler metal alloy and scaling powder is 100:1～3.
Embodiment 3:
A kind of solder stick for aluminium and aluminum alloy soft soldering is made up of scaling powder two parts of outer field brazing filler metal alloy and inner core, wherein:
Raw material components and the percentage by weight of outer brazing filler metal alloy are: tin 16Kg, silver-colored 2Kg, plumbous 82Kg;
The raw material components of inner core scaling powder and percentage by weight are: zinc fluoride 1.2Kg, stannous fluoride 7.2Kg, fluoridize the hydrofluoride 90Kg of bismuth 1.6Kg, multi-hydroxy ethyl amine.
The preparation method is as follows for present embodiment inner core scaling powder:
In the present embodiment, polyhydroxy amine is made up of diethanol amine and triisopropanolamine,
⑴ mix diethanol amine and triisopropanolamine and place in the evaporation boiler of corrosion-resistant finishes according to the ratio (weight ratio) of 1:3, be dissolved in water, and the weight ratio of multi-hydroxy ethyl amine and water is 1:1;
⑵ dropwise add concentration in the evaporation boiler is 10～15% hydrofluoric acid, prevents from splashing, and regulates pH value to 6～8;
⑶ heating evaporation material to 140～150 ℃;
⑷ treat that material is cooled to 110～120 ℃, pours the polypropylene containers cooling into, gets white waxy solid, is the hydrofluoride of described multi-hydroxy ethyl amine;
⑸ prepare scaling powder: take by weighing the hydrofluoride of above-mentioned polyhydroxy amine and drop into reactor by specified wt (90Kg), be heated to 110～130 ℃, treat that it melts the back fully and adds zinc fluoride 1.2Kg, stannous fluoride 7.2Kg and copper fluoride 1.6Kg; Treat that it dissolves the back fully and stirs 10min, cooled and solidified then;
The preparation process of above-mentioned solder stick for aluminium and aluminum alloy soft soldering is:
⑴ prepare brazing filler metal alloy: tin, lead, silver are weighed in proportion, and melting forms uniform brazing filler metal alloy, is cast into ingot casting under 320～380 ℃ of conditions;
⑵ draw solder stick: utilize extruder that scaling powder is pressed into brazing filler metal alloy as inner core, cool off back rolling, wire drawing, make the solder stick of required diameter, the weight ratio that feeds intake of brazing filler metal alloy and scaling powder is 40:1.
Detect test
With pressing the made solder stick brazed aluminum joint of embodiment 1～3, water cleans up joint then, carries out salt spray test by the aluminium soldering joint of GB GB/T242.3.17-2008, and salt fog concentration is 5%NaCl solution, and test temperature is 35 ℃.
Result of the test is listed in table 1, lists file names with the result of the test of some reference examples in the table 1:
Table 1: soldered fitting corrosion resistance
Claims (7)
1. scaling powder that is used for aluminium and aluminum alloy soft soldering, it is characterized in that: raw material components and the percentage by weight of forming described scaling powder are:
Heavy metal fluoride activating agent 5～15%
The hydrofluoride 85～95% of polyhydroxy amine.
2. the scaling powder for aluminium and aluminum alloy soft soldering according to claim 1, it is characterized in that: the preparation method of the hydrofluoride of described polyhydroxy amine is as follows
⑴ place polyhydroxy amine in the evaporation boiler of corrosion resistant coating, is dissolved in water, and the weight ratio of polyhydroxy amine and water is 1:1;
⑵ dropwise add the hydrofluoric acid that concentration is 10-15wt% in evaporation boiler, be adjusted to 6～8 until the pH value;
⑶ will stop heating behind material heating evaporation to 140～150 in the evaporation boiler ℃; ,
⑷ be cooled to 100～110 ℃ with material in the pot, pours polyacrylic container into and continue to be cooled to room temperature, gets white waxy solid, is the hydrofluoride of described polyhydroxy amine;
⑸ drop into reactor with the hydrofluoride of polyhydroxy amine, is heated to 110～130 ℃, after the hydrofluoride for the treatment of polyhydroxy amine melts fully, add described heavy metal fluoride activating agent, treat that the heavy metal fluoride activating agent dissolves fully after, stir, cooled and solidified namely gets scaling powder then.
3. the scaling powder for aluminium and aluminum alloy soft soldering according to claim 1 and 2 is characterized in that: optional 1～3 kind the composition from monoethanolamine, diethanol amine, triethanolamine, AEEA, dihydroxy ethyl ethylenediamine, tetrahydroxyethy-lethylenediamine, triisopropanolamine or trishydroxymethylaminomethane of described polyhydroxy amine.
4. the scaling powder for aluminium and aluminum alloy soft soldering according to claim 1, it is characterized in that: described heavy metal fluoride activating agent is selected from zinc fluoride, stannous fluoride, fluoridizes bismuth and any at least two kinds combination of copper fluoride.
5. a solder stick that is used for aluminium and aluminum alloy soft soldering is made up of brazing filler metal alloy and scaling powder, it is characterized in that:
Percentage by weight between described brazing filler metal alloy composition and the composition is: tin 15～30%, silver 1～3%, surplus lead;
Described scaling powder is the described scaling powder of one of claim 1-4.
6. the solder stick for aluminium and aluminum alloy soft soldering according to claim 5, it is characterized in that: the weight ratio of described brazing filler metal alloy and scaling powder is 40～100:1.
7. according to claim 5 or 6 described solder sticks for aluminium and aluminum alloy soft soldering, it is characterized in that: the preparation method is as follows:
⑴ prepare brazing filler metal alloy: tin, lead, silver are weighed in proportion, and melting forms uniform brazing filler metal alloy, is cast into ingot casting under 320～380 ℃ of conditions, obtains brazing filler metal alloy;
⑵ synthesize solder stick: utilize extruder that scaling powder is pressed into brazing filler metal alloy as inner core, will be pressed into brazing filler metal alloy cooling back rolling, the wire drawing of scaling powder, make the solder stick of required diameter.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201310247992 CN103317254A (en) | 2013-06-20 | 2013-06-20 | Soldering flux and solder wire for aluminum and aluminum alloy soldering |
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| CN 201310247992 CN103317254A (en) | 2013-06-20 | 2013-06-20 | Soldering flux and solder wire for aluminum and aluminum alloy soldering |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104690441A (en) * | 2015-02-09 | 2015-06-10 | 深圳市兴鸿泰锡业有限公司 | Solder wire and preparation method thereof |
| CN106695160A (en) * | 2016-12-20 | 2017-05-24 | 深圳市兴鸿泰锡业有限公司 | Automatic tin soldering wire of robot |
| CN113182728A (en) * | 2021-04-29 | 2021-07-30 | 烟台固邦新材料有限公司 | Low-melting-point tin solder material capable of welding aluminum and preparation method thereof |
-
2013
- 2013-06-20 CN CN 201310247992 patent/CN103317254A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104690441A (en) * | 2015-02-09 | 2015-06-10 | 深圳市兴鸿泰锡业有限公司 | Solder wire and preparation method thereof |
| CN106695160A (en) * | 2016-12-20 | 2017-05-24 | 深圳市兴鸿泰锡业有限公司 | Automatic tin soldering wire of robot |
| CN113182728A (en) * | 2021-04-29 | 2021-07-30 | 烟台固邦新材料有限公司 | Low-melting-point tin solder material capable of welding aluminum and preparation method thereof |
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Application publication date: 20130925 |