CN104942474B - A kind of cadmium-free silver brazing alloy of stanniferous, silicon, zinc and praseodymium and preparation method thereof - Google Patents
A kind of cadmium-free silver brazing alloy of stanniferous, silicon, zinc and praseodymium and preparation method thereof Download PDFInfo
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- CN104942474B CN104942474B CN201510390217.2A CN201510390217A CN104942474B CN 104942474 B CN104942474 B CN 104942474B CN 201510390217 A CN201510390217 A CN 201510390217A CN 104942474 B CN104942474 B CN 104942474B
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- praseodymium
- cadmium
- zinc
- silicon
- stanniferous
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/302—Cu as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
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Abstract
The invention discloses cadmium-free silver brazing alloy of a kind of stanniferous, silicon, zinc and praseodymium and preparation method thereof, solder proportioning by weight percent, by 0.02%～0.3% Pr, 30.0% Ag, 31.8% Zn, 1.85% Sn, 0.15% Si, remaining is constituted for Cu.The preparation method is, first according to Pr：Cu=1：1.2 ratio is smelted and obtains Cu Pr Binary Alloy Melts；Then Ag, Zn, Sn, the Si in Cu Pr Binary Alloy Melts and proportioning component and remaining Cu are put in smelting furnace carries out smelting, casts, and obtains the cadmium-free silver brazing alloy ingot casting of stanniferous, silicon, zinc and praseodymium.The solder of the present invention has good spreading property, weld properties and solid-liquid phase line temperature.Save silver-colored resource simultaneously, reduce the cost of solder.
Description
Technical field
The present invention relates to a kind of solder, more specifically, is the cadmium-free silver brazing alloy for being related to a kind of stanniferous, silicon, zinc and praseodymium.It is suitable
Share in the soldering of red copper, brass, copper alloy, carbon steel and stainless steel and other metal materials.Belong to brazing material and technology of preparing
Field.
Background technology
With information technology, aeronautical and space technology and household electrical appliances industrial expansion, soldering tech is with its unique superiority
And flexibility, it is widely used in the welding of the workpiece of the solderabilities such as some labyrinths, fine structure difference.For many green woods
For material, complex component, soldering is sometimes the interconnection technique of its unique feasible.Certainly, soldering tech is for modern work
Industry has the meaning of uniqueness, it might even be possible to say the development for affecting modern industry to a certain extent.
Silver solder is a most widely used class hard solder, with good mechanical property, electrical and thermal conductivity, corrosion resistance,
It is widely used in soldering mild steel, structural steel, stainless steel, copper and copper alloy etc..In many silver solders, containing cadmium brazing silver alloy because of tool
There are very moderate fusing point, good processing characteristics, excellent wettability and good mechanical property, thus navigate in aviation
My god, the field such as electric apparatus manufacture and household electric appliances obtain extremely wide application.In recent years, due to economic fast development, silver
The demand of solder drastically expands.
But, on the one hand, silver is noble metal, price costly, it is traditional containing cadmium brazing silver alloy as silver content is higher, lead
Cost is caused to remain high always；On the other hand, due to European Union " WEEE " and " ROHS " double instructions promulgation, prohibited bag
Application of the cadmium in six kinds of interior noxious materials in Electronic products manufacturing is included, wherein the requirement to cadmium is even more is less than 100ppm.
China is taken the lead with prime information Estate Division, and six related departments also combine and put into effect relevant policies, forbid the application of cadmium.Therefore,
The research and development of the low silver-colored cadmium-free silver brazing alloy of " greenization " have become the focus of recent domestic soldering circle concern.The present invention's
" cadmium-free silver brazing alloy of a kind of stanniferous, silicon, zinc and praseodymium and preparation method thereof ", is to complete under this technical background.
The content of the invention
The purpose of the present invention is to overcome the problem and defect that above-mentioned prior art is present, there is provided a kind of function admirable contains
Cadmium-free silver brazing alloy of tin, silicon, zinc and praseodymium and preparation method thereof.
To reach above-mentioned purpose, the present invention realizes that the technical scheme of purpose is：
The cadmium-free silver brazing alloy of a kind of stanniferous, silicon, zinc and praseodymium, proportioning is its chemical composition by weight percent：0.02%～
0.3% Pr, 30.0% Ag, the Sn of 31.8% Zn, 1..85%, 0.15% Si, remaining be Cu, gross mass percentage
For 100%.
The purity of Cu described above and Pr is 99.99%.
To reach above-mentioned purpose, the present invention realizes that another technical scheme of purpose is：
The preparation method of the cadmium-free silver brazing alloy of a kind of stanniferous of the present invention, silicon, zinc and praseodymium, comprises the steps：
The first step, preparation Cu-Pr Binary Alloy Melts
(1) fall the oxide layer on cathode copper (Cu) and metal praseodymium (Pr) surface using sand papering, then surpassed with alcohol
Sound wave is cleaned；
(2) by the Pr and Cu Jing after processing according to Pr：Cu=1：1.2 ratio, in input vacuum arc furnace ignition, vacuumize,
100% pure argon (Ar) is filled with, smelting obtains Cu-Pr Binary Alloy Melts；
Second step, the cadmium-free silver brazing alloy for preparing stanniferous, silicon, zinc and praseodymium
(1) Ag, Zn, Sn, Si in the Cu-Pr Binary Alloy Melts and proportioning component that obtain the first step and remaining
Cu carries out smelting in being put into smelting furnace, casts, and obtains the cadmium-free silver brazing alloy ingot casting of stanniferous, silicon, zinc and praseodymium；
(2) by the cadmium-free silver brazing alloy ingot casting of the tin for obtaining, silicon, zinc and praseodymium by extruding, drawing, pickling, obtain it is stanniferous,
The cadmium-free silver brazing alloy silk material of silicon, zinc and praseodymium.
The purity of argon gas described in the above-mentioned first step is 100%.
Smelting furnace described in above-mentioned second step is intermediate frequency smelting furnace.
Compared with the prior art the present invention has advantages below and beneficial effect：
1st, the content of silver-colored (Ag), cost performance compared with now widely used B-Ag45CuZn solders, are effectively reduced
It is high；
2nd, verification experimental verification, the solder of the present invention have good spreading property, weld properties and solid-liquid phase line temperature.
3rd, due to adding trace rare-earth element praseodymium (Pr), find praseodymium (Pr) sprawling with surface-active for silver-base solder
Effect, i.e., can reduce the surface tension of liquid solder, improve solder spreadability.Meanwhile, praseodymium (Pr) easily with solder in have
The reactions such as evil impurity S, Bi generate rare earth and are mingled with, and can effectively remove impact of the impurity element to solder.The rare-earth phase of generation again may be used
To play a part of equiax crystal, so as to crystal grain thinning, the mechanical property of solder is improved.
4th, by contrast test, it is determined that the addition scope of Rare Earth Elements of Praseodymium (Pr).Test finds that praseodymium (Pr's) adds
Dosage is controlled in proper range, and combination property is optimal, when the amount that praseodymium (Pr) is added is higher than certain limit, then can be produced
The rare-earth phase of many fragility, reduces the combination property of solder on the contrary.
Description of the drawings
Fig. 1 sprawls specificity analysis figure for the Ag-Cu-Zn-Sn-Si-Pr solders of Ag45CuZn and different praseodymium (Pr) contents
Spectrum.
Fig. 2 is Ag45CuZn and the solid liquid phase temperature profile of the Ag-Cu-Zn-Sn-Si solders of different praseodymium (Pr) contents.
Fig. 3 is Ag45CuZn and the mechanics property analysis collection of illustrative plates of the Ag-Cu-Zn-Sn-Si solders of different praseodymium (Pr) contents.
Fig. 4 is microscopic structure (2000 times) structure chart containing Ag-Cu-Zn-Sn-Si-Pr solders during praseodymium (Pr) 0.02%.
Fig. 5 is microscopic structure (2000 times) structure chart containing Ag-Cu-Zn-Sn-Si-Pr solders during praseodymium (Pr) 0.08%.
Fig. 6 is microscopic structure (2000 times) structure chart containing Ag-Cu-Zn-Sn-Si-Pr solders during praseodymium (Pr) 0.15%.
Fig. 7 is microscopic structure (2000 times) structure chart containing Ag-Cu-Zn-Sn-Si-Pr solders during praseodymium (Pr) 0.3%.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments and accompanying drawing, it is right
The present invention is described in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and
It is not used in the restriction present invention.
A kind of cadmium-free silver brazing alloy of the stanniferous, silicon, zinc and praseodymium of the present invention, proportioning by weight percent, by 0.02%～
0.3% Pr, 30.0% Ag, the Sn of 31.8% Zn, 1..85%, 0.15% Si, remaining be Cu composition, gross mass hundred
Fraction is 100%.
1st, the present invention is described in further detail in conjunction with the embodiments
Embodiment 1
First, proportioning by weight percent
The composition of the present embodiment solder is：30.0% silver medal (Ag), 31.8% zinc (Zn), 1.85% tin (Sn), 0.15% silicon
(Si)、
0.02% praseodymium (Pr), remaining is copper (Cu).
2nd, preparation method
The first step：Prepare Cu-Pr Binary Alloy Melts
1st, fall the oxide layer on cathode copper (Cu) and metal praseodymium (Pr) surface using sand papering, then ultrasound is carried out with alcohol
Ripple is cleaned, and obtains Cu and Pr that purity is 99.99%；
2nd, by the Pr and Cu Jing after processing according to Pr：Cu=1：1.2 ratio, in input vacuum arc furnace ignition, vacuumizes, fills
Enter 100% pure argon (Ar), smelting obtains Cu-Pr Binary Alloy Melts；
Second step：Prepare the cadmium-free silver brazing alloy of stanniferous, silicon, zinc and praseodymium
1st, Ag, Zn, Sn, Si in the Cu-Pr Binary Alloy Melts and proportioning component that obtain the first step and remaining
Cu carries out smelting in being put into intermediate frequency smelting furnace, casts, and obtains the cadmium-free silver brazing alloy ingot casting of stanniferous, silicon, zinc and praseodymium；
2nd, by the cadmium-free silver brazing alloy ingot casting of the tin for obtaining, silicon, zinc and praseodymium by extruding, drawing, pickling, obtain stanniferous, silicon,
The cadmium-free silver brazing alloy silk material of zinc and praseodymium.
3rd, beneficial effect
The cadmium-free silver brazing alloy of stanniferous, silicon, zinc and praseodymium that the present embodiment is obtained, its solidus temperature are 675 DEG C, liquidus curve temperature
Spend for 765 DEG C, coordinate FB102 (QJ102) brazing flux, Joint intensity：Brass-brass (σb=330MPa).
Embodiment 2
First, proportioning by weight percent
The composition of the present embodiment solder is：30.0% silver medal (Ag), 31.8% zinc (Zn), 1.85% tin (Sn), 0.15% silicon
(Si), 0.08% praseodymium (Pr), remaining is copper (Cu).
2nd, preparation method is with embodiment 1.
3rd, beneficial effect
The cadmium-free silver brazing alloy of stanniferous, silicon, zinc and praseodymium that the present embodiment is obtained, its solidus temperature are 670 DEG C, liquidus curve temperature
Spend for 755 DEG C, coordinate FB102 (QJ102) brazing flux, Joint intensity：Brass-brass (σ b=360MPa).
Embodiment 3
First, proportioning by weight percent
The composition of the present embodiment solder is：30.0% silver medal (Ag), 31.8% zinc (Zn), 1.85% tin (Sn), 0.15% silicon
(Si), 0.15% praseodymium (Pr), remaining is copper (Cu).
2nd, preparation method is with embodiment 1.
3rd, beneficial effect
The cadmium-free silver brazing alloy of stanniferous, silicon, zinc and praseodymium that the present embodiment is obtained, its solidus temperature are 670 DEG C, liquidus curve temperature
Spend for 755 DEG C, coordinate FB102 (QJ102) brazing flux, Joint intensity：Brass-brass (σb=370MPa).
Embodiment 4
First, proportioning by weight percent
The composition of the present embodiment solder is：30.0% silver medal (Ag), 31.8% zinc (Zn), 1.85% tin (Sn), 0.15% silicon
(Si), 0.3% praseodymium (Pr), remaining is copper (Cu).
2nd, preparation method is with embodiment 1.
3rd, beneficial effect
The cadmium-free silver brazing alloy of stanniferous, silicon, zinc and praseodymium that the present embodiment is obtained, its solidus temperature are 670 DEG C, liquidus curve temperature
Spend for 755 DEG C, coordinate FB102 (QJ102) brazing flux, Joint intensity：Brass-brass (σb=320MPa).
2nd, accompanying drawing is combined, the present invention is described in further detail
Shown in accompanying drawing 1, it is that the characteristic test result of sprawling of the Ag-Cu-Zn-Sn-Si-Pr solders of different praseodymiums (Pr) content is divided
Analysis collection of illustrative plates, according to GB《Solder spreadability and joint filling experimental technique》(GB/T 11364-2008) carries out spreadability experiment.
Shown in accompanying drawing 2, be test solder solid-liquid phase line experiment (DTA) including following step：
(1) solder to having smelted carries out cutting, and is weighed with electronics Libra, test solder quality for (20 ±
5)mg；
(2) symmetrical measured solder alcohol carries out ultrasonic wave and cleans, and dries；
(3) differential thermal analysis experiment (DTA) is carried out to solder, programming rate is 15 DEG C/min, obtains fusion temperature curve；
The mechanical property of the Ag-Cu-Zn-Sn-Si-Pr solders of Ag45CuZn and different praseodymium (Pr) contents shown in accompanying drawing 3
Experiment is according to basis《Soldering joint strength experimental technique》(GB/T 11363-2008) is tested, mother metal be respectively brass and
Red copper, selects docking mode to carry out soldered fitting mechanical property tests.
Shown in accompanying drawing 4 to accompanying drawing 7, be plus praseodymium (Pr) Ag-Cu-Zn-Sn-Si-Pr solders afterwards microscopic structure, find with
The increase of praseodymium (Pr) content, crystal boundary are substantially refined, and grain size is improved.The strong acicular constituent of script directionality is reduced, and is taken and generation
Be vermiform tissue, find that grain boundaries Elemental redistributions is (19.22%Cu, 26.73%Zn, 51.06% by energy spectrum analysis
Ag, 1.07%Sn, 0.92%Pr, balance of Si), it was demonstrated that praseodymium (Pr) segregation, in crystal boundary, plays invigoration effect.
The above, preferably specific embodiment only of the invention.Certainly, the present invention can also have other various enforcements
Example, in the case of without departing substantially from spirit of the invention and its essence, any those familiar with the art, when can be according to this
Various corresponding equivalent changes and deformation are made in invention, should all belong to the protection domain of appended claims of the invention.
Claims (4)
1. the cadmium-free silver brazing alloy of a kind of stanniferous, silicon, zinc and praseodymium, it is characterised in that：Proportioning by weight percent, by 0.02%～
0.3% Pr, 30.0% Ag, 31.8% Zn, 1.85% Sn, 0.15% Si, remaining be Cu composition, gross mass percentage
Number is 100%.
2. the cadmium-free silver brazing alloy of stanniferous, silicon according to claim 1, zinc and praseodymium, it is characterised in that：Described Cu's and Pr
Purity is 99.99%.
3. the preparation method of the cadmium-free silver brazing alloy of a kind of stanniferous, silicon according to claim 1, zinc and praseodymium, it is characterised in that
Comprise the steps：
The first step, preparation Cu-Pr Binary Alloy Melts
(1) cathode copper, i.e. Cu and metal praseodymium, the i.e. oxide layer on Pr surfaces are fallen using sand papering, then ultrasound is carried out with alcohol
Ripple is cleaned；
(2) by the Pr and Cu Jing after processing according to Pr：Cu=1：1.2 ratio, in input vacuum arc furnace ignition, vacuumizes, is filled with
100% pure argon, smelting obtain Cu-Pr Binary Alloy Melts；
Second step, the cadmium-free silver brazing alloy for preparing stanniferous, silicon, zinc and praseodymium
(1) Ag, Zn, Sn, the Si and remaining Cu in the Cu-Pr Binary Alloy Melts and proportioning component that obtain the first step is put
Carry out smelting in entering smelting furnace, cast, obtain the cadmium-free silver brazing alloy ingot casting of stanniferous, silicon, zinc and praseodymium；
(2) by the cadmium-free silver brazing alloy ingot casting of the tin for obtaining, silicon, zinc and praseodymium by extruding, drawing, pickling obtains stanniferous, silicon, zinc
With the cadmium-free silver brazing alloy silk material of praseodymium.
4. the preparation method of the cadmium-free silver brazing alloy of stanniferous, silicon according to claim 3, zinc and praseodymium, it is characterised in that：Second
Smelting furnace described in step is intermediate frequency smelting furnace.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510390217.2A CN104942474B (en) | 2015-07-06 | 2015-07-06 | A kind of cadmium-free silver brazing alloy of stanniferous, silicon, zinc and praseodymium and preparation method thereof |
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|---|---|---|---|
| CN201510390217.2A CN104942474B (en) | 2015-07-06 | 2015-07-06 | A kind of cadmium-free silver brazing alloy of stanniferous, silicon, zinc and praseodymium and preparation method thereof |
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| CN104942474A CN104942474A (en) | 2015-09-30 |
| CN104942474B true CN104942474B (en) | 2017-04-05 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101132881A (en) * | 2004-12-01 | 2008-02-27 | 爱尔发加热有限公司 | Solder alloy |
| CN101733581A (en) * | 2009-11-12 | 2010-06-16 | 蒋汝智 | Cadmium-free silver brazing alloy containing calcium, silicon and erbium |
| CN101780613A (en) * | 2010-03-25 | 2010-07-21 | 杭州华光焊料有限公司 | Special rare earth alloy silver-brazing filler metal |
| CN103252595A (en) * | 2013-05-28 | 2013-08-21 | 安徽众汇制冷有限公司 | Brazing filler metal for connecting copper and stainless steel, application of brazing filler metal and method for welding silencer |
| CN104439753A (en) * | 2014-11-13 | 2015-03-25 | 杭州华光焊接新材料股份有限公司 | Multi-element silver soldering material containing indium and tin and preparation method of multi-element silver soldering material |
-
2015
- 2015-07-06 CN CN201510390217.2A patent/CN104942474B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101132881A (en) * | 2004-12-01 | 2008-02-27 | 爱尔发加热有限公司 | Solder alloy |
| CN101733581A (en) * | 2009-11-12 | 2010-06-16 | 蒋汝智 | Cadmium-free silver brazing alloy containing calcium, silicon and erbium |
| CN101780613A (en) * | 2010-03-25 | 2010-07-21 | 杭州华光焊料有限公司 | Special rare earth alloy silver-brazing filler metal |
| CN103252595A (en) * | 2013-05-28 | 2013-08-21 | 安徽众汇制冷有限公司 | Brazing filler metal for connecting copper and stainless steel, application of brazing filler metal and method for welding silencer |
| CN104439753A (en) * | 2014-11-13 | 2015-03-25 | 杭州华光焊接新材料股份有限公司 | Multi-element silver soldering material containing indium and tin and preparation method of multi-element silver soldering material |
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| CN104942474A (en) | 2015-09-30 |
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