CN101524793A - Cadmium-free silver filler containing lithium and niobium and production method thereof - Google Patents
Cadmium-free silver filler containing lithium and niobium and production method thereof Download PDFInfo
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- CN101524793A CN101524793A CN200910097817A CN200910097817A CN101524793A CN 101524793 A CN101524793 A CN 101524793A CN 200910097817 A CN200910097817 A CN 200910097817A CN 200910097817 A CN200910097817 A CN 200910097817A CN 101524793 A CN101524793 A CN 101524793A
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Abstract
The invention belongs to the field of welding material, in particular relating to a cadmium-free silver filler containing lithium and niobium and a production method thereof; the chemical composition of the cadmium-free silver filler is as follows according to mass percent: 35.0%-40.0% of Cu, 42.0%-52.0% of Zn, 4.0%-6.0% of Sn, 0.001%-0.1% of Li, 0.001%-0.1% of Nb, and the balancing of Ag. In the invention, Nb and Li are added in sequence, so that the purity of the tissue of the silver filler can be obviously improved, thus improving the wettability and spreadability of the silver filler. The invention has low silver content, excellent braze welding performance, no toxic cadmium in the welded parts during welding or after welding, can replace Bag35CuZnCd brazing filler and Bag25CuZn brazing filler, and is applicable to braze welding for metal materials such as copper, brass, carbon steel, stainless steel, and nickel base alloy, etc.
Description
Technical field
The invention belongs to the welding material class, be specifically related to a kind of cadmium-free silver brazing alloy and production method thereof that contains lithium and niobium.
Background technology
At present, normally used welding filler metal is generally and contains cadmium brazing silver alloy BAg35CuZnCd and BAg40CuZnCd in welding process both at home and abroad, all contains a large amount of " poisonous element " cadmiums (Cd) in its chemical composition.Owing to contain toxicity every solder, all begin to forbid this use of solder in household appliances that contains cadmium both at home and abroad, therefore, must research and develop out the substitute products that do not contain cadmium.But, general all more than 25% (mass percent) although developed some cadmium-free silver brazing alloy new products both at home and abroad now because the silver content of these products is all higher, thus material cost is improved greatly.In order to reduce manufacturing cost, improve competitiveness of product, research and develop therefore that silver content is low, the cadmium-free silver brazing alloy of superior performance has been the task of top priority.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of and do not contain the cadmium-free silver brazing alloy that contains lithium and niobium poisonous element cadmium, that brazing property is good, silver content is low, and disclose its production method.
Technical scheme of the present invention is as follows:
A kind of cadmium-free silver brazing alloy that contains lithium and niobium, it is characterized in that: the mass percent of each chemical composition is in the solder: 35.0%～40.0% copper (Cu), 42.0%～52.0% zinc (Zn), 4.0%～6.0% tin (Sn), 0.001%～0.1% lithium (Li), 0.001%～0.1% niobium (Nb), all the other are silver (Ag).
A kind of production method that contains the cadmium-free silver brazing alloy of lithium and niobium of the present invention, it is characterized in that: after the raw material that will contain Ag, Cu, Zn, Sn is smelted by said ratio, add Nb, Li more successively, can cast or horizontal casting after stirring, to cast rod or ingot casting then by extruding, drawing, promptly obtain needed solder wire material.What pay particular attention to is: the addition sequence of lithium and niobium and adding mode must be after Ag, Cu, Zn, Sn quaternary alloy have been smelted, before casting or horizontal casting, add Nb by elder generation, the order that adds Li again adds successively, can cast or horizontal casting after stirring.
The cadmium-free silver brazing alloy solidus temperature that contains lithium and niobium of the present invention is at 725 ℃～735 ℃, and liquidus temperature is at 760 ℃～770 ℃.With the BAg25CuZn solder is object of reference, cooperates the FB102 brazing flux, suitable with it to wetability, the spreadability of mother metal during combined materials such as soldering red copper-brass, brass-carbon steel, stainless steel-nickel-base alloy, the suitable with it (tensile strength sigma of brazed seam mechanical property
bAt 185～350MPa, shearing strength τ is 160～320MPa).
This invention has mainly solved following several key problems:
1) the present invention utilizes its " deoxidation " that has, " degassing " ability by adopting lithium (Li) element that adds trace in smelting process, improves " degree of purity " of the tissue of neoteric silver solder, thereby improves the wettability and the spreading property of silver solder.In the present invention, under " synergy " of high-melting-point elemental niobium (Nb), when being controlled at the elemental lithium addition in 0.001%～0.1% scope, silver solder of the present invention has excellent wetting capacity energy and spreading property.
2) abandoned traditional " interpolation rare earth element " crystal grain, improved the plasticity of silver solder and the thinking of comprehensive mechanical property with the refinement silver solder.By being added on the elemental niobium (Nb) that domestic and international someone never added in the silver solder, reached than " interpolation rare earth element " better effect.Discover: niobium element fusing point height, and be difficult for oxidation, in the casting cooling procedure after the silver solder smelting is finished, play the effect of " forming core particle ", the rapid crystallization that helps silver solder, thereby played the crystal grain of refinement silver solder, improved the plasticity and the comprehensive mechanical property of cadmium-free silver brazing alloy.
3) by optimizing the chemical composition of " cadmium-free silver brazing alloy that contains lithium and niobium ", obtained mother metal wetability, good, the brazed seam mechanical property (σ of spreadability
b, τ) good cadmium-free silver brazing alloy.Especially in the present invention, the addition of Sn is when 4.0%～6.0% scope in the cadmium-free silver brazing alloy, and the addition of Zn still can and have good plasticity up to 42.0%～52.0%.Thereby make the melting range of cadmium-free silver brazing alloy of the present invention be reduced to 725 ℃～770 ℃ on the one hand, on the other hand, because Li and Nb " synergy " makes cadmium-free silver brazing alloy of the present invention still have good processing properties.
Find by a large amount of tests, in the solder that the present invention produces, owing to added dystectic elemental niobium (Nb) earlier, add the Li element (0.001%～0.1% of trace again, mass percent), " degree of purity " of the tissue of silver solder just can be significantly improved, thereby improves the wettability and the spreading property of silver solder.Silver content of the present invention is low, brazing property is good, the welding position in brazing process and after the soldering does not have poisonous element cadmium fully, alternative BAg35CuZnCd solder, BAg25CuZn solder, wetability, spreadability to mother metal are suitable with it, the novel cadmium-free silver brazing alloy that the brazed seam mechanical property is suitable with it is applicable to the cadmium-free silver brazing alloy of metal material solderings such as red copper, brass, carbon steel, stainless steel and nickel-base alloy.
The specific embodiment
A kind of cadmium-free silver brazing alloy that contains lithium and niobium of the present invention, adopt following examples to obtain:
Embodiment 1:
Press the mass percent proportioning, its composition is: 35.0%Cu, and 42.0%Zn, 6.0%Sn, 0.001%Li, 0.01%Nb, all the other are Ag.
" cadmium-free silver brazing alloy that contains lithium and niobium " solidus temperature that the mentioned component proportioning obtains about 730 ℃, liquidus temperature (considered experimental error) about 765 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=200 ± 15MPa, τ=170 ± 10MPa), brass-carbon steel (σ
b=280 ± 15MPa, τ=250 ± 10MPa), stainless steel-nickel-base alloy (σ
b=335 ± 15MPa, τ=310 ± 10MPa).
Embodiment 2:
Press the mass percent proportioning, its composition is: 40.0%Cu, and 42.0%Zn, 4.0%Sn, 0.001%Li, 0.1%Nb, all the other are Ag.
" cadmium-free silver brazing alloy that contains lithium and niobium " solidus temperature that the mentioned component proportioning obtains about 735 ℃, liquidus temperature (considered experimental error) about 770 ℃, cooperate FB102 (QJ102) brazing flux, the brazed seam intensity when the soldering mother metal is following the combination is seen data in the bracket: red copper-brass (σ
b=200 ± 15MPa, τ=170 ± 10MPa), brass-carbon steel (σ
b=280 ± 15MPa, τ=250 ± 10MPa), stainless steel-nickel-base alloy (σ
b=335 ± 15MPa, τ=310 ± 10MPa).
Embodiment 3:
Press the mass percent proportioning, its composition is: 40.0%Cu, and 52.0%Zn, 5.0%Sn, 0.01%Li, 0.001%Nb, all the other are Ag.
" cadmium-free silver brazing alloy that contains lithium and niobium " solidus temperature that the mentioned component proportioning obtains about 725 ℃, liquidus temperature (considered experimental error) about 760 ℃, cooperate FB102 (QJ102) brazing flux, soldering is identical with embodiment 1 with mother metal and brazed seam intensity data.
Embodiment 4:
Press the mass percent proportioning, its composition is: 40.0%Cu, and 50.0%Zn, 4.5%Sn, 0.01%Li, 0.01%Nb, all the other are Ag.
" cadmium-free silver brazing alloy that contains lithium and niobium " solidus temperature that the mentioned component proportioning obtains about 725 ℃, liquidus temperature (considered experimental error) about 765 ℃, cooperate FB102 (QJ102) brazing flux, soldering is identical with embodiment 1 with mother metal and brazed seam intensity data.
Embodiment 5:
Press the mass percent proportioning, its composition is: 38.0%Cu, and 49.0%Zn, 6.0%Sn, 0.001%Li, 0.001%Nb, all the other are Ag.
" cadmium-free silver brazing alloy that contains lithium and niobium " solidus temperature that the mentioned component proportioning obtains about 725 ℃, liquidus temperature (considered experimental error) about 760 ℃, cooperate FB102 (QJ102) brazing flux, soldering is identical with embodiment 1 with mother metal and brazed seam intensity data.
Embodiment 6:
Press the mass percent proportioning, its composition is: 40.0%Cu, and 51.0%Zn, 4.2%Sn, 0.015%Li, 0.012%Nb, all the other are Ag.
" cadmium-free silver brazing alloy that contains lithium and niobium " solidus temperature that the mentioned component proportioning obtains about 725 ℃, liquidus temperature (considered experimental error) about 765 ℃, cooperate FB102 (QJ102) brazing flux, soldering is identical with embodiment 1 with mother metal and brazed seam intensity data.
Embodiment 7:
Press the mass percent proportioning, its composition is: 36.0%Cu, and 48.0%Zn, 4.2%Sn, 0.045%Li, 0.022%Nb, all the other are Ag.
" cadmium-free silver brazing alloy that contains lithium and niobium " solidus temperature that the mentioned component proportioning obtains about 730 ℃, liquidus temperature (considered experimental error) about 765 ℃, cooperate FB102 (QJ102) brazing flux, soldering is identical with embodiment 1 with mother metal and brazed seam intensity data.
Embodiment 8:
Press the mass percent proportioning, its composition is: 36.0%Cu, and 50.5%Zn, 5.1%Sn, 0.05%Li, 0.015%Nb, all the other are Ag.
" cadmium-free silver brazing alloy that contains lithium and niobium " solidus temperature that the mentioned component proportioning obtains about 730 ℃, liquidus temperature (considered experimental error) about 765 ℃, cooperate FB102 (QJ102) brazing flux, soldering is identical with embodiment 1 with mother metal and brazed seam intensity data.
Embodiment 9:
Press the mass percent proportioning, its composition is: 37.5%Cu, and 43.5%Zn, 5.5%Sn, 0.08%Li, 0.035%Nb, all the other are Ag.
" cadmium-free silver brazing alloy that contains lithium and niobium " solidus temperature that the mentioned component proportioning obtains about 730 ℃, liquidus temperature (considered experimental error) about 765 ℃, cooperate FB102 (QJ102) brazing flux, soldering is identical with embodiment 1 with mother metal and brazed seam intensity data.
Embodiment 10:
Press the mass percent proportioning, its composition is: 39.5%Cu, and 51.5%Zn, 4.5%Sn, 0.08%Li, 0.01%Nb, all the other are Ag.
" cadmium-free silver brazing alloy that contains lithium and niobium " solidus temperature that the mentioned component proportioning obtains about 725 ℃, liquidus temperature (considered experimental error) about 770 ℃, cooperate FB102 (QJ102) brazing flux, soldering is identical with embodiment 1 with mother metal and brazed seam intensity data.
Embodiment 11:
Press the mass percent proportioning, its composition is: 35.5%Cu, and 50.8%Zn, 4.8%Sn, 0.1%Li, 0.08%Nb, all the other are Ag.
" cadmium-free silver brazing alloy that contains lithium and niobium " solidus temperature that the mentioned component proportioning obtains about 728 ℃, liquidus temperature (considered experimental error) about 765 ℃, cooperate FB102 (QJ102) brazing flux, soldering is identical with embodiment 1 with mother metal and brazed seam intensity data.
Embodiment 12:
Press the mass percent proportioning, its composition is: 35.6%Cu, and 44.8%Zn, 5.8%Sn, 0.02%Li, 0.06%Nb, all the other are Ag.
" cadmium-free silver brazing alloy that contains lithium and niobium " solidus temperature that the mentioned component proportioning obtains about 732 ℃, liquidus temperature (considered experimental error) about 770 ℃, cooperate FB102 (QJ102) brazing flux, soldering is identical with embodiment 1 with mother metal and brazed seam intensity data.
Embodiment 13:
Press the mass percent proportioning, its composition is: 38.2%Cu, and 48.6%Zn, 4.9%Sn, 0.018%Li, 0.006%Nb, all the other are Ag.
" cadmium-free silver brazing alloy that contains lithium and niobium " solidus temperature that the mentioned component proportioning obtains about 732 ℃, liquidus temperature (considered experimental error) about 765 ℃, cooperate FB102 (QJ102) brazing flux, soldering is identical with embodiment 1 with mother metal and brazed seam intensity data.
Embodiment 14:
Press the mass percent proportioning, its composition is: 37.4%Cu, and 49.3%Zn, 4.7%Sn, 0.025%Li, 0.016%Nb, all the other are Ag.
" cadmium-free silver brazing alloy that contains lithium and niobium " solidus temperature that the mentioned component proportioning obtains about 735 ℃, liquidus temperature (considered experimental error) about 770 ℃, cooperate FB102 (QJ102) brazing flux, soldering is identical with embodiment 1 with mother metal and brazed seam intensity data.
Above-mentioned 14 embodiment contain the production method of the cadmium-free silver brazing alloy of lithium and niobium, use commercially available silver, cathode copper, zinc ingot metal, tin slab, proportioning on demand, adopt conventional intermediate frequency smelting furnace to smelt, add successively Nb alloy, Li alloy, can cast or horizontal casting after stirring, to cast rod (ingot casting) then by extruding, drawing, promptly obtain needed solder wire material.
The cadmium-free silver brazing alloy that contains lithium and niobium of the present invention, no matter adopt gas brazing, induction brazing, furnace brazing, or conventional method for welding such as resistance brazing, during soldering to red copper, brass, carbon steel, stainless steel, nickel-base alloy all has good wettability respectively, so cadmium-free silver brazing alloy that contains lithium and niobium of the foregoing description production, in soldering red copper-red copper, red copper-brass, brass-carbon steel, brass-stainless steel, carbon steel-stainless steel, carbon steel-nickel-base alloy, stainless steel-nickel-base alloy, red copper-nickel-base alloy, during different combined material such as brass-nickel-base alloy, combined material to institute's soldering all has good wettability, and soldered fitting has the good mechanical performance.
Claims (2)
1, a kind of cadmium-free silver brazing alloy that contains lithium and niobium is characterized in that: each chemical composition mass percent is 35.0%～40.0% Cu in the solder, 42.0%～52.0% Zn, 4.0%～6.0% Sn, 0.001%～0.1% Li, 0.001%～0.1% Nb, all the other are Ag.
2, a kind of method of the cadmium-free silver brazing alloy that contains lithium and niobium of production claim 1, it is characterized in that: after the raw material that will contain Ag, Cu, Zn, Sn is smelted by proportioning, add Nb, Li more successively, can cast or horizontal casting after stirring, to cast rod or ingot casting then by extruding, drawing, promptly obtain needed solder wire material.
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| CN2009100978174A CN101524793B (en) | 2009-04-20 | 2009-04-20 | Cadmium-free silver filler containing lithium and niobium |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100978174A CN101524793B (en) | 2009-04-20 | 2009-04-20 | Cadmium-free silver filler containing lithium and niobium |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103909362A (en) * | 2014-03-17 | 2014-07-09 | 金华市三环焊接材料有限公司 | Low-silver brazing filler metal containing nickel and indium |
| CN103909361A (en) * | 2014-03-17 | 2014-07-09 | 金华市三环焊接材料有限公司 | Low-silver-content cadmium-free solder |
| CN109894771A (en) * | 2019-04-03 | 2019-06-18 | 南京理工大学 | A kind of low silver-colored cadmium-free silver brazing alloy |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1018342B (en) * | 1990-06-14 | 1992-09-23 | 国家建筑材料工业局人工晶体研究所 | Soldering flux and soldering paste diamond tool |
| CN101342644B (en) * | 2007-07-13 | 2012-05-23 | 浙江信和科技股份有限公司 | High-ductility environment friendly silver-saving medium-temperature brazing filler metal |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103909362A (en) * | 2014-03-17 | 2014-07-09 | 金华市三环焊接材料有限公司 | Low-silver brazing filler metal containing nickel and indium |
| CN103909361A (en) * | 2014-03-17 | 2014-07-09 | 金华市三环焊接材料有限公司 | Low-silver-content cadmium-free solder |
| CN109894771A (en) * | 2019-04-03 | 2019-06-18 | 南京理工大学 | A kind of low silver-colored cadmium-free silver brazing alloy |
| CN109894771B (en) * | 2019-04-03 | 2020-10-30 | 南京理工大学 | Low-silver cadmium-free silver solder |
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