CN101985193A - Cadmium-free silver solder and preparation method thereof - Google Patents
Cadmium-free silver solder and preparation method thereof Download PDFInfo
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- CN101985193A CN101985193A CN 201010550704 CN201010550704A CN101985193A CN 101985193 A CN101985193 A CN 101985193A CN 201010550704 CN201010550704 CN 201010550704 CN 201010550704 A CN201010550704 A CN 201010550704A CN 101985193 A CN101985193 A CN 101985193A
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Abstract
The invention discloses a cadmium-free silver solder and a preparation method thereof, and belongs to the technical field of soldering materials. The cadmium-free silver solder comprises the following chemical components in percentage by mass: 37.0 to 41.0 percent of Ag, 23.0 to 25.0 percent of Cu, 0.2 to 2.0 percent of Ni, 1.5 to 5.0 percent of Mn, 0.001 to 0.1 percent of Si, 0.001 to 0.1 percent of Al, 0.001 to 0.1 percent of Ba, 0.001 to 0.1 percent of Zr and the balance of Zn. The preparation method comprises the following steps of: putting the following chemical components in percentage by mass: 37.0 to 41.0 percent of Ag, 23.0 to 25.0 percent of Cu, 0.2 to 2.0 percent of Ni, 1.5 to 5.0 percent of Mn and the balance of Zn into a smelting furnace to form Ag-Cu-Zn-Mn-Ni quinary alloy melt, then putting copper foil wrapped silicon-aluminum-barium alloy and silicon-zirconium alloy serving as deoxidizing agents into the quinary alloy melt, and controlling the oxygen content of the cadmium-free silver solder at 0.005 to 0.012 mass percent. The cadmium-free silver solder has excellent plasticity and strength, the silver resource is saved and the cost of the solder is reduced.
Description
Technical field
The invention belongs to technical field of soldering materials, be specifically related to a kind ofly be used for substituting the BAg49CuZnMnNi solder and be suitable for, and relate to the preparation method of this cadmium-free silver brazing alloy the Hardmetal materials soldering and cadmium-free silver brazing alloy that have good plasticity and excellent intensity.
Background technology
Standard is the silver solder BAg49CuZnMnNi of GB/T 10046-2008 " silver solder " recommendation use for example, its brazing property is good, solid-liquid phase line temperature is moderate, and particularly the wettability to carbide alloy is strong, therefore is widely used in the soldering of sintered-carbide tool.
Yet, along with the fast development of China's " instrument manufacturing ", the continuous progress of manufacture level, the output steady-state growth, particularly the continuous of silver price risen in recent years, and the cost performance of silver solder is had higher requirement.As, the quality percentage composition of silver reduces by 1% in the silver solder, can save 60 yuans material cost.Meanwhile, along with the progress of sintered-carbide tool manufacture level, more harsh requirement has been proposed for the plasticity and the intensity of solder.Therefore, must take into account raising BAgCuZnMnNi in the silver content in researching and solving reduction BAg49CuZnMnNi silver solder is the plasticity and the intensity index of silver solder, otherwise can produce the problem of attending to one thing and lose sight of another, technical scheme described below is based on producing under this prerequisite.
Summary of the invention
Task of the present invention be to provide a kind of wettability to carbide alloy is strong, solid-liquid phase line temperature is moderate and silver content than BAg49CuZnMnNi low and cadmium-free silver brazing alloy that have good plasticity and intensity.
Also task of the present invention is to provide a kind of preparation method of cadmium-free silver brazing alloy, and this method can ensure comprehensive embodiment of the described technique effect of cadmium-free silver brazing alloy.
Task of the present invention is finished like this, a kind of cadmium-free silver brazing alloy, its chemical composition by the mass percent proportioning is: 37.0%～41.0% Ag, 23.0%～25.0% Cu, 0.2%～2.0% Ni, 1.5%～5.0% Mn, 0.001%～0.1% Si, 0.001%～0.1% Al, 0.001%～0.1% Ba, 0.001%～0.1% Zr, all the other are Zn.
An also task of the present invention is finished like this, a kind of preparation method of cadmium-free silver brazing alloy, at first, 37.0%～41.0% Ag with the mass percent proportioning of following chemical composition, 23.0%～25.0% Cu, 0.2%～2.0% Ni, 1.5%～5.0% Mn is that Zn input smelting furnace is smelted into Ag-Cu-Zn-Mn-Ni quinary alloy melt with surplus, then, to drop in the described quinary alloy melt as deoxidier by silicon-aluminium-barium alloy and the silicozirconium that Copper Foil coats, the mass percent of the oxygen content in the cadmium-free silver brazing alloy is controlled at 0.005%～0.012%.
Smelting furnace of the present invention is the intermediate frequency smelting furnace.
Compared with the prior art cadmium-free silver brazing alloy provided by the invention has following technique effect: wettability is strong, solidus temperature is 670-682 ℃, liquidus temperature is 705-726 ℃, oxygen content is 0.005%～0.012% in the solder, the solder percentage elongation reach 20.07%～22.0 and percentage elongation raising rate reach 10.4-20.9% (comparing) with BAg49CuZnMnNi, solder tensile strength reaches 690-735MPa and tensile strength raising rate reaches 20.9-30.1% (comparing with BAg49CuZnMnNi), silver content has reduced by 10% (comparing with BAg49CuZnMnNi), thereby not only shown good plasticity and intensity, and saved silver-colored resource and reduced the cost of solder.
The specific embodiment
Following two key technical problems are found and solved to technical scheme provided by the invention:
1) found that oxygen content is the rule that influences of cadmium-free silver brazing alloy plasticity and intensity to BAgCuZnMnNi in the cadmium-free silver brazing alloy: promptly the oxygen content in the cadmium-free silver brazing alloy to BAgCuZnMnNi be in the influence of cadmium-free silver brazing alloy plasticity and intensity and the copper alloy oxygen content to copper alloy plasticity to influence rule similar, but the difference of matter is arranged again.As, the oxygen content in the oxygen-free copper low more (promptly＜0.003%), the plasticity of oxygen-free copper is good more, but concerning BAgCuZnMnNi is cadmium-free silver brazing alloy, an optimum range is arranged then.
2) adopt silicon-aluminium-barium alloy and silicozirconium as deoxidier, except can accurately controlling BAgCuZnMnNi is the oxygen content in the cadmium-free silver brazing alloy, residual silicon after the deoxidier deoxidation, aluminium, barium and zr element, has good alloying performance, it is that the plasticity and the intensity of cadmium-free silver brazing alloy is improved simultaneously that their synergy can make BAgCuZnMnNi, thereby has invented out silver content 39% (having reduced by 10% silver content than BAg49CuZnMnNi), wettability to carbide alloy is strong, moderate and the novel cadmium-free silver brazing alloy of solid-liquid phase line temperature with good plasticity and intensity.
The method for preparing cadmium-free silver brazing alloy provided by the invention: (1), commercially available silver, cathode copper, zinc ingot metal, nickel plate and the manganese metal (or cupromanganese) of use, proportioning on demand, adopt the intermediate frequency smelting furnace to smelt after the Ag-Cu-Zn-Mn-Ni quinary alloy melt earlier, coat commercially available silicon-aluminium-barium alloy and silicozirconium as deoxidier with commercially available Copper Foil again, the oxygen content of cadmium-free silver brazing alloy is controlled at 0.005%～0.012% scope.Adopt conventional casting method or horizontal continuous casting method ingot casting, extruding, drawing, promptly obtain required solder wire material.Ingot casting is squeezed into band earlier,, can be prepared into band (strip) again through roughing and finish rolling.Solder has good plasticity and higher intensity, can improve 10.0%～20.0% than BAg49CuZnMnNi solder percentage elongation, and solder intensity can improve 20.0%～30.0%.
Find in the test, adopt silicon-aluminium-barium alloy or silicozirconium as deoxidier separately, perhaps adopt other deoxidier, the BAgCuZnMnNi for preparing does not have high-ductility and high strength, and bad to the wettability of carbide alloy yet.Have only when adopting silicon-aluminium-barium alloy and silicozirconium at the same time, just can reach aforesaid technique effect as deoxidier.Test is also found, the ratio that silicon-aluminium-barium alloy and silicozirconium add is extremely small to influential effect of the present invention, in other words, as long as the amount that silicon-aluminium-barium alloy and silicozirconium add satisfies its remaining quantity 0.001%～0.1% Si is arranged in the BAgCuZnMnNi brazing filler metal, 0.001%～0.1% Al, 0.001%～0.1% Ba, 0.001%～0.1% Zr gets final product.This discovery, the control of product quality during for batch process provides convenience.
(2), the BAgCuZnMnNi that has found simple and efficient and low-cost preparation to have good plasticity and intensity is the effective way of cadmium-free silver brazing alloy.
As a kind of silver solder of producing in enormous quantities and using, can prepare product with the simplest method and minimum cost with optimum performance, be only and be subjected to manufacturer and user's favor most.Domestic and international many researchers still often are difficult to apply in production reality by adopting advanced production equipment or by a series of complexity, strict production technology, having invented, researched and developed some silver solders with various particular characteristics.
The present invention is on system, deep experimental basis, by to the screening of deoxidier, the optimizing components of microalloy, the control of solder oxygen content and the research of property relationship, final adopt the simplest method to solve to look the very complicated technology difficult problem that seems: promptly adopt the intermediate frequency smelting furnace to smelt after the Ag-Cu-Zn-Mn-Ni quinary alloy earlier, coat commercially available silicon-aluminium-barium alloy and silicozirconium as deoxidier with commercially available Copper Foil, the oxygen content of cadmium-free silver brazing alloy is controlled at 0.005%～0.012% scope.Evidence, control BAgCuZnMnNi be oxygen content in the silver solder in 0.005%～0.012% scope, be the key of this invention success.It not only thinks that with in the past invention or research the low more good more viewpoint of oxygen content is different in copper alloy or the silver solder, and has proved that the optimum range of its oxygen content should be controlled at 0.005%～0.012% scope.And the control method that adopts of the present invention promptly is by adopting with the commercially available silicon-aluminium-barium alloy of commercially available Copper Foil coating and silicozirconium as deoxidier, as long as 0.001%～0.1% Si is arranged in the BAgCuZnMnNi brazing filler metal as long as the amount that silicon-aluminium-barium alloy and silicozirconium are added satisfies its remaining quantity, 0.001%～0.1% Al, 0.001%～0.1% Ba, 0.001%～0.1% Zr gets final product, and do not need to go to consider grain refinement and alloy strengthening scheduling theory problem again, produce thereby be easier to instruct.
Embodiment 1:
At first, according to chemical composition the mass percent proportioning is: 37% Ag, 25.0% Cu, 5.0% Mn, 0.2% Ni and surplus be the ratio requirement of Zn, with silver, cathode copper, manganese metal (or cupromanganese), the nickel plate drops into the interior smelting of intermediate frequency smelting furnace (melting) with zinc ingot metal and becomes Ag-Cu-Zn-Mn-Ni quinary alloy melt, then will be by putting in the described quinary alloy melt as deoxidier by commercially available silicon-aluminium-barium alloy and silicozirconium equally that commercially available Copper Foil coats, by sample examination, the oxygen content of cadmium-free silver brazing alloy or the quality percentage composition of title oxygen content are controlled to be 0.005%～0.012% scope.Wherein: Si, Al, Ba and the Zr quality percentage composition in solder is respectively: 0.001% Si, 0.1% Al, 0.001% Ba, 0.1% Zr, adopt conventional casting method or horizontal continuous casting method ingot casting, extruding and drawing, obtain cadmium-free silver brazing alloy silk material, perhaps ingot casting is squeezed into band earlier, through roughing and finish rolling, obtain band (strip) again.Is object of reference by the resulting cadmium-free silver brazing alloy of present embodiment with the BAg49CuZnMnNi silver solder, except to the wettability of carbide alloy by force, also have the technical indicator of all excellence shown in the table 1.
Embodiment 2:
The mass percent proportioning of chemical composition changes into: 41.0% Ag, 23.0% Cu, 1.5% Mn, 2.0% Ni and surplus are Zn, Si, Al, Ba and the Zr quality percentage composition in solder changes into: 0.1% Si, 0.001% Al, 0.1% Ba and 0.001% Zr, all the other are all with the description of embodiment 1.
Embodiment 3:
The mass percent of each chemical composition in the solder is: 40.0% Ag, 24.0% Cu, 2.5% Mn, 1.0% Ni, 0.01% Si, 0.01% Al, 0.05% Ba, 0.05% Zr, and all the other are Zn, all the other are all with the description of embodiment 1.
Embodiment 4:
The mass percent of each chemical composition in the solder is: 38.0% Ag, 23.8% Cu, 3.2% Mn, 1.2% Ni, 0.005% Si, 0.08% Al, 0.006% Ba, 0.07% Zr, all the other are Zn, and all the other are all with the description of embodiment 1.
Embodiment 5:
The mass percent of each chemical composition in the solder is: 38.8% Ag, 24.1% Cu, 3.0% Mn, 1.5% Ni, 0.015% Si, 0.018% Al, 0.016% Ba, 0.017% Zr, all the other are Zn, and all the other are all with the description of embodiment 1.
Embodiment 6:
The mass percent of each chemical composition in the solder is: 39.8% Ag, 24.6% Cu, 2.0% Mn, 1.8% Ni, 0.012% Si, 0.014% Al, 0.006% Ba, 0.007% Zr, all the other are Zn, and all the other are all with the description of embodiment 1.
Embodiment 7:
The mass percent of each chemical composition in the solder is: 40.2% Ag, 23.3% Cu, 3.7% Mn, 0.8% Ni, 0.002% Si, 0.004% Al, 0.026% Ba, 0.028% Zr, all the other are Zn, and all the other are all with the description of embodiment 1.
Embodiment 8:
The mass percent of each chemical composition in the solder is: 40.5% Ag, 24.1% Cu, 4.7% Mn, 1.5% Ni, 0.012% Si, 0.014% Al, 0.046% Ba, 0.048% Zr, all the other are Zn, and all the other are all with the description of embodiment 1.
Table 1 is the performance comparison (measured value) of BAg49CuZnMnNi silver solder in embodiments of the invention 1-8 and the prior art
Claims (3)
1. cadmium-free silver brazing alloy, it is characterized in that its chemical composition by the mass percent proportioning is: 37.0%～41.0% Ag, 23.0%～25.0% Cu, 0.2%～2.0% Ni, 1.5%～5.0% Mn, 0.001%～0.1% Si, 0.001%～0.1% Al, 0.001%～0.1% Ba, 0.001%～0.1% Zr, all the other are Zn.
2. the preparation method of a cadmium-free silver brazing alloy as claimed in claim 1, it is characterized in that: at first, 37.0%～41.0% Ag with the mass percent proportioning of following chemical composition, 23.0%～25.0% Cu, 0.2%～2.0% Ni, 1.5%～5.0% Mn is that Zn input smelting furnace is smelted into Ag-Cu-Zn-Mn-Ni quinary alloy melt with surplus, then, to drop in the described quinary alloy melt as deoxidier by silicon-aluminium-barium alloy and the silicozirconium that Copper Foil coats, the mass percent of the oxygen content in the cadmium-free silver brazing alloy is controlled at 0.005%～0.012%.
3. the preparation method of cadmium-free silver brazing alloy according to claim 1 is characterized in that described smelting furnace is the intermediate frequency smelting furnace.
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| CN201010550704A CN101985193B (en) | 2010-11-18 | 2010-11-18 | Cadmium-free silver solder and preparation method thereof |
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| CN201010550704A CN101985193B (en) | 2010-11-18 | 2010-11-18 | Cadmium-free silver solder and preparation method thereof |
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| CN101985193B CN101985193B (en) | 2012-09-05 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921838A (en) * | 2016-06-30 | 2016-09-07 | 四川广正科技有限公司 | Induction brazing method for edge scraper of shielding tunneling machine |
| CN110369909A (en) * | 2019-08-27 | 2019-10-25 | 常熟市华银焊料有限公司 | A kind of low silver-colored cadmium-free silver brazing alloy containing Ga and In |
| CN112004638A (en) * | 2018-04-23 | 2020-11-27 | 田中贵金属工业株式会社 | Silver solder and bonding method using the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01313198A (en) * | 1988-06-10 | 1989-12-18 | Mitsubishi Steel Mfg Co Ltd | Low melting low silver brazing filler metal |
| DE19725956A1 (en) * | 1996-07-20 | 1998-01-22 | Degussa | Manganese-containing copper-zinc-silver brazing alloy for highly stressed steel pipe |
| JP2001121288A (en) * | 1999-10-27 | 2001-05-08 | Tanaka Kikinzoku Kogyo Kk | Silver brazing filler metal for joining cemented carbide |
| CN1456415A (en) * | 2003-06-10 | 2003-11-19 | 李嘉珍 | High-strength silver-base brazing alloy and use thereof |
| CN1616182A (en) * | 2004-12-08 | 2005-05-18 | 哈尔滨工业大学 | Medium temperature Ag base brazing filler metal and its preparing method |
| CN101693325A (en) * | 2009-10-14 | 2010-04-14 | 郑州机械研究所 | High-toughness cadmium-free silver solder and preparation method thereof |
-
2010
- 2010-11-18 CN CN201010550704A patent/CN101985193B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01313198A (en) * | 1988-06-10 | 1989-12-18 | Mitsubishi Steel Mfg Co Ltd | Low melting low silver brazing filler metal |
| DE19725956A1 (en) * | 1996-07-20 | 1998-01-22 | Degussa | Manganese-containing copper-zinc-silver brazing alloy for highly stressed steel pipe |
| JP2001121288A (en) * | 1999-10-27 | 2001-05-08 | Tanaka Kikinzoku Kogyo Kk | Silver brazing filler metal for joining cemented carbide |
| CN1456415A (en) * | 2003-06-10 | 2003-11-19 | 李嘉珍 | High-strength silver-base brazing alloy and use thereof |
| CN1616182A (en) * | 2004-12-08 | 2005-05-18 | 哈尔滨工业大学 | Medium temperature Ag base brazing filler metal and its preparing method |
| CN101693325A (en) * | 2009-10-14 | 2010-04-14 | 郑州机械研究所 | High-toughness cadmium-free silver solder and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921838A (en) * | 2016-06-30 | 2016-09-07 | 四川广正科技有限公司 | Induction brazing method for edge scraper of shielding tunneling machine |
| CN105921838B (en) * | 2016-06-30 | 2019-03-08 | 四川广正科技有限公司 | A kind of shield machine edge doctor induction brazing method |
| CN112004638A (en) * | 2018-04-23 | 2020-11-27 | 田中贵金属工业株式会社 | Silver solder and bonding method using the same |
| KR20200140906A (en) * | 2018-04-23 | 2020-12-16 | 다나카 기킨조쿠 고교 가부시키가이샤 | Silver solder and bonding method using the silver solder |
| KR102426529B1 (en) * | 2018-04-23 | 2022-07-29 | 다나카 기킨조쿠 고교 가부시키가이샤 | Silver brazing material and joining method using the silver brazing material |
| CN110369909A (en) * | 2019-08-27 | 2019-10-25 | 常熟市华银焊料有限公司 | A kind of low silver-colored cadmium-free silver brazing alloy containing Ga and In |
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| CN101985193B (en) | 2012-09-05 |
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