CN101716705A - Multi-alloy cadmium-free phosphor-free copper-based solder - Google Patents
Multi-alloy cadmium-free phosphor-free copper-based solder Download PDFInfo
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Abstract
The invention belongs to solder materials, in particular to a multi-alloy cadmium-free phosphor-free copper-based solder comprising the following components in percentage by weight: zinc: 36.0-40.0%, silver: 4.0-5.0%, tin: 1.0-2.0%, gallium: 1.0-2.0%, indium: 1.0-2.0%, nickel: 0.3-0.7%, zirconium: 0.05-0.2%, germanium: 0.001-0.1%, cerium: 0.05-0.1% and the balance of copper. The multi-alloy cadmium-free phosphor-free copper-based solder has equivalent wetting performance and extensibility performance to a base mental and welding-line mechanical performance to BAg20CuZn when matched with FB102(QJ102) soldering acid to braze combined materials of red copper-red copper, brass-brass, and the like; in addition the multi-alloy cadmium-free phosphor-free copper-based solder has superior wetting performance and extensibility performance to the base mental and equivalent welding-line mechanical performance to the BAg20CuZn when brazing carbon-steel combined materials.
Description
Technical field
The present invention relates to a kind of brazing material, specifically is a kind of multi-alloy cadmium-free phosphor-free copper-based solder.
Background technology
Because cadmium limits for the use that contains cadmium material in the world to the adverse effect of the illeffects and the environmental pollution of health, the exploitation solder without cadmium has positive effect for improving dynamo-electric competitiveness of product of soldering and protection environment and human health.Present solder without cadmium mainly is silver-base solder and copper base solder, and wherein silver-base solder is based on silver, copper and three kinds of alloy constituent elements of zinc, by adding or not adding other alloying element, constitutes a series of brazing materials.But owing to forbidden the use of cadmium element, the content that such solder will increase precious metals ag usually could obtain and contain the suitable soldering processes performance of cadmium solder, and this has also consumed a large amount of rare noble metals when making the increase of solder product cost.Copper based solder without cadmium mainly is to be main alloy constituent element with copper, reduces the fusing point of solder by adding phosphorus and other group of alloys unit, improves its wetting and spreading performance and mechanical property.Such solder without cadmium cost is lower, but on the one hand copper-phosphorus brazing alloy fragility is bigger, contains phosphorus brazing alloy when ferrous metal such as weldable steel on the other hand, easily at the compound that forms fragility at the interface.Like this, traditional copper-phosphorus brazing alloy can not be used for material devices such as soldering steel and stainless steel, has limited its use.Therefore, seek with copper be the not phosphorous solder without cadmium of main alloy constituent element will have on the cost and range of application on advantage.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide that a kind of cost is low, the wetting and spreading performance and mechanical property is excellent, applied range multi-alloy cadmium-free phosphor-free copper-based solder.
The present invention is the expensive problem of solder of major components in order to solve with silver, and using instead with copper is main solder constituent element, but because copper base solder has higher fusion temperature, must reduce the solder fusing point and improve solder performance by adding other alloying elements.
Technical scheme of the present invention is as follows:
A kind of multi-alloy cadmium-free phosphor-free copper-based solder, constitute by weight percentage by following ingredients: zinc: 36.0%-40.0%, silver: 4.0%-5.0%, tin: 1.0%-2.0%, gallium: 1.0%-2.0%, indium: 1.0%-2.0%, nickel: 0.3%-0.7%, zirconium: 0.05%-0.2%, germanium: 0.001%-0.1%, cerium: 0.05%-0.1%, surplus is a copper.
Key technical problem solved by the invention is:
(1) the multi-element Cu-base solder without cadmium of Yan Zhikaifaing does not have cadmium Ag-Cu-Zn solder with tradition and compares, silver content reduces greatly, reduced the solder cost, saved the noble metal resource, simultaneously copper base solder of the present invention has lower fusion temperature, good wetting and spreading performance and weld properties, and alternative silver content is 20% cadmium-free silver-base solder B-Ag20CuZn;
(2) by alloy formula optimization, comprehensively adjust solder performance to adding an amount of more trace elements in the solder, separately the effect in solder of multiple alloy constituent element is described below:
Add gallium, indium and tin: 29.8 ℃ of the fusing points of gallium, the fusing point of indium and tin are respectively 156.6 ℃ and 232 ℃.The main effect of adding these three kinds of alloying elements is to reduce the solder fusion temperature, and Ga and In can also improve the wettability of solder at copper and copper alloy surface, is difficult to processing but Sn and In too high levels will cause solder embrittlement.
Add the unlimited solid solution of nickel: Ni energy in Cu, can improve corrosion resistance, resistance to elevated temperatures and the processability of solder, improve the wettability of solder at ferrous metal surface simultaneously, the Ni that adds trace can not cause the solder temperature to raise.
Add zirconium: the fusing point of zirconium is 1855 ℃, the dystectic trickle intermetallic compound particle that forms with copper in the solder process of setting has improved the nucleation rate of solder as the forming core core, makes its crystal grain fined, simultaneously can form precipitation strength, improve its mechanical property brazing filler metal alloy.
The fusing point that adds germanium: Ge is 938.3 ℃, and Ge and copper can form solid solution, can form eutectic with Zn, Ag, adds micro-Ge and can not cause the solder fusing point to raise and mechanical properties decrease in solder.Ge and Sn are congeners in addition, and both crystal structures are identical, can suppress when solder solidifies rich Sn grow up mutually make crystal grain become tiny evenly, thereby improve solder owing to add the fragility increase that Sn causes.The surface-active of Ge makes it accumulate in the liquid solder surface to present positive absorption, and the liquid solder surface free energy is reduced, thereby improves the wettability of solder.
Add rare earth: rare earth element can reduce the activity of alloying element in Cu such as Zn, Sn, Ni, increases its solubility, helps the alloying of these elements and then suppresses its precipitation from solid solution, has improved the mechanical property of solder; In addition, rare earth exists crystal boundary poly-partially in metal, can strengthen crystal boundary, and can suppress grain growth; Rare earth also can reduce the liquid solder surface tension, promotes its wetting and spreading on the test specimen surface.
What the present invention was different with other no cadmium copper base solders is to have added various trace elements comprehensively to adjust solder performance, has particularly added Ge and Zr.Solder microstructure of the present invention is even, has plasticity preferably, and the welding wire that can be prepared into diameter and be 1.0-2.0mm after the soldering, can obtain the soldered fitting intensity suitable with traditional solder without cadmium B-Ag20CuZn for welding.The present invention solves silver content and other rare precious metals too high levels of cadmium-free silver brazing alloy, and copper phosphorus solder without cadmium can not the soldering ferrous metal problem, a kind of no cadmium copper base of middle temperature solder of multicomponent alloy is provided, satisfy material devices such as soldering red copper, brass, carbon steel, stainless steel and nickel-base alloy, have no cadmium copper base solder with the suitable combination property of BAg20CuZn solder of silver content 20%.
Multi-alloy cadmium-free phosphor-free copper-based solder of the present invention cooperates FB102 (QJ102) brazing flux, and is during combinations of materials such as soldering red copper-red copper, brass-brass, suitable to wettability, spreading property, weld properties and the BAg20CuZn of mother metal; When soldering carbon steel-carbon steel material made up, solder of the present invention was better than BAg20CuZn to wettability, the spreading property of mother metal, and weld properties is suitable with it.
The specific embodiment
The present invention is made of by weight percentage following ingredients: zinc: 36.0%-40.0%, silver: 4.0%-5.0%, tin: 1.0%-2.0%, gallium: 1.0%-2.0%, indium: 1.0%-2.0%, nickel: 0.3%-0.7%, zirconium: 0.05%-0.2%, germanium: 0.001%-0.1%, cerium: 0.05%-0.1%, surplus is a copper.
Solder of the present invention is made by the following method: according to the prescription of afore mentioned rules, adopt commercially available cathode copper, zinc ingot metal, silver, metallic tin, gallium, indium metal, metallic nickel, germanium metal, copper zirconium alloy and copper Ce-La mixed rare earth alloy, prepare burden, adopt conventional intermediate frequency smelting furnace to carry out melting, be cast into ingot casting after the melting, through ingot casting is carried out peeling, cut-out, adopt eddy-current heating that ingot casting is pushed preheating, adopt the mode of hot extrusion that solder is processed into a material then, make the welding wire of required diameter through repeatedly stretching.According to producing needs, also metallic tin, gallium, indium metal, germanium metal can be smelted into alloy respectively in advance, add again and smelt in the Ag-Cu-Zn alloy and cast, by extruding and drawing process, acquisition solder welding wire.
Embodiment 1
Press the brazing filler metal alloy ingredient composition, the percentage by weight of alloying component consists of: zinc: 38.0%, and silver: 4.5%, tin: 2.0%, gallium: 2.0%, indium: 1.0%, nickel: 0.7%, zirconium: 0.05%, germanium: 0.05%, cerium: 0.1%, surplus is a copper.Be processed into the silk material of diameter 2.0mm, cooperate the FB102 brazing flux, with conventional method copper brazing alloy and steel, solder wettability on mother metal is good, and the intensity data that soldering is docked the brazed seam joint is: red copper-red copper σ
b=172MPa, brass-brass σ
b=319MPa, Q235 carbon steel-Q235 carbon steel σ
b=332MPa.
Embodiment 2
Press the brazing filler metal alloy ingredient composition, the percentage by weight of alloying component consists of: zinc: 40.0%, and silver: 5.0%, tin: 1.5%, gallium: 1.0%, indium: 1.0%, nickel: 0.6%, zirconium: 0.1%, germanium: 0.02%, cerium: 0.1%, surplus is a copper.Be processed into the silk material of diameter 2.0mm, cooperate the FB102 brazing flux, with conventional method copper brazing alloy and steel, solder wettability on mother metal is good, and the intensity data of butt joint brazed seam joint is: red copper-red copper σ
b=169MPa, brass-brass σ
b=310MPa, Q235 carbon steel-Q235 carbon steel σ
b=321MPa.
Embodiment 3
Press the brazing filler metal alloy ingredient composition, the percentage by weight of alloying component consists of: zinc: 39.0%, and silver: 4.5%, tin: 1.5%, gallium: 2.0%, indium: 2.0%, nickel: 0.5%, zirconium: 0.08%, germanium: 0.03%, cerium: 0.1%, surplus is a copper.Be processed into the silk material of diameter 2.0mm, cooperate the FB102 brazing flux, with conventional method copper brazing alloy and steel, solder wettability on mother metal is good, and the intensity data of butt joint brazed seam joint is: red copper-red copper σ
b=170MPa, brass-brass σ
b=308MPa, Q235 carbon steel-Q235 carbon steel σ
b=315MPa.
Embodiment 4
Press the brazing filler metal alloy ingredient composition, the percentage by weight of alloying component consists of: zinc: 40.0%, and silver: 4.5%, tin: 2.0%, gallium: 1.0%, indium: 1.5%, nickel: 0.5%, zirconium: 0.05%, germanium: 0.05%, cerium: 0.1%, surplus is a copper.Be processed into the silk material of diameter 2.0mm, cooperate the FB102 brazing flux, with conventional method copper brazing alloy and steel, solder wettability on mother metal is good, and the intensity data of butt joint brazed seam joint is: red copper-red copper σ
b=165MPa, brass-brass σ
b=290MPa, Q235 carbon steel-Q235 carbon steel σ
b=305MPa.
Embodiment 5
Press the brazing filler metal alloy ingredient composition, the percentage by weight of alloying component consists of: zinc: 40.0%, and silver: 5.0%, tin: 1.5%, gallium: 1.5%, indium: 2.0%, nickel: 0.3%, zirconium: 0.06%, germanium: 0.02%, cerium: 0.1%, surplus is a copper.Be processed into the silk material of diameter 2.0mm, cooperate the FB102 brazing flux, with conventional method copper brazing alloy and steel, solder wettability on mother metal is good, and the intensity data of butt joint brazed seam joint is: red copper-red copper σ
b=170MPa, brass-brass σ
b=296MPa, Q235 carbon steel-Q235 carbon steel σ
b=295MPa.
Embodiment 6
Press the brazing filler metal alloy ingredient composition, the percentage by weight of alloying component consists of: zinc: 38.0%, and silver: 4.8%, tin: 1.8%, gallium: 1.5%, indium: 2.0%, nickel: 0.5%, zirconium: 0.05%, germanium: 0.1%, cerium: 0.1%, surplus is a copper.Be processed into the silk material of diameter 2.0mm, cooperate the FB102 brazing flux, with conventional method copper brazing alloy and steel, solder wettability on mother metal is good, and the intensity data of butt joint brazed seam joint is: red copper-red copper σ
b=165MPa, brass-brass σ
b=285MPa, Q235 carbon steel-Q235 carbon steel σ
b=300MPa.
Embodiment 7
Press the brazing filler metal alloy ingredient composition, the percentage by weight of alloying component consists of: zinc: 40.0%, and silver: 5.2%, tin: 1.0%, gallium: 1.0%, indium: 1.0%, nickel: 0.6%, zirconium: 0.07%, germanium: 0.03%, cerium: 0.1%, surplus is a copper.Be processed into the silk material of diameter 2.0mm, cooperate the FB102 brazing flux, with conventional method copper brazing alloy and steel, solder wettability on mother metal is good, and the intensity data of butt joint brazed seam joint is: red copper-red copper σ
b=170MPa, brass-brass σ
b=291MPa, Q235 carbon steel-Q235 carbon steel σ
b=321MPa.
Embodiment 8
Press the brazing filler metal alloy ingredient composition, the percentage by weight of alloying component consists of: zinc: 36.0%, and silver: 4.5%, tin: 1.5%, gallium: 2.0%, indium: 2.0%, nickel: 0.4%, zirconium: 0.05%, germanium: 0.05%, cerium: 0.1%, surplus is a copper.Be processed into the silk material of diameter 2.0mm, cooperate the FB102 brazing flux, with conventional method copper brazing alloy and steel, solder wettability on mother metal is good, and the intensity data of butt joint brazed seam joint is: red copper-red copper σ
b=150MPa, brass-brass σ
b=280MPa, Q235 carbon steel-Q235 carbon steel σ
b=304MPa.
Embodiment 9
Press the brazing filler metal alloy ingredient composition, the percentage by weight of alloying component consists of: zinc: 39.0%, and silver: 5.0%, tin: 1.0%, gallium: 1.5%, indium: 1.5%, nickel: 0.6%, zirconium: 0.10%, germanium: 0.1%, cerium: 0.1%, surplus is a copper.Be processed into the silk material of diameter 2.0mm, cooperate the FB102 brazing flux, with conventional method copper brazing alloy and steel, solder wettability on mother metal is good, and the intensity data of butt joint brazed seam joint is: red copper-red copper σ
b=165MPa, brass-brass σ
b=296MPa, Q235 carbon steel-Q235 carbon steel σ
b=312MPa.
Embodiment 10
Press the brazing filler metal alloy ingredient composition, the percentage by weight of alloying component consists of: zinc: 40.0%, and silver: 5.5%, tin: 2.0%, gallium: 1.0%, indium: 1.0%, nickel: 0.5%, zirconium: 0.15%, germanium: 0.03%, cerium: 0.1%, surplus is a copper.Be processed into the silk material of diameter 2.0mm, cooperate the FB102 brazing flux, with conventional method copper brazing alloy and steel, solder wettability on mother metal is good, and the intensity data of butt joint brazed seam joint is: red copper-red copper σ
b=169MPa, brass-brass σ
b=320MPa, Q235 carbon steel-Q235 carbon steel σ
b=324MPa.
Embodiment 11
Press the brazing filler metal alloy ingredient composition, the percentage by weight of alloying component consists of: zinc: 40.0%, and silver: 5.2%, tin: 1.5%, gallium: 1.0%, indium: 2.0%, nickel: 0.5%, zirconium: 0.12%, germanium: 0.04%, cerium: 0.1%, surplus is a copper.Be processed into the silk material of diameter 2.0mm, cooperate the FB102 brazing flux, with conventional method copper brazing alloy and steel, solder wettability on mother metal is good, and the intensity data of butt joint brazed seam joint is: red copper-red copper σ
b=158MPa, brass-brass σ
b=294MPa, Q235 carbon steel-Q235 carbon steel σ
b=303MPa.
Embodiment 12
Press the brazing filler metal alloy ingredient composition, the percentage by weight of alloying component consists of: zinc: 37.0%, and silver: 4.5%, tin: 2.0%, gallium: 2.0%, indium: 2.0%, nickel: 0.4%, zirconium: 0.05%, germanium: 0.1%, cerium: 0.1%, surplus is a copper.Be processed into the silk material of diameter 2.0mm, cooperate the FB102 brazing flux, with conventional method copper brazing alloy and steel, solder wettability on mother metal is good, and the intensity data of butt joint brazed seam joint is: red copper-red copper σ
b=158MPa, brass-brass σ
b=294MPa, Q235 carbon steel-Q235 carbon steel σ
b=300MPa.
From above-mentioned embodiment as can be seen, by optimizing the alloying component proportioning, add an amount of alloying elements such as Ga, In, Sn, Ni, Zr, Ge and rare earth, solder product of the present invention can obtain the good wetting performance of mating formation on red copper, brass, base metal of carbon steel surface, and strength of joint is higher after the soldering.At the wettability of steel surface, solder product of the present invention is better than BAg20CuZn especially.Constant product quality of the present invention, the soldering high conformity, brazing process parameter and performance indications are close with the BAg20CuZn solder, can replace the application of BAg20CuZn in industry.By " multi-alloy cadmium-free phosphor-free copper-based solder " solidus temperature (reference value) about 700 ℃ that the mentioned component proportioning obtains, liquidus temperature is (reference value) about 810 ℃.
Claims (1)
1. multi-alloy cadmium-free phosphor-free copper-based solder, constitute by weight percentage by following ingredients: zinc: 36.0%-40.0%, silver: 4.0%-5.0%, tin: 1.0%-2.0%, gallium: 1.0%-2.0%, indium: 1.0%-2.0%, nickel: 0.3%-0.7%, zirconium: 0.05%-0.2%, germanium: 0.001%-0.1%, cerium: 0.05%-0.1%, surplus is a copper.
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| CN102601542A (en) * | 2012-03-28 | 2012-07-25 | 华南理工大学 | Brass brazing alloy |
| CN102626837A (en) * | 2012-05-09 | 2012-08-08 | 哈尔滨工业大学 | Moderate temperature copper-based solder and preparation method thereof |
| CN102862003A (en) * | 2012-10-08 | 2013-01-09 | 佛山市泓实机械制造有限公司 | Silver-free copper based solder and preparation method thereof |
| CN103231183A (en) * | 2013-03-28 | 2013-08-07 | 安庆天瑞新材料科技股份有限公司 | Copper-based amorphous brazing material and preparation method thereof, as well as strip and preparation method thereof |
| CN103506771A (en) * | 2012-11-23 | 2014-01-15 | 广东美芝制冷设备有限公司 | Solder composition and preparing method and application thereof |
| CN107262961A (en) * | 2016-03-30 | 2017-10-20 | 通用电气公司 | Brazing composition and correlation technique and device for ductility braze-welded structure |
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| CN102601542A (en) * | 2012-03-28 | 2012-07-25 | 华南理工大学 | Brass brazing alloy |
| CN102626837A (en) * | 2012-05-09 | 2012-08-08 | 哈尔滨工业大学 | Moderate temperature copper-based solder and preparation method thereof |
| CN102626837B (en) * | 2012-05-09 | 2014-06-04 | 哈尔滨工业大学 | Moderate temperature copper-based solder and preparation method thereof |
| CN102862003A (en) * | 2012-10-08 | 2013-01-09 | 佛山市泓实机械制造有限公司 | Silver-free copper based solder and preparation method thereof |
| CN103506771A (en) * | 2012-11-23 | 2014-01-15 | 广东美芝制冷设备有限公司 | Solder composition and preparing method and application thereof |
| CN103506771B (en) * | 2012-11-23 | 2016-08-31 | 广东美芝制冷设备有限公司 | Solder composition and its production and use |
| CN103231183A (en) * | 2013-03-28 | 2013-08-07 | 安庆天瑞新材料科技股份有限公司 | Copper-based amorphous brazing material and preparation method thereof, as well as strip and preparation method thereof |
| CN107262961A (en) * | 2016-03-30 | 2017-10-20 | 通用电气公司 | Brazing composition and correlation technique and device for ductility braze-welded structure |
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