CN106736003A - 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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- CN106736003A CN106736003A CN201611156602.1A CN201611156602A CN106736003A CN 106736003 A CN106736003 A CN 106736003A CN 201611156602 A CN201611156602 A CN 201611156602A CN 106736003 A CN106736003 A CN 106736003A
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- low
- brazing
- melting point
- solder
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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 and is by weight percent：24 26% Ag, 30 41% Cu, 0.05 0.13% Cd, 0.001 0.005% In, 0.001 0.005% Ga, remaining is Zn.With good wetting and spreading, reduce as rare element indium and gallium content, abandoned tin element and the features such as with excellent brazed seam mechanical property, there is relatively low fusion temperature scope than BAg25CuZn, BAg25CuZnSn solder, so that solder is easily operated in soldering, reduce the technical difficulty of brazing operator, the soldering of other industrial products being particularly well-suited in addition to the industry such as electronic electric equipment of RoHS instruction limitations, it is to avoid the problems such as workpiece oxidation caused because brazing temperature is too high even softens, soldering joint strength declines.
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 technology
Prior art such as (GB/T 10046-2008《Silver solder》) in recommend BAg25CuZnCd solders fusion temperature
Scope is 607 DEG C of solidus, 682 DEG C of liquidus curve, and easy to operate, technique is simple when the fusion temperature scope of its " relatively low " causes soldering
Just, it was once one of solder that solder user dotes on.But, due to RoHS instructions and the order of Environment Protect in China portion the 39th
The limitation that (August was implemented from 1 day in 2016) is used Cd elements, the application of BAg25CuZnCd solders is affected, then,
Following two solders are by " substitute " as BAg25CuZnCd solders：One is BAg25CuZn solders；Two is BAg25CuZnSn
Solder.The former (i.e. BAg25CuZn solders) due to the essential element in its chemical composition be Ag, Cu, Zn, and Ag contents are
24.0%~26.0%, thus its fusion temperature scope is 700 DEG C of solidus, 790 DEG C of liquidus curve；And the latter is (i.e.
BAg25CuZnSn solders) although with the addition of 1.5%~2.5% Sn elements so that its fusion temperature scope 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 solders, 682 DEG C of liquidus curve it is molten
Change temperature range.Therefore, how to reduce the fusion temperature scope of silver solder and make it have excellent wetting, spreading property and pricker
Seam mechanical property and using meet industrial 4.0 epoch soldered fitting to high-performance, high efficiency, low cost requirement into industry pass
Note and expect the problem for breaking through.
The applicant has carried out literature search, although being seen in the technology of silver solder in published Chinese patent literature
Information, slightly to enumerate " cadmium-free silver brazing alloy containing gallium and cerium " recommended such as CN100377832C, its 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,
, at 640 DEG C~650 DEG C, liquidus temperature is at 685 DEG C~710 DEG C for its solidus temperature；CN100420538C introduce " one kind contains
The cadmium-free silver-base solder of gallium, indium and cerium ", at 650 DEG C~665 DEG C, liquidus temperature is at 730 DEG C~745 DEG C for its solidus temperature
Etc..
Cadmium-free silver brazing alloy in prior art can reduce being total to for fusion temperature (or solidus temperature, liquidus temperature)
It is that one or more low melting point element such as Sn, Ga, In that quality % ratios are at least more than 1% are with the addition of in formula with feature
Deng.But, because Ga, In belong to rare element, global annual production is extremely limited, and price is suitable with silver even above white
Silver, therefore, do not possess the value of high volume applications；Sn elements are inexpensive and rich reserves, but, a large amount of additions easily form hard
And crisp intermetallic compound Cu6Sn5, silver solder processing difficulties are caused, can except the addition of the Sn in BAg60CuSn solders
To reach outside 9.5%~10.5%, in Ag-Cu-Zn-Sn series solders general addition 1.5%~2.5%, individually
If the addition of Sn in BAg56CuZnSn is for 4.5%~5.5% (referring to GB/T10046-2008《Silver solder》Table 2).
But, including the prior art including aforementioned patent literature in main composition be Ag, Cu, Zn element (not phosphorous unit
Element, classifies as the silver solder of GB/T 10046-2008) and all silver solders of Ga, In, Sn constituent content less than 0.15%,
It is insufficient to allow liquidus temperature≤710 DEG C and uses close to 682 DEG C of the liquidus temperature of BAg25CuZnCd solders " without cadmium
Silver solder ".Therefore, the applicant has carried out deep exploration and the experiment for having made repeatedly, technical side described below
Case is produced under this background.
The content of the invention
Task of the invention is that offer is a kind of to be helped to significantly reduce fusing point, is conducive to embodying excellent wetting and spreading
Property, the content for being beneficial to significantly reduce indium and gallium and abandon the low cadmium brazing silver alloy of low melting point of tin element.
What task of the invention was performed by, a kind of low cadmium brazing silver alloy of low melting point, its chemical composition presses quality percentage
Counting proportioning is：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, its chemical composition matches and is by weight percent：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, its chemical composition matches and is by weight percent：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, its chemical composition matches and is by weight percent：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, its chemical composition matches and is by weight percent：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, its chemical composition matches and is by weight percent：24.3% Ag, 39.6%
Cu, 0.11% Cd, 0.004% In, 0.002% Ga, remaining is Zn.
The present invention provide the low cadmium brazing silver alloy of low melting point relative to the BAg25CuZn in prior art, BAg25CuZnSn,
For BAg25CuZnCd solders, not only with good wetting and spreading, significantly reduce as the indium and gallium of rare element
Content, abandoned tin element and the features such as with excellent brazed seam mechanical property, but also than BAg25CuZn,
BAg25CuZnSn solders have " relatively low fusion temperature scope " so that solder is more easily operated in soldering, reduces pricker
The technical difficulty of operative employee is welded, other industry being particularly well-suited in addition to the industries such as the electronic electric equipment that RoHS instructions are limited are produced
The soldering of product, it is to avoid the problems such as workpiece oxidation caused because brazing temperature is too high even softens, soldering joint strength declines.
Specific embodiment
Ag contents in the low cadmium brazing silver alloy formula of low melting point that the present invention is provided are for 24-26%, Cd content are less than 0.15%
(to meet Unite States Standard AWS A5.8/A5.8M：2004 tables 1 are required), solder liquidus temperature " as far as possible " approach
BAg25CuZnCd solders and with good wetting, spreading property and soldered fitting mechanical property, can meet non-electronic, non-
Household electric appliances (industry of non-RoHS instructions limitation) some specialities brazing requirements.
Analyze, compare RoHS instructions clause and GB/T 10046-2008《Silver solder》, Unite States Standard AWS A5.8/
A5.8M：2004 are understood, for the limitation of the elements such as Cd, primarily directed to " electronic electric equipment ", non-electronic electrical equipment is produced
Product still can be using the solder containing cadmium, and this is also GB/T 10046-2000《Silver solder》In only 5 kinds containing cadmium brazing silver alloy (ginseng
See GB/T 10046-2000 tables 4), and GB/T 10046-2008 editions then has 10 kinds to contain cadmium brazing silver alloy (referring to GB/T10046-
2008 tables 2), Unite States Standard AWS A5.8/A5.8M：Then there are 7 kinds to contain cadmium brazing silver alloy (referring to AWSA5.8/A5.8M in 2004：
2004 tables 1) the reason for.From from the point of view of science, the use containing cadmium solder is although restricted, but, be " having ready conditions " limit.
So, it is believed that present GB/T 10046-2008《Silver solder》By in the silver solder of all non-" Ag-Cu-Zn-Cd " models
Cadmium content be limited to 0.010% scope without exception, it is clear that be excessively harsh.Because AWS A5.8/A5.8M：It is non-in 2004 tables 1
Cd contents in Ag-Cu-Zn-Cd solders do not make specific requirement, and simply define " other element total amounts "≤0.15%.
Even if the EU criteria DIN EN1044 of version prevailing for the time being in force:1999《Brazing—Filler metals》For silver in table 3
The requirement of the impurity element Cd of solder is also≤0.030%, than 0.010% " width " 0.020% of CNS.
The present inventor has found in actual production, sale, the use of silver solder, in the soldering of general industry product
In, even the soldering of " food machinery " is manufactured, in addition to 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%.The cadmium-free silver brazing alloy for exporting the U.S. is even more
With Unite States Standard AWS A5.8/A5.8M：2004 used as acceptance of delivery standard, if strictly controlling other impurity elements, cadmium unit
The allowance of element can be in theory≤0.15%.
Based on Unite States Standard AWS A5.8/A5.8M：The technical indicator of 2004 tables 1, by theory analysis and experiment, finds
In Unite States Standard AWS A5.8/A5.8M：Under the regulation of 2004 tables 1, on the premise of " meeting Unite States Standard ", can be by adding
Plus Ga, In element of micro cadmium element, denier, by " alloy optimization ", it is finally obtained the low cadmium silver pricker of low melting point of the present invention
The solid, liquid liquidus temperature of material is close to BAg25CuZnCd solders.
Embodiment 1：
Chemical composition is matched by weight percent：24.0% Ag's, 41.0% Cu, 0.05% Cd, 0.001%
In, 0.005% Ga, balance of Zn.
The solidus temperature of the low cadmium brazing silver alloy of low melting point that the present embodiment is obtained is in 630 DEG C~645 DEG C scopes, liquidus curve temperature
Degree is in 695 DEG C~710 DEG C scopes (considering evaluated error).Using gas brazing mode, coordinate FB102 brazing fluxes, 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), the stainless steel of brass -304 (σb=260 ±
25MPa, τ=280 ± 30MPa).
Embodiment 2：
Chemical composition is matched by weight percent：26.0% Ag's, 30.0% Cu, 0.13% Cd, 0.001%
In, 0.001% Ga, balance of Zn.
The solidus temperature of the low cadmium brazing silver alloy of low melting point that the present embodiment is obtained is in 630 DEG C~645 DEG C scopes, liquidus curve temperature
Degree is in 695 DEG C~710 DEG C scopes (considering evaluated error).Using gas brazing mode, coordinate FB102 brazing fluxes, 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), the stainless steel of brass -304 (σb=260 ±
25MPa, τ=280 ± 30MPa).
Embodiment 3：
Chemical composition is matched by weight percent：25.0% Ag's, 36.0% Cu, 0.10% Cd, 0.005%
In, 0.005% Ga, balance of Zn.
The solidus temperature of the low cadmium brazing silver alloy of low melting point that the present embodiment is obtained is in 630 DEG C~645 DEG C scopes, liquidus curve temperature
Degree is in 695 DEG C~710 DEG C scopes (considering evaluated error).Using gas brazing mode, coordinate FB102 brazing fluxes, 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), the stainless steel of brass -304 (σb=260 ±
25MPa, τ=280 ± 30MPa).
Embodiment 4：
Chemical composition is matched by weight percent：25.2% Ag's, 40.3% Cu, 0.12% Cd, 0.002%
In, 0.003% Ga, balance of Zn.
The solidus temperature of the low cadmium brazing silver alloy of low melting point that the present embodiment is obtained is in 630 DEG C~645 DEG C scopes, liquidus curve temperature
Degree is in 695 DEG C~710 DEG C scopes (considering evaluated error).Using gas brazing mode, coordinate FB102 brazing fluxes, 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), the stainless steel of brass -304 (σb=260 ±
25MPa, τ=280 ± 30MPa).
Embodiment 5：
Chemical composition is matched by weight percent：24.3% Ag's, 39.6% Cu, 0.11% Cd, 0.004%
In, 0.002% Ga, balance of Zn.
The solidus temperature of the low cadmium brazing silver alloy of low melting point that the present embodiment is obtained is in 630 DEG C~645 DEG C scopes, liquidus curve temperature
Degree is in 695 DEG C~710 DEG C scopes (considering evaluated error).Using gas brazing mode, coordinate FB102 brazing fluxes, 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), the stainless steel of brass -304 (σb=260 ±
25MPa, τ=280 ± 30MPa).
Above-described embodiment 1 to 5 using silver plate, cathode copper, zinc ingot metal, cadmium ingot, indium metal, the gallium that purity is 99.99%,
Added in intermediate frequency smelting furnace crucible by composition proportion.Smelted using conventional intermediate frequency smelting process, casting, then by extruding,
Drawing, that is, obtain required solder silk material.Silver solder solidus temperature of the invention is in 630 DEG C~645 DEG C scopes, liquidus curves
In 695 DEG C~710 DEG C scopes, (solidus temperature is 700 DEG C to temperature, and liquidus temperature is 790 to be significantly less than BAg25CuZn
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
Many RoHS instructions do not have the soldering processes needs of products such as conditional " non-electronic electrical equipments ".
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
With the comparative experimental data of BAg25CuZn, BAg25CuZnSn, BAg25CuZnCd solder as shown in following table：
In sum, the low cadmium brazing silver alloy of low melting point that the present invention is provided solves following key technical problem：
Although 1) the Cd elements used containing RoHS instruction limitations in solder composition, Cd constituent content≤0.13%,
And meet Unite States Standard AWS A5.8/A5.8M：2004 pairs of regulations of silver-containing solder, and with compared with low melting point, wetting and spreading
Can excellent, brazed seam excellent in mechanical performance the characteristics of.
2) by adding Ga the and In elements of appropriate ratio in low cadmium brazing silver alloy so that low cadmium brazing silver alloy of the invention exists
Excellent wetting and spreading performance, spreading area, brazed seam are respectively provided with red copper, brass (such as H62 brass), Q235 steel, 304 stainless steels
Joint bending stiffness is all higher than BAg25CuZn solders, BAg25CuZnSn solders, suitable with BAg25CuZnCd solders.
Compared with research in the past, substantive distinguishing features of the protrusion of the low cadmium brazing silver alloy of low melting point that the present invention is provided and significant
It is in place of progressive：
1st, during research is found that addition mass fraction is 0.05% micro Cd elements to BAg25CuZn solders, solder
Wetting and spreading performance is to be significantly increased, and fusion temperature is also decreased significantly.With the increase of Cd contents, the wetting of solder spreads
Developable surface product increases, and brazing filler metal melts temperature drop amplitude increases.Can by theory analysis Cu-Cd, Zn-Cd binary alloy phase diagram
Know, it because Cu and Cd can form fusing point is 549 DEG C that this is, can to form fusing point be 266 DEG C " low melting point eutectics " to Zn and Cd
It is caused.
Based on Unite States Standard AWS A5.8/A5.8M：The consideration of 2004 " other element total amount≤0.15% ", Cd elements
Addition control is advisable 0.013%.
2nd, research is found that the profit of Ga, In element of addition denier and " synergy " of Cd elements to low cadmium brazing silver alloy
The affecting laws of wet spreading property, brazed seam mechanical property.By optimizing the addition scope of Ga, In element, by the addition of Ga, In
Control that spreading area, the brazed seam joint of the low cadmium brazing silver alloy of low melting point of the invention can be made in 0.001%~0.005% scope
Shearing strength is all higher than BAg25CuZn solders, BAg25CuZnSn solders, suitable with BAg25CuZnCd solders.
By theory analysis Cd-In, Cd-Ga binary alloy phase diagram, this is to be because Cd and In can form fusing point
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 unit of denier
" synergy " of element is not enough to make a significant impact the fusing point of solder of the present invention, but, " alloy strengthening " effect can show
Write the spreading area of the low cadmium brazing silver alloy of increase and improve brazed seam joint bending stiffness.
Claims (6)
1. the low cadmium brazing silver alloy of a kind of low melting point, it is characterised in that its chemical composition matches and is by weight percent：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. the low cadmium brazing silver alloy of a kind of low melting point, it is characterised in that its chemical composition matches and is by weight percent：24% Ag,
41% Cu, 0.05% Cd, 0.001% In, 0.005% Ga, remaining is Zn.
3. the low cadmium brazing silver alloy of a kind of low melting point, it is characterised in that its chemical composition matches and is by weight percent：26% Ag,
30% Cu, 0.13% Cd, 0.001% In, 0.001% Ga, remaining is Zn.
4. the low cadmium brazing silver alloy of a kind of low melting point, it is characterised in that its chemical composition matches and is by weight percent：25% Ag, 36%
Cu, 0.1% Cd, 0.005% In, 0.005% Ga, remaining is Zn.
5. the low cadmium brazing silver alloy of a kind of low melting point, it is characterised in that its chemical composition matches and is by weight percent：25.2% Ag,
40.3% Cu, 0.12% Cd, 0.002% In, 0.003% Ga, remaining is Zn.
6. the low cadmium brazing silver alloy of a kind of low melting point, it is characterised in that its chemical composition matches and is by weight percent：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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| CN201611156602.1A CN106736003B (en) | 2016-12-15 | 2016-12-15 | The low cadmium brazing silver alloy of low melting point |
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| 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 |
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| 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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2016
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|---|---|---|---|---|
| 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 |
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