CN106736003B - The low cadmium brazing silver alloy of low melting point - Google Patents
The low cadmium brazing silver alloy of low melting point Download PDFInfo
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- CN106736003B CN106736003B CN201611156602.1A CN201611156602A CN106736003B CN 106736003 B CN106736003 B CN 106736003B CN 201611156602 A CN201611156602 A CN 201611156602A CN 106736003 B CN106736003 B CN 106736003B
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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
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Abstract
A kind of low cadmium brazing silver alloy of low melting point, belongs to solder bonding metal field of material technology.Its chemical composition matches by weight percent are as follows: the Ga of the In of the Cd of the Cu of the Ag of 24-26%, 30-41%, 0.05-0.13%, 0.001-0.005%, 0.001-0.005%, remaining is Zn.Have the characteristics that good wetting and spreading, reduce as rare element indium and gallium content, abandoned tin element and have excellent brazed seam mechanical property, there is lower fusion temperature range than BAg25CuZn, BAg25CuZnSn solder, so that solder is easily operated during the brazing process, reduce the technical difficulty of brazing operator, especially suitable for the soldering of other industrial products in addition to the industries such as the electronic electric equipment of RoHS instruction limitation, the problems such as workpiece because caused by brazing temperature is excessively high aoxidizes even softening, soldering joint strength decline is avoided.
Description
Technical field
The invention belongs to solder bonding metal field of material technology, and in particular to a kind of low cadmium brazing silver alloy of low melting point.
Background technique
The fusion temperature for the BAg25CuZnCd solder recommended in prior art such as (GB/T 10046-2008 " silver solder ")
Range is 607 DEG C of solidus, and 682 DEG C of liquidus curve, the fusion temperature range of " lower " is easy to operate when to be brazed, technique is simple
Just, it was once one of solder that solder user dotes on.But since RoHS instruction and portion of Environment Protect in China portion the 39th enable
The application of the limitation that (implementing from August 1st, 2016) uses Cd element, BAg25CuZnCd solder is affected, then,
Following two solder is by " substitute " as BAg25CuZnCd solder: one is BAg25CuZn solder；Two be BAg25CuZnSn
Solder.The former (i.e. BAg25CuZn solder) since the essential element in its chemical component is Ag, Cu, Zn, and Ag content is
24.0%~26.0%, thus its fusion temperature range is 700 DEG C of solidus, 790 DEG C of liquidus curve；And the latter is (i.e.
BAg25CuZnSn solder) although being added to 1.5%~2.5% Sn element, so that its fusion temperature range is reduced to solidus
680 DEG C, 760 DEG C of liquidus curve, but still be much higher than 607 DEG C of the solidus of BAg25CuZnCd solder, 682 DEG C of liquidus curve it is molten
Change temperature range.Therefore, how to reduce the fusion temperature range of silver solder and make it have excellent wetting, spreading property and pricker
It stitches mechanical property and uses and meet requirement of the industrial 4.0 epoch soldered fittings to high-performance, high efficiency, low cost into industry pass
It infuses and it is expected the project broken through.
The applicant has carried out literature search, although being seen in the technology of silver solder in published Chinese patent literature
Information, slightly " cadmium-free silver brazing alloy containing gallium and cerium " recommended such as CN100377832C to enumerate, solidus temperature is at 605 DEG C
~615 DEG C, liquidus temperature is at 635 DEG C~645 DEG C；" cadmium-free silver brazing alloy containing gallium, indium and cerium " that CN100352597C is provided,
Its solidus temperature is at 640 DEG C~650 DEG C, and liquidus temperature is at 685 DEG C~710 DEG C；CN100420538C introduce " one kind contains
The cadmium-free silver-base solder of gallium, indium and cerium ", solidus temperature is at 650 DEG C~665 DEG C, and liquidus temperature is at 730 DEG C~745 DEG C
Etc..
Cadmium-free silver brazing alloy in prior art can reduce being total to for fusion temperature (or solidus temperature, liquidus temperature)
It is one or more low melting point elements such as Sn, Ga, the In for being added to quality % ratio in formula and being at least 1% or more with feature
Deng.But since Ga, In belong to rare element, global annual output is extremely limited, and price is quite even higher than white with silver
Therefore silver does not have the value of high volume applications；Sn element is inexpensive and rich reserves are still largely added and easily formed firmly
And crisp intermetallic compound Cu6Sn5, silver solder processing difficulties are caused, it can in addition to the additive amount of the Sn in BAg60CuSn solder
To reach outside 9.5%~10.5%, general additive amount is 1.5%~2.5% in Ag-Cu-Zn-Sn series solder, individually
If the additive amount of Sn in BAg56CuZnSn is 4.5%~5.5% (referring to GB/T10046-2008 " silver solder " table 2).
But the main composition in the prior art including aforementioned patent literature is Ag, Cu, Zn element (not phosphorous member
Element is classified as the silver solder of GB/T 10046-2008) and all silver solders of Ga, In, Sn constituent content lower than 0.15%,
It is insufficient to allow liquidus temperature≤710 DEG C and uses 682 DEG C of liquidus temperature of " no cadmium close to BAg25CuZnCd solder
Silver solder ".For this purpose, the applicant has carried out deep exploration and has made test repeatedly, technical side described below
Case generates in this background.
Summary of the invention
Task of the invention lies in provide it is a kind of facilitate significantly reduce fusing point, be conducive to embody excellent wetting and spreading
Property, be beneficial to the content for significantly reducing indium and gallium and the low cadmium brazing silver alloy of low melting point for abandoning tin element.
The task of the present invention is in this way to complete, and a kind of low cadmium brazing silver alloy of low melting point, chemical composition presses quality percentage
Number proportion are as follows: the In of the Cd of the Cu of the Ag of 24-26%, 30-41%, 0.05-0.13%, 0.001-0.005%, 0.001-
0.005% Ga, remaining is Zn.
A kind of low cadmium brazing silver alloy of low melting point, chemical composition match by weight percent are as follows: 24% Ag, 41% Cu,
0.05% Cd, 0.001% In, 0.005% Ga, remaining is Zn.
A kind of low cadmium brazing silver alloy of low melting point, chemical composition match by weight percent are as follows: 26% Ag, 30% Cu,
0.13% Cd, 0.001% In, 0.001% Ga, remaining is Zn.
A kind of low cadmium brazing silver alloy of low melting point, chemical composition match by weight percent are as follows: 25% Ag, 36% Cu,
0.1% Cd, 0.005% In, 0.005% Ga, remaining is Zn.
A kind of low cadmium brazing silver alloy of low melting point, chemical composition match by weight percent are as follows: 25.2% Ag, 40.3%
Cu, 0.12% Cd, 0.002% In, 0.003% Ga, remaining is Zn.
A kind of low cadmium brazing silver alloy of low melting point, chemical composition match by weight percent are as follows: 24.3% Ag, 39.6%
Cu, 0.11% Cd, 0.004% In, 0.002% Ga, remaining is Zn.
The low cadmium brazing silver alloy of low melting point provided by the invention relative in prior art BAg25CuZn, BAg25CuZnSn,
For BAg25CuZnCd solder, not only with good wetting and spreading, significantly reduce indium and gallium as rare element
Content has abandoned tin element and has had the characteristics that excellent brazed seam mechanical property, but also than BAg25CuZn,
BAg25CuZnSn solder has " lower fusion temperature range ", so that solder more easily operates during the brazing process, reduces pricker
The technical difficulty for welding operative employee is produced especially suitable for other industry in addition to the industries such as the electronic electric equipment of RoHS instruction limitation
The soldering of product avoids the problems such as workpiece oxidation because caused by brazing temperature is excessively high even softens, soldering joint strength declines.
Specific embodiment
Ag content in the low cadmium brazing silver alloy formula of low melting point provided by the invention is that 24-26%, Cd content are lower than 0.15%
(meet the requirement of Unite States Standard AWS A5.8/A5.8M:2004 table 1), solder liquidus temperature " as far as possible " are close
BAg25CuZnCd solder and there is good wetting, spreading property and soldered fitting mechanical property, is able to satisfy non-electronic, non-
Household electric appliances (industry of non-RoHS instruction limitation) certain specialities brazing requirements.
It analyzes, compare RoHS instruction clause and GB/T 10046-2008 " silver solder ", Unite States Standard AWS A5.8/
A5.8M:2004 is it is found that limitation for elements such as Cd, and primarily directed to " electronic electric equipment ", non-electronic electrical equipment is produced
The solder containing cadmium still can be used in product, this is also to only have 5 kinds in GB/T 10046-2000 " silver solder " containing cadmium brazing silver alloy (ginseng
See GB/T 10046-2000 table 4), and GB/T 10046-2008 editions then have 10 kinds to contain cadmium brazing silver alloy (referring to GB/T10046-
2008 tables 2), then have in Unite States Standard AWS A5.8/A5.8M:2004 7 kinds containing cadmium brazing silver alloy (referring to AWSA5.8/A5.8M:
2004 tables 1) the reason of.From the point of view of science, although the solder containing cadmium use it is restricted, be " having ready conditions " limit.
So, it is believed that present GB/T 10046-2008 " silver solder " will be in the silver solder of all non-" Ag-Cu-Zn-Cd " models
Cadmium content be limited to 0.010% range without exception, it is clear that be excessively harsh.Because non-in AWS A5.8/A5.8M:2004 table 1
Cd content in Ag-Cu-Zn-Cd solder does not make specific requirement, and only defines " other element total amounts "≤0.15%.
Even if for silver in EU criteria DIN EN1044:1999 " Brazing-Filler metals " table 3 of version prevailing for the time being in force
The requirement of the impurity element Cd of solder is also≤0.030%, than 0.010% " width " 0.020% of chinese national standard.
The present inventor has found in the actual production, sale, use of silver solder, in the soldering of general industry product
In, even when the soldering manufacture of " food machinery ", other than clearly proposing to need to use " without cadmium " silver solder, to not by cadmium
As the cadmium content in the silver solder of main alloy element, and failed call≤0.010%.Outlet the U.S. cadmium-free silver brazing alloy be even more
Using Unite States Standard AWS A5.8/A5.8M:2004 as acceptance of delivery standard, if the other impurity elements of strict control, cadmium member
The allowance of element theoretically can be≤0.15%.
Based on the technical indicator of Unite States Standard AWS A5.8/A5.8M:2004 table 1, by theory analysis and test, discovery
It, can be by adding under the premise of " meeting Unite States Standard " under the regulation of Unite States Standard AWS A5.8/A5.8M:2004 table 1
Ga, In element for adding micro cadmium element, denier are finally obtained the low cadmium silver pricker of low melting point of the present invention by " alloy optimization "
The solid, liquid liquidus temperature of material is close to BAg25CuZnCd solder.
Embodiment 1:
Chemical composition matches by weight percent are as follows: 24.0% Ag, 41.0% Cu, 0.05% Cd, 0.001%
In, 0.005% Ga, surplus Zn.
The solidus temperature of the low cadmium brazing silver alloy of the low melting point that the present embodiment obtains is in 630 DEG C~645 DEG C ranges, liquidus curve temperature
Degree is in 695 DEG C~710 DEG C ranges (considering evaluated error).Using gas brazing mode, cooperate FB102 brazing flux, soldering is female
Joint intensity when material is following combination is shown in data in bracket: red copper-H62 brass (σb=225 ± 25MPa, τ=215 ±
30MPa), brass-Q235 steel (σb=280 ± 25MPa, τ=300 ± 30MPa), -304 stainless steel (σ of brassb=260 ±
25MPa, τ=280 ± 30MPa).
Embodiment 2:
Chemical composition matches by weight percent are as follows: 26.0% Ag, 30.0% Cu, 0.13% Cd, 0.001%
In, 0.001% Ga, surplus Zn.
The solidus temperature of the low cadmium brazing silver alloy of the low melting point that the present embodiment obtains is in 630 DEG C~645 DEG C ranges, liquidus curve temperature
Degree is in 695 DEG C~710 DEG C ranges (considering evaluated error).Using gas brazing mode, cooperate FB102 brazing flux, soldering is female
Joint intensity when material is following combination is shown in data in bracket: red copper-H62 brass (σb=225 ± 25MPa, τ=215 ±
30MPa), brass-Q235 steel (σb=280 ± 25MPa, τ=300 ± 30MPa), -304 stainless steel (σ of brassb=260 ±
25MPa, τ=280 ± 30MPa).
Embodiment 3:
Chemical composition matches by weight percent are as follows: 25.0% Ag, 36.0% Cu, 0.10% Cd, 0.005%
In, 0.005% Ga, surplus Zn.
The solidus temperature of the low cadmium brazing silver alloy of the low melting point that the present embodiment obtains is in 630 DEG C~645 DEG C ranges, liquidus curve temperature
Degree is in 695 DEG C~710 DEG C ranges (considering evaluated error).Using gas brazing mode, cooperate FB102 brazing flux, soldering is female
Joint intensity when material is following combination is shown in data in bracket: red copper-H62 brass (σb=225 ± 25MPa, τ=215 ±
30MPa), brass-Q235 steel (σb=280 ± 25MPa, τ=300 ± 30MPa), -304 stainless steel (σ of brassb=260 ±
25MPa, τ=280 ± 30MPa).
Embodiment 4:
Chemical composition matches by weight percent are as follows: 25.2% Ag, 40.3% Cu, 0.12% Cd, 0.002%
In, 0.003% Ga, surplus Zn.
The solidus temperature of the low cadmium brazing silver alloy of the low melting point that the present embodiment obtains is in 630 DEG C~645 DEG C ranges, liquidus curve temperature
Degree is in 695 DEG C~710 DEG C ranges (considering evaluated error).Using gas brazing mode, cooperate FB102 brazing flux, soldering is female
Joint intensity when material is following combination is shown in data in bracket: red copper-H62 brass (σb=225 ± 25MPa, τ=215 ±
30MPa), brass-Q235 steel (σb=280 ± 25MPa, τ=300 ± 30MPa), -304 stainless steel (σ of brassb=260 ±
25MPa, τ=280 ± 30MPa).
Embodiment 5:
Chemical composition matches by weight percent are as follows: 24.3% Ag, 39.6% Cu, 0.11% Cd, 0.004%
In, 0.002% Ga, surplus Zn.
The solidus temperature of the low cadmium brazing silver alloy of the low melting point that the present embodiment obtains is in 630 DEG C~645 DEG C ranges, liquidus curve temperature
Degree is in 695 DEG C~710 DEG C ranges (considering evaluated error).Using gas brazing mode, cooperate FB102 brazing flux, soldering is female
Joint intensity when material is following combination is shown in data in bracket: red copper-H62 brass (σb=225 ± 25MPa, τ=215 ±
30MPa), brass-Q235 steel (σb=280 ± 25MPa, τ=300 ± 30MPa), -304 stainless steel (σ of brassb=260 ±
25MPa, τ=280 ± 30MPa).
Silver plate, cathode copper, zinc ingot metal, cadmium ingot, indium metal, gallium of the above-described embodiment 1 to 5 using purity for 99.99%,
It is added in intermediate frequency smelting furnace crucible by composition proportion.Smelted using conventional intermediate frequency smelting process, casting, then by squeezing,
Drawing to get arrive required solder silk material.Silver solder solidus temperature of the invention is in 630 DEG C~645 DEG C ranges, liquidus curves
Temperature is in 695 DEG C~710 DEG C ranges, and being significantly less than BAg25CuZn, (solidus temperature is 700 DEG C, liquidus temperature 790
DEG C), BAg25CuZnSn (solidus temperature is 680 DEG C, and liquidus temperature is 760 DEG C) solid, liquid liquidus temperature of solder, very
Close to the solid, liquid liquidus temperature (solidus temperature is 607 DEG C, and liquidus temperature is 682 DEG C) of BAg25CuZnCd, meet perhaps
The soldering processes of the products such as more RoHS instructions " the non-electronic electrical equipment " that there is no limit need.
Spreading property of the low cadmium brazing silver alloy of low melting point obtained by above-described embodiment 1 to 5 on several typical materials and
Comparative experimental data with BAg25CuZn, BAg25CuZnSn, BAg25CuZnCd solder is as shown in following table:
In conclusion the low cadmium brazing silver alloy of low melting point provided by the invention solves following key technical problem:
Although 1) the Cd element used in solder ingredient containing RoHS instruction limitation, Cd constituent content≤0.13%,
And meet Unite States Standard AWS A5.8/A5.8M:2004 to the regulation of silver-containing solder, and have compared with low melting point, wetting and spreading
Can excellent, brazed seam excellent in mechanical performance the characteristics of.
2) by the way that Ga the and In element of appropriate ratio is added in low cadmium brazing silver alloy, so that low cadmium brazing silver alloy of the invention exists
Red copper, Q235 steel, all has excellent wetting and spreading performance, spreading area, brazed seam on 304 stainless steels at brass (such as H62 brass)
Joint bending stiffness is all larger than BAg25CuZn solder, BAg25CuZnSn solder, suitable with BAg25CuZnCd solder.
Compared with previous research, substantive distinguishing features outstanding of the low cadmium brazing silver alloy of low melting point provided by the invention and significant
Progress place is:
1, research, which has found, adds the micro Cd element that mass fraction is 0.05% into BAg25CuZn solder, solder
Wetting and spreading performance is significantly increased, and fusion temperature is also decreased significantly.With the increase of Cd content, the wetting of solder is spread
Developable surface product increases, and brazing filler metal melts temperature fall increases.It can by theory analysis Cu-Cd, Zn-Cd binary alloy phase diagram
Know, this is because Cu and Cd can be formed, fusing point is 549 DEG C, Zn and Cd can form " low melting point eutectic " that fusing point is 266 DEG C
It is caused.
Based on the considerations of Unite States Standard AWS A5.8/A5.8M:2004 " other element total amount≤0.15% ", Cd element
Additive amount control is advisable 0.013%.
2, research has found the profit of " synergistic effect " to low cadmium brazing silver alloy of Ga, In element and Cd element that add denier
The affecting laws of wet spreading property, brazed seam mechanical property.By optimizing the addition range of Ga, In element, by the additive amount of Ga, In
Control can make spreading area, the brazed seam connector of the low cadmium brazing silver alloy of low melting point of the invention in 0.001%~0.005% range
Shearing strength is all larger than BAg25CuZn solder, BAg25CuZnSn solder, suitable with BAg25CuZnCd solder.
By theory analysis Cd-In, Cd-Ga binary alloy phase diagram it is found that this is because Cd and In can form fusing point is
127.7 DEG C, Cd and Ga can be formed caused by " low melting point eutectic " that fusing point is 282 DEG C.Ga, In element and the Cd member of denier
" synergistic effect " of element is not enough to make a significant impact the fusing point of solder of the present invention, and still, " alloy strengthening " effect can be shown
It writes the spreading area for increasing low cadmium brazing silver alloy and improves brazed seam joint bending stiffness.
Claims (6)
1. a kind of low cadmium brazing silver alloy of low melting point, it is characterised in that its chemical composition matches by weight percent are as follows: the Ag of 24-26%,
The Ga of the In of the Cd of the Cu of 30-41%, 0.05-0.13%, 0.001-0.005%, 0.001-0.005%, remaining is Zn.
2. a kind of low cadmium brazing silver alloy of low melting point, it is characterised in that its chemical composition matches by weight percent are as follows: 24% Ag,
41% Cu, 0.05% Cd, 0.001% In, 0.005% Ga, remaining is Zn.
3. a kind of low cadmium brazing silver alloy of low melting point, it is characterised in that its chemical composition matches by weight percent are as follows: 26% Ag,
30% Cu, 0.13% Cd, 0.001% In, 0.001% Ga, remaining is Zn.
4. a kind of low cadmium brazing silver alloy of low melting point, it is characterised in that its chemical composition matches by weight percent are as follows: 25% Ag, 36%
Cu, 0.1% Cd, 0.005% In, 0.005% Ga, it is remaining be Zn.
5. a kind of low cadmium brazing silver alloy of low melting point, it is characterised in that its chemical composition matches by weight percent are as follows: 25.2% Ag,
40.3% Cu, 0.12% Cd, 0.002% In, 0.003% Ga, remaining is Zn.
6. a kind of low cadmium brazing silver alloy of low melting point, it is characterised in that its chemical composition matches by weight percent are as follows: 24.3% Ag,
39.6% Cu, 0.11% Cd, 0.004% In, 0.002% Ga, remaining is Zn.
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| CN201611156602.1A CN106736003B (en) | 2016-12-15 | 2016-12-15 | The low cadmium brazing silver alloy of low melting point |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089356A (en) * | 1990-09-17 | 1992-02-18 | The Research Foundation Of State Univ. Of New York | Carbon fiber reinforced tin-lead alloy as a low thermal expansion solder preform |
| JPH08118066A (en) * | 1994-10-25 | 1996-05-14 | Honda Motor Co Ltd | Production of joined body consisting of permanent magnet having rust preventability and member of different material kind |
| CN1775459A (en) * | 2005-11-25 | 2006-05-24 | 常熟市华银焊料有限公司 | Cadmium-free silver solder comprising Ga, Im and Ce |
| CN1962160A (en) * | 2006-11-26 | 2007-05-16 | 常熟市华银焊料有限公司 | Cadmium-free silver solder containing gallium, indium and cerium |
| CN1962159A (en) * | 2006-11-26 | 2007-05-16 | 常熟市华银焊料有限公司 | Cadmium-free silver based solder containing gallium, indium and cerium |
| CN101049656A (en) * | 2007-05-14 | 2007-10-10 | 骆华明 | Silver solder of containing gallium, indium, and rare earth silicon and neodymium without cadmium |
-
2016
- 2016-12-15 CN CN201611156602.1A patent/CN106736003B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089356A (en) * | 1990-09-17 | 1992-02-18 | The Research Foundation Of State Univ. Of New York | Carbon fiber reinforced tin-lead alloy as a low thermal expansion solder preform |
| JPH08118066A (en) * | 1994-10-25 | 1996-05-14 | Honda Motor Co Ltd | Production of joined body consisting of permanent magnet having rust preventability and member of different material kind |
| CN1775459A (en) * | 2005-11-25 | 2006-05-24 | 常熟市华银焊料有限公司 | Cadmium-free silver solder comprising Ga, Im and Ce |
| CN1962160A (en) * | 2006-11-26 | 2007-05-16 | 常熟市华银焊料有限公司 | Cadmium-free silver solder containing gallium, indium and cerium |
| CN1962159A (en) * | 2006-11-26 | 2007-05-16 | 常熟市华银焊料有限公司 | Cadmium-free silver based solder containing gallium, indium and cerium |
| CN101049656A (en) * | 2007-05-14 | 2007-10-10 | 骆华明 | Silver solder of containing gallium, indium, and rare earth silicon and neodymium without cadmium |
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| CN106736003A (en) | 2017-05-31 |
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